The Pitfalls of Pit Contacts: Electroless Metallization for c-Si Solar Cells

by Kate Fisher B.E, Photovoltaics and Solar Energy, 2004

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Abstract

This thesis focuses on improving the adhesion of electroless metal layers plated to pit contacts in interdigitated, backside buried contact (IBBC) solar cells. In an electrolessly plated, pit contact IBBC cell, the contact grooves are replaced with lines of pits which are interconnected by the plated metal. It is shown, however, that electroless metal layers, plated by the standard IBBC plating sequence, are not adherent on pit contact IBBC solar cells. The cause of this adhesion problem is investigated by examining the adhesive properties of each of the metal layers in the electroless metallization sequence on planar test structures. This investigation reveals that Pd activation of heavily P diffused Si impedes Ni silicide growth and that, in the absence of a silicide at the Ni/Si interface, an electrolessly plated Cu layer will cause the underlying Ni layer to peel away from the substrate. It is also found that the Ni silicidation process itself intermittently causes the unreacted Ni to spontaneously peel away from the substrate. An electroless metallization sequence that results in thick, adhesive Cu deposits on planar <100> surfaces is developed in this thesis. It is shown that this process leads to the formation of a Ni silicide on both n- and p- type, heavily diffused surfaces. Fully plated, pit contact IBBC solar cells were not able to be fabricated during the course of this work but it is reasonable to expect that the modied plating sequence developed in this work will result in the metal layers being adhesive on these cells.

Dedication

...to a world with fewer problems...

vii

Acknowledgements

Firstly, I would like to thank my supervisor, Dr Jeffery Cotter for providing me with the opportunity to carry out this research. I would not have been able to undertake it without the nancial support of employment in the same eld (and physical space) as my research. My understanding of solar cells and skills in the laboratory have beneted from this employment opportunity and your guidance as a boss and a supervisor has helped very much in realising this thesis. Thanks also goes to Dr Tom Puzzer for training and enlightening discussions on electron microscopy and willingness to divulge an astonishing wealth of information about analytical measurement techniques. Particular thanks also to Jenny Norman and other staff at the electron microscope unit for helping me wrestle with the Cambridge (it was a beast but Im still sad to see it go). Special thanks to Stuart Wenham for being so forthcoming with processing tips and tricks for buried contact solar cells. Thanks also for the historical information. I would also like to thank Malcom Abbott for his ne proof reading skills and ability to utilise them to great effect at very short notice. Thanks to Florence Chen and Jeff also on this front. I would like to acknowledge the love, support and not inconsiderable cooking skills of my partner Sami. Parents, as usual, thanks.

List of Abbreviations

AED BGD BPSG BSF BSG CMOS c-Si CZ DSBC EB EDS EDTA EWT FZ IBBC IC PCD PERL PGD PSG

Autocatalytic Electroless Deposition Boron Groove Diffusion Boro-Phospho-Silicate Glass Back Surface Field Boro-Silicate Glass Complementary Metal Oxide Semiconductor Crystalline silicon Czochralski Double-Sided Buried Contact Electron Beam Energy Dispersive Spectroscopy Ethyl-Diamine-Tetraacetic Acid Emitter Wrap Through Float zoned Interdigitated Backside Buried Contact Intergrated Circuit Photoconductance Decay Passivated Rear Locally Diffused Phosphorus Groove Diffusion Phospho-Silicate Glass

ix

RIE RTP SEI SEM SPM SSBC TCA UNSW Voc

Reactive Ion Etching Rapid Thermal Processing Secondary Electron Image Scanning Electron Microscope Sulfuric Peroxide Mixture Single-Sided Buried Contact Trichloroethane University of New South Wales Open Circuit Voltage

Contents

Chapter 1 Introduction 1.1 1.2 1.3 1.4 2 Motivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Thesis Statement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Thesis Contributions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Thesis Outline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 1 4 4 6 7 7 8 9 11 14 15 18 20 22 24 27

Literature Review: Electroless Metallization 2.1 2.2 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Electroless Plating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.1 2.2.2 2.3 Palladium Immersion Activation . . . . . . . . . . . . . . . . . . . . . Autocatalytic Electroless Depositions . . . . . . . . . . . . . . . . . .

Ni Silicidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3.1 2.3.2 Silicidation of Pure Ni Deposits . . . . . . . . . . . . . . . . . . . . . Silicidation of AEDs . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.4

Electroless Metallization of Silicon Solar Cells . . . . . . . . . . . . . . . . . 2.4.1 2.4.2 Planar AED Contacts . . . . . . . . . . . . . . . . . . . . . . . . . . . Buried AED Contacts . . . . . . . . . . . . . . . . . . . . . . . . . .

2.5

Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

xi 3 Research Methodology 3.1 3.2 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Background Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2.1 3.2.2 3.3 Buried Contact Solar Cell Structures . . . . . . . . . . . . . . . . . . . Plating Buried Contact Solar Cells . . . . . . . . . . . . . . . . . . . . 28 28 28 28 31 34 35 36 39 40 41 43 43 44 44 45 47 53 53 55 56 57 57 59 63 64 66

Experimental Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3.1 3.3.2 3.3.3 3.3.4 Electroless Plating . . . . . . . . . . . . . . . . . . . . . . . . . . . . Ni Sintering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Ni Cleaning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Pd Cleaning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

3.4 4

Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Experimental Results and Discussion 4.1 4.2 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Preliminary Experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2.1 4.2.2 4.2.3 4.3 Pits and Grooves: a Structural Comparison . . . . . . . . . . . . . . . Pits and Grooves: a Photoconductance Comparison . . . . . . . . . . . Metal Adhesion Problems of Pit Contacts . . . . . . . . . . . . . . . .

Metallization of Pit Contacts . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.3.1 4.3.2 4.3.3 4.3.4 Ni Plated Pits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Ni Sintered Pits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Pd Activated Pits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

4.4

Ni Silicidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.4.1 4.4.2 4.4.3 4.4.4 Effect of Surface Activation . . . . . . . . . . . . . . . . . . . . . . . Effect of Pd Sintering . . . . . . . . . . . . . . . . . . . . . . . . . . . Effect of Ni Plating Temperature . . . . . . . . . . . . . . . . . . . . . Unreacted Ni . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

xii 4.4.5 4.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67 68 69 70 72 73 75

Cu Plated Layers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.5.1 4.5.2 4.5.3 Without Ni Silicide . . . . . . . . . . . . . . . . . . . . . . . . . . . . With Ni Silicide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

4.6 5

Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Conclusion and Future Work

Appendix A SEM and EDS 79

Bibliography

81

List of Tables

Table 2.1 Summary of Ni silicide phase transitions and sheet resistivity results from various authors. All substrates are (100), c-Si . . . . . . . . . . . . . . . . . . . . 2.2 Phenomena observed for AEDs of Ni plated to (100) substrates and sintered at various temperatures. Deposition 1 refers to 30-40 nm of NiP plated on EBNi seed layers on n-type substrates [46], Deposition 2 refers to 30-40 nm of NiP plated to Pd activated, n-type substrates [46] and Deposition 3 refers to 800-3000 nm of NiP plated directly onto p-type 1-10cm substrates [57]. . . . 2.3 Summary of processing parameters of various c-Si solar cells with planar, photolithographically dened, electrolessly plated contacts. . . . . . . . . . . . . . 2.4 Summary of processing parameters of various c-Si solar cells with buried, electrolessly plated contacts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1 3.2 3.3 IBBC solar cells processing sequence prior to metallization. . . . . . . . . . . Silicidation test structure types. . . . . . . . . . . . . . . . . . . . . . . . . . . Bath constituents of an ammonia-based, proprietary electroless Ni plating solution from Transene [22]. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.4 Bath constituents of a proprietary electroless Cu plating solution from Enthone [64]. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1 4.2 Summary of results from Section 4.3 . . . . . . . . . . . . . . . . . . . . . . . Summary of the experiment. The results are shown in Figure 4.16. . . . . . . . 35 59 60 35 25 30 34 23 19 17

xiv 4.3 Sheet resistivity variation with Ni sintering temperature. Measurements were taken before the plating sequence (ie: this is the sheet resistivity of the phosphorus diffusion), and after the unreacted Ni had been removed (ie: this is the resistivity of the phosphorus diffusion and the Ni silicide in parallel). . . . . . . 4.4 4.5 4.6 Pd sintering on boron diffused test structures. . . . . . . . . . . . . . . . . . . Summary of results from Sections 4.4.1 and 4.4.3 . . . . . . . . . . . . . . . . Ni plating and sintering parameters for three SSBC PGD test structures with photolithographically dened contacts. 4.7 . . . . . . . . . . . . . . . . . . . . . 71 61 64 68

Sheet resistivity measurements of the various layers formed on photolithographically dened contacts. Sample 2 was sintered at 300 C and Sample 3 was sintered at 400 C. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72

List of Figures

Figure 2.1 2.2 Schematic of the electroless plating sequence for IBBC solar cells. . . . . . . . Adhesion of an AED of Ni plated to variously doped substrates, activated with various Pd solutions. The Pd layer was sintered for 30 minutes at 200 C prior to the Ni plate. Adhesion as a function of (a) surface concentration and dopant type for various Pd activation solutions and (b) Pd solution type for various Ni plating times and temperatures. The substrates here are 4 .cm, p-type (after [42]). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3 Adhesion of an AED of Ni plated to variously doped substrates, with and without Pd activation. The activation solution is NH4 F-based and the Pd deposit was sintered for 30 minutes at 200 C prior to the Ni plate. The surface concentration of the n-type substrates was 4-8 x 1015 /cm3 and for p-type substrates, 1-2 x 1016 /cm3 . P+ denotes a boron diffused surface and N+ denotes a phosphorus diffused surface both with surface concentrations >1020 /cm3 . All substrates are (111). The graphs show adhesion of a 2 minute, AED of Ni plated from an alkaline, hypophosphite bath at 90-95 C onto (a) n-type surfaces and (b) p-type surfaces (after [41]). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4 A summary of the most commonly reported phases of Ni silicide and their temperatures of formation, [10], [16], [18], [28], [38], [39], [55], [58], [60], [61]. In general, x1 < x2 < x3 and the Si rich phase, formed at higher temperatures, tends to agglomerate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17 12 12 8

xvi 2.5 Schematic of various electroless plated contacts. Dotted lines indicate diffused Si, light grey areas indicate the dielectric and dark grey areas indicate the plated metal. Photolithographically dened contacts with a planar homogeneous emitter, a planar selective emitter, and a buried selective emitter are shown in a), b), and c), respectively. A scribed contact with a selective emitter is shown in d). . 3.1 Schematic of a SSBC solar cell showing 1) random pyramid textured, front surface, diffused with 100 /sq. phosphorus emitter and passivated with SiO2 , 2) laser scribed grooves, diffused to < 5 /sq with phosphorus, 3) random pyramid textured rear surface with an aluminium back surface eld, 4) Ni and Cu plating in the front surface grid and 5) Ni and Cu plated over the entire rear surface. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2 Schematic of a IBBC solar cell showing 1) random pyramid textured, front surface, diffused to 100 /sq. with phosphorus and passivated with SiO2 , 2) saw damage etched, rear surface, diffused with 100 /sq. boron emitter and passivated with SiO2 , 3) laser scribed grooves, diffused to < 5 /sq with phosphorus, 4) laser scribed grooves, diffused to < 10 /sq. with boron and 5) Pd, Ni and Cu plating in both rear grids. . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3 3.4 Schemaitic of an elephant. . . . . . . . . . . . . . . . . . . . . . . . . . . . . The effects of O2 on electroless plated Ni when heated. The samples have been Ni plated and (a) no sintered, (b) sintered at 200 C without the use of an elephant, (c) sintered at 400 C without the use of an elephant, (d) sintered at 400 C without the use of an elephant and with the furnace N2 turned down. . . 3.5 3.6 Temperature prole of furnace used for Ni silicide formation . . . . . . . . . . Three sections of a boron diffused sample that has been Ni plated. Section a) shows the Ni plate intact, b) shows the Ni plate removed with RCA2 and c) shows the Ni plate removed with SPM. . . . . . . . . . . . . . . . . . . . . . . 40 38 38 29 37 29 22

xvii 3.7 A boron diffused wafer a) after Pd activation and b) the same wafer after cleaning. The left side of b) has been swabbed with a cotton bud soaked in IPA and the right side has been SPM cleaned and then swabbed with a cotton bud soaked in IPA. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1 Ni and Cu plated 50 m deep groove on an IBBC solar cell showing the void at the centre of the trench and 50 m of overplating. . . . . . . . . . . . . . . . . 4.2 SEM micrograph of (a) the plane view and b) the cross section of etched pits. The pits were scribed with a laser wavelength of 1064 nm and hence end up being 20 m across. The pits are spaced 50 m apart and hence the adjacent pits are out of the frame of this image. Note the oxide overhang in the plane view and the Si overhang in the cross section. The border with rounded corners in the plane view corresponds to the Si overhang and there is no oxide overhang in the cross section because the oxide was thinner to begin with and hence got etched back to the edges. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.3 4.4 Injection-level dependence lifetime curves of the various contact types. . . . . . Saturation current contribution from the diffused regions as a function of contact type. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.5 SEM micrograph of poorly adhesive electroless Ni and Cu plated on the pits of several ngers of an IBBC cell. The rst and third ngers are phosphorus diffused and the second and fourth ngers are boron diffused. . . . . . . . . . . 4.6 a) A busbar on a pit IBBC cell showing how the Cu plating has fallen out of the pits and b) a close-up of the top left hand corner of the same busbar. The numbers refer to the pit to the right of the number. . . . . . . . . . . . . . . . . 4.7 A nger on a pit IBBC cell showing the Cu plate detaching from the Ni plate in the pit. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.8 SEIs and EDS maps of the pits labeled Pit 1, Pit 2 and Pit 3 in Figure 4.6 b). . . 51 51 50 49 48 46 48 46 41

xviii 4.9 An example of badly deglazed a) phosphorus and b) a boron diffused pits, plated with electroless Ni. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.10 An example of well deglazed a) phosphorus and b) a boron diffused pits, plated with electroless Ni. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.11 Pit contacts that have a) had no plating at all and b) been Ni plated at 90-95 C and the Ni removed in a standard RCA2 etch (no sintering). . . . . . . . . . . . 4.12 An a) phosphorus diffused and b) a boron diffused pit that has been Ni plated at 90-95 C after sintering at 350 C and removal of the excess Ni in RCA2 solution. 56 4.13 Ni plated onto the eld oxide. The bottom left pit is plated with Cu but all other pits and the areas between them were determined to be Ni by EDS mapping. . . 4.14 A well deglazed, Pd activated a) phosphorus and b) boron diffused pit, with Pd activation and electroless Ni plating at 80 C. . . . . . . . . . . . . . . . . . . . 4.15 The Pd activated a) phosphorus and b) boron diffused pits after sintering and RCA2 to remove the unreacted Ni. . . . . . . . . . . . . . . . . . . . . . . . . 4.16 P-type substrates with SSBC PGD of 3 /sq. across the whole surface. The samples had different Pd treatments prior to electroless Ni plating at 80 C for 4 minutes. The samples were sintered for 10 minutes at the temperatures indicated and the unreacted Ni removed in a 50% SPM. . . . . . . . . . . . . . . . 4.17 Boron groove diffused samples that have been Pd activated and the Pd sintered for a) 10 minutes at 250 C and b) 40 minutes at 200 C. Both samples then underwent SPM cleaning prior to Ni plating and at 300 C. Finally, the unreacted Ni was removed in SPM. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.18 Silicide formation on an a) IBBC phosphorus and b) boron test structure that was Pd activated and the Pd sintered at 250 C for 20 minutes. . . . . . . . . . 4.19 The three different test structures with three different surface treatments prior to electroless Ni plating at 90-92 C for 4 minutes. The samples were sintered at 350 C for 5 minutes and the unreacted Ni removed in a SPM. . . . . . . . . 66 65 64 62 58 58 58 56 54 54

xix 4.20 IBBC phosphorus diffused test structures with three different surface treatments prior to electroless Ni plating at 90-92 C for 4 minutes. The samples were sintered at 300 C for 5 minutes and the unreacted Ni removed in a SPM. . . . . 4.21 A photograph of Ni aking off a test structure after sintering at 300 C for 7 minutes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.22 Cu plated layers on phosphorus diffused IBBC test structures that were rst plated with Ni at a) 80 C and b) 90 C. . . . . . . . . . . . . . . . . . . . . . . 4.23 Cross sectional schematic of the photolithographically dened pattern used in Section 4.5.2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.24 Plan view of two SSBC PGD test structures that were photolithographically patterned and metallized. After the initial Ni deposition, both samples were sintered at 300 C for 10 minutes and the unreacted Ni was a) left on and b) removed in an SPM before further processing. . . . . . . . . . . . . . . . . . . A.1 X-ray spectrum generated on a Ni plated pit at low magnication (black spectrum) and at high magnication (grey spectrum). . . . . . . . . . . . . . . . . A.2 X-ray maps of a Ni plated pit; a) the SEI image of the mapped area, b) the Si signal, c) the Ni signal and d) the phosphorus signal. . . . . . . . . . . . . . . A.3 X-ray maps of a pit where the Ni has been sintered and the unreacted Ni removed with RCA2; a) the SEI image of the mapped area, b) the Si signal, c) the Ni signal and d) the phosphorus signal. . . . . . . . . . . . . . . . . . . . . . . 80 80 80 71 70 69 67 66

Chapter 1 Introduction

1.1

Motivation
Metallization is an important area of solar cell research because energy is extracted from

a solar cell through its metal contacts. A good metallization scheme is one that provides low recombination, has low contact and series resistance and incurs low shading losses. The metal contacts must also adhere well to the surface of the cell. Ideally, they will be easy to manufacture, enable high through-put and incur minimal manufacturing costs. Many different metallization schemes are employed in photovoltaic devices. Vacuum evaporated, Ti-Pd-Ag contacts are utilised in high efciency laboratory devices such as PERL cells [74]. Many cells also use vacuum evaporated or sputtered Al contacts (see [3] for example). Vacuum evaporation yields high purity, low resistivity contacts but they are expensive to manufacture and are not suitable for use in high through-put production lines. The majority of photovoltaic devices in the market today use screen printed contacts. This is because the high throughput capabilities of this technique make it highly suitable for use in commercial production lines. Screen printed contacts are applied to the cell surface by forcing a metal paste through an emulsion screen using a squeegee. Screen printed contacts incur substantial shading losses and have high bulk resistivity [31]. This thesis looks in detail at another metallization technique: electroless plating. In order to electrolessly plate metal to a solar cell, the Si must be exposed in the contact areas and

2 masked everywhere else. An electroless deposition of Ni is then plated to the contact areas and sintered in a furnace to form a low resistance Ni silicide at the contact interface. Another layer of Ni is then plated to the rst layer as a strike. This ensures that the subsequent Cu plate, which comprises the bulk of the metal contact, will initiate on the Ni surface. Cu is used as the bulk material because of its low bulk resistivity. A thin layer of Ag is often plated over the Cu to better facilitate soldering. Electrolessly plated contacts have many advantages compared to screen printed contacts. The maximum processing temperature is 400 C whereas screen printed contacts are typically red at 800 C. Low temperature processing reduces the thermal budget and the probability of contamination. Screen printed pastes incorporate solvents and frits [31] that result in printed contacts having much higher series resistance than plated contacts. Electroless metallization schemes utilise Ni silicide at the contact interface, which has the advantage of providing low contact resistance [28]. Shading losses from screen printed contacts are also high because the minimum line width is 120 m [72]. Electroless plated contacts can be much narrower because they are dened photolithographically [17], [69], or dened by laser or mechanical scribing [3], [70]. The main disadvantage of electroless metallization, compared to screen printing, is that there are more steps in the processing sequence. One example of photovoltaic devices that utilise electroless metallization schemes are the buried contact solar cells. Buried contacts (BCs) are photovoltaic devices in which contact is made to the cell by applying metal into grooves scribed into the wafer surface either mechanically or with a laser. Burying the metal contact areas vertically inside the substrate reduces the opaque area on the front surface, which reduces shading losses. The grooves are scribed through the surface dielectric, which acts as a mask for a heavy diffusion in the contact areas. This ensures low contact resistance between the metal and the semiconductor [66]. It also means that the doping level in the emitter can be as low as 100 /sq, which results in good utilisation of the solar spectrum [70]. There are three buried contact solar cell structures - the single sided buried contact

3 (SSBC), the double sided buried contact (DSBC) and the interdigitated backside buried contact (IBBC). SSBCs comprise a phosphorus emitter on a p-type substrate with emitter contact grooves scribed through the passivating dielectric [70]. The base contact is realised with a thin Al alloyed region over the entire rear surface. This results in voltage limitations for thin cells with long diffusion lengths, because the rear surface recombination velocity high [32]. The DSBC seeks to overcome this limitation by replacing the Al rear contact with a well-passivated, light phosphorus diffusion on the rear surface [52]. This diffusion acts as a oating junction, which has been shown to provide excellent surface passivation [32]. The base contact is realised with a heavily, boron diffused, buried contact grid scribed through the oating junction. It was found, however that diffusion induced, boron mist dislocations, formed during this heavy diffusion, severely limit the performance of these cells because they cause asymmetric Schottky-Read-Hall (asymmetric-SRH) recombination in the bulk [15]. The IBBC solar cell comprises an n-type base, lightly diffused boron emitter, lightly diffused phosphorus front surface eld and both heavy boron and phosphorus contact diffusions in an interdigitated pattern on the rear surface [29]. N-type, IBBCs are not affected by asymmetric-SRH recombination in the way that p-type DSBCs are, because the capture-cross section of holes is much lower than that of electrons (see [13], for example). IBBCs also incur no shading losses because the contacts are on the rear surface and efciencies approaching 20% on 180 m thick, 1 cm FZ wafers have been demonstrated with this cell structure [29]. A common way to increase the performance of high efciency, c-Si solar cells is to reduce the surface area of the heavily diffused contact regions by using points of contact instead of lines or whole surfaces of contact [65], [74]. Point contact IBBC structures could potentially be made for no extra cost, simply by changing the laser scribing code. Instead of creating a groove in the wafer surface, the new code would create a line of pits, which would need to be electrically connected by the metallization scheme. Cells with this type of grid design are called pit contact IBBC solar cells. Realisation of pit contact IBBC solar cells by electroless metallization is the subject of this thesis.

1.2

Thesis Statement
The aim of this thesis is to develop a reliable electroless metallization scheme that en-

ables maximal current extraction from pit contact, IBBC solar cells. A reliable process is one in which the same outcome is achieved for the same processing parameters, every time the process is run. Developing a reliable process generally requires the effects of the rst and second order parameters of the process to be known and controllable. The electroless metallization scheme of the IBBC solar cell is comprised of a sequence of distinct processes. The most important ones are Ni plating of Si, Ni silicide formation and Cu plating of Ni. It is necessary to understand the main parameters of each one in order to gain control over the process as a whole. To achieve the main goal of producing an electrically operational, pit contact, IBBC solar cell, four intermediate goals were identied: 1. To determine the main parameters affecting electroless Ni plating of heavily phosphorus and boron diffused silicon. 2. To develop a reliable method for simultaneously plating electroless Ni to heavily phosphorus and heavily boron diffused Si. 3. To develop a process that allows a silicide to form, from a layer of electrolessly plated Ni, simultaneously on heavily phosphorus and heavily boron diffused Si. 4. To develop a method of electrolessly plating thick layers (> 50 m) of Cu to a heavily diffused Si/silicide/Ni region.

1.3

Thesis Contributions
During the course of this thesis, the main parameters of each of the processes of the

IBBC, electroless metallization scheme and their interdependency were identied experimentally. The main contributions of this work can be summarised as follows:

5 Bath activation greatly affects the initiation of autocatalytic electroless depositions of both Ni and Cu. Ni plating bath temperature greatly affects silicide formation. Pd activation of heavily phosphorus diffused (100) Si impedes silicide formation for furnace sintering temperatures up to 450o C and sintering times of less than 10 minutes. Incomplete silicidation can cause the unreacted Ni to peel away from the underlying silicide. Plating thick Cu layers to Ni plated layers on planar Si substrates causes adhesion failure at the Ni/Si interface unless the Ni layer is bonded to the substrate by silicidation. An electroless plating sequence was developed that allowed adhesive layers of thick Cu to be plated to planar, (100) test structures. In addition to these ndings, several processing techniques were developed during this work to allow the parameters of each of the processes to be examined. Inclusion of the groove diffusion dummy wafers into the metallization processing sequence, not only greatly improved the platability of the samples, but allowed for a macroscopic view of the silicidation process. It was shown that Ni silicide formation could be examined on planar dummy wafers by plating and sintering a Ni layer and then removing the unreacted Ni in a selective wet chemical etch. This allowed for a macroscopic view of the silicidation process and proved to be a much more efcient way of examining problems with the metallization process than manufacturing batches of cells. The main objective of producing an operational, pit contact, IBBC solar cell was not achieved during the course of this work. This thesis shows, however, that such a device is unlikely to ever be realised by electroless metallization.

1.4

Thesis Outline
This thesis has three main chapters. Chapter 2 presents a review of published work per-

taining to the electroless metallization of Si solar cells. Different types of electroless plating are reviewed in Section 2.2, the silicidation of Ni is reviewed in Section 2.3 and a discussion of the application of these is presented in Section 2.4. Chapter 3 describes the experimental method used in this thesis. A review of the contact structures used in UNSW buried contact solar cells is presented in Section 3.2 and the electroless plating, Ni sintering and metal cleaning techniques used in this work are presented in Section 3.3. Chapter 4 describes and discusses the experiments carried out during the course of this work. The potential benits of pit contact IBBC solar cells and the problems encountered in their metallization is presented in Section 4.2. Section 4.3 describes an experiment that shows that Pd activation of heavily diffused boron pits is necessary to avoid excessive Si migration during Ni sintering. Section 4.4 presents the results of experiments that show how Pd activation inhibits Ni silicide formation on heavily phosphorus diffused surfaces and how unreacted Ni may be one potential source of poor adhesion in the IBBC electroless metallization scheme. Section 4.5 presents evidence that a lack of Ni silicide at the Ni/Si interface is another potential source of adhesion failure and shows that proper silicidation in conjunction with the removal of the unreacted Ni after silicidation imporves the adhesion of subsequent Cu plated layers. The main ndings of this work are summarised in Chapter 5 and options for future work are discussed.

Chapter 2 Literature Review: Electroless Metallization

2.1

Introduction
This chapter presents a review of the literature that is relevant to the experimental work

carried out in this thesis. The main aim of this thesis is to improve the adhesion of electrolessly plated layers to pit contact IBBCs. The electroless plating sequence utilised in IBBC solar cells is broken down into its constituent parts and the literature pertaining to each part is reviewed in order to gain an understanding of the mechanisms affecting each of the layers. A schematic of the steps in the IBBC solar cell metallization sequence is shown in Figure 2.1. All oxide is removed from the contact areas leaving bare Si exposed (a). Activation of the contact areas with Pd (b), is employed to better facilitate Ni plating and improve contact adhesion. A thin layer of Ni is then plated to the contact areas (c) and sintered to form a silicide at the Ni/Si interface (d). A second layer of Ni is then plated over the top of the rst layer (e) to better facilitate Cu plating. A thick layer of Cu is then plated to the second Ni layer (f). Formation of the Ni silicide reduces the contact resistance between the metal and the Si and anchors the metal to the cell. Cu is used as a low resistance current carrier because its bulk resistivity is 4 times lower than that of Ni and it is much cheaper than lower resistivity metals such as Ag or Au. The literature pertaining to electroless metallization of IBBC has been reviewed and grouped into three topic areas. The rst is electroless plating. Plating mechanisms and the

a) Si

b) Pd

c) Ni

d) NiSi

e) Ni

f) Cu

Figure 2.1: Schematic of the electroless plating sequence for IBBC solar cells.

properties of each of the metal deposits are presented in Section 2.2. Section 2.2.1 discusses how Pd activation can affect the adhesive properties of subsequent metal deposits. The effect of plating bath parameters on the properties of electroless Ni and Cu depositions is presented in Section 2.2.2. The second topic to be reviewed is Ni silicide formation. After Ni has been plated to an IBBC solar cell it is sintered to form Ni silicide at the contact interface. In Section 2.3 an understanding of the mechanisms involved in Ni silicidation is sought from the prolic amount of literature available pertaining to silicidation in CMOS devices. These are mostly concerned with vacuum deposits of Ni sintered by rapid thermal processing (RTP). The few publications that have considered the silicidation of AEDs of Ni by furnace processing are then reviewed to gain some insight into the actual silicidation process occurring on IBBC devices. The third topic is to be reviewed is the electroless metallization of c-Si solar cells in general and buried contacts in particular. The purpose of this section is to highlight the benets of electroless metallization in comparison to other metallization schemes and to identify some of the known problems associated with the process.

2.2

Electroless Plating
Electroless plating refers to the deposition of metal onto a substrate from an aqueous

medium without the use of an external bias potential to drive the reaction. There are two types of electroless plating that are utilised in solar cell metallization and they proceed by different mechanisms. The rst is referred to as immersion plating or immersion activation. The plating

9 rate from an immersion plating bath is typically low and the layers are generally used as a seed layer for a subsequent autocatalytic deposit. Autocatalytic electroless depositions, (AEDs), which plate a much greater rates, are used to plate the bulk of the conductor. The mechanisms behind immersion plating and the type of immersion plating utilised in IBBC solar cells are discussed in Section 2.2.2. The mechanisms behind autocatalytic electroless deposition and the properties of Ni and Cu AED baths and deposits are discussed in Section 2.2.1.

2.2.1

Palladium Immersion Activation

Pd is often used as a seed layer for subsequent AEDs on non-catalytic substrates or

substrates where nucleation is minimal. For example, non-conductive materials, that would otherwise not be able to be plated by an autocatalytic process, can rst be activated with a thin layer of Pd (see: [12], [23], [33] and [36] for example). The Pd layer, which acts as a catalyst for many AED solutions, allows the non-conductive substrate to be metallized. It has been shown that p-type Si has a lower electroless Ni nucleation density than n-type Si [41]. This is due to the electronegativity of p-type Si being greater than that of n-type which causes the plating rate to be much lower on p-type surfaces than on n-type [34]. The higher the concentration of p-type dopants, the worse this problem becomes. Pd immersion is therefore useful for activating heavily boron diffused Si, because it increases the Ni nucleation density. The chemical equation for the reduction of Pd ions to Pd metal is given by Equation 2.1. Pd has a relatively high, positive redox potential which means that the forward reaction of Equation 2.1 is more likely to proceed than the reverse reaction [24]. Pd ions will be reduced to Pd metal on any substrate from which they can gain electrons. Pd has a much greater propensity to plate out of solution than Ni, for example, which has a negative redox potential.

Pd 2+ + 2e

Pd

E o = 0.83 V

(2.1)

To plate Pd to insulating or otherwise non-catalytic substrates (such as printed circuit boards), where the transfer of electrons is limited, the substrate is rst sensitized with Sn then

10 activated with Pd and the Sn removed at the end in a acceleration step (for examples see: [12], [23], [33] and [36]). When the substrate is Si, however, a much simpler process is possible due to fact that Si dissolves in HF according to Equation 2.2 [24].

Si + 6F

SiF6 2

E o = 1.24 V

(2.2)

When Si is immersed in a mixture of Pd and HF, a galvanic reaction proceeds where anodic dissolution of the substrate (Equation 2.2) enables cathodic reduction of the metal ions from the solution (Equation 2.1) by transferring electrons through the substrate [11], [43], [56]. There have been reports of Pd activation of Si in HF-free solutions but without discussion of the plating mechanism [19], [47]. Several authors found that Pd activation of Si is not possible without the inclusion of HF in the solution [11], [56]. It has been shown that Au, Cu and Pd are all able to be immersion plated to p-type, (100) Si from sulfate solutions (with HF) and that the HF concentration greatly affects the nucleation rate for the case of Cu [56]. One study found that for c-Si and a-Si surfaces (of unspecied dopant concentrations) the HF concentration did not affect the size and distribution of the Pd aggregates plated from a chloride-based solution but the number of dissolution etch pits increased with increasing HF concentration [11]. Defects on or near the surface (such as diffusions) have also been found to cause inhomogeneous Si dissolution during Pd activation [69]. A comprehensive study of the effects of HF-based Pd activation on the adhesion of subsequent AED layers has been carried out by Karmalkar et. al. [40] - [43]. Various substrates were activated with Pd from various bath types, sintered to form a Pd silicide and swabbed with iso-propyl alcohol to remove any residue, prior to AEDs of Pd and Ni. They found that the adhesion of subsequent AEDs on Pd activated samples is not governed by the HF concentration but by the Pd complex. The Pd-diamine complex was found to improve adhesion compared to the Pd-chlorine complex while the Pd-tetramine complex inhibits subsequent plating [40]. This means that too little NH4 F or NH4 OH for a given volume of PdCl2 will result in a high level of chlorine complexes and the subsequent AED may be non adherent. Too much of these additives

11 will convert all the diamine complexes to tetramine complexes which can result in the AED not plating as fast or at all. The Pd bath used in the standard IBBC plating sequence is Bath F from [40]. Figures 2.2 and 2.3 show a summary of the results of Karmalkar et al. that are relevant to the adhesion of plated layers activated by Pd immersion. Figure 2.2 a) shows a comparison of activation baths on various surfaces. Diamine-based baths improve the adhesion of AEDs of Ni in comparison to HF based ones for p-type surfaces but dont affect the adhesion on heavily doped n-type surfaces. Figure 2.3 shows that diamine-based activation does not signicantly improve the adhesion of AEDs of Ni on n-type, (111) surfaces in comparison to no activation but does improve adhesion on p-type surfaces, especially when heavily doped. This suggest that the nucleation density of the Ni plate on heavily diffused boron surfaces is increased by Pd activation - a phenomenon that is demonstrated experimentally in Section 4.3 of this work. Interestingly, Pd immersion plating was found to improve the adhesion of AEDs of Ni more than AEDs of Pd and adhesion of both metals was reduced if the immersion layer was not sintered [43]. This is a potential cause of poor adhesion in the pit contact IBBCs and is investigated in Section 4.4.2. Figure 2.2 b) shows that lowering the AED plating temperature also reduces adhesion. This may be related to the results of Section 4.4.3 which shows that silicide formation does not occur on unactivated samples plated at low temperatures. Figure 2.2 b) also shows that increasing the thickness of the Ni AED reduces the adhesion which is probably due to increased stress in the deposits [5]. For this reason, a thinner Ni layer was used in the experiments of Chapter 4 than in the standard IBBC plating sequence.

2.2.2

Autocatalytic Electroless Depositions

Cu is used in integrated circuits due to its low resistivity and superior resistance to

electromigration. It is a fast diffuser in Si however, and if located near a junction, can act as a trap, decreasing the minority carrier lifetime and increasing junction leakage [67], [73]. For this reason, Ni and Ni silicide is used as an interlayer between Cu contacts and Si substrates in Si solar cells. Ni and Cu contacts can both be plated by AED onto Si, Pd and each other.

12

a)

b)

Figure 2.2: Adhesion of an AED of Ni plated to variously doped substrates, activated with various Pd solutions. The Pd layer was sintered for 30 minutes at 200 C prior to the Ni plate. Adhesion as a function of (a) surface concentration and dopant type for various Pd activation solutions and (b) Pd solution type for various Ni plating times and temperatures. The substrates here are 4 .cm, p-type (after [42]).

a)

b)

Figure 2.3: Adhesion of an AED of Ni plated to variously doped substrates, with and without Pd activation. The activation solution is NH4 F-based and the Pd deposit was sintered for 30 minutes at 200 C prior to the Ni plate. The surface concentration of the n-type substrates was 4-8 x 1015 /cm3 and for p-type substrates, 1-2 x 1016 /cm3 . P+ denotes a boron diffused surface and N+ denotes a phosphorus diffused surface both with surface concentrations >1020 /cm3 . All substrates are (111). The graphs show adhesion of a 2 minute, AED of Ni plated from an alkaline, hypophosphite bath at 90-95 C onto (a) n-type surfaces and (b) p-type surfaces (after [41]).

13 The mechanism that drives AED is much the same as that of immersion plating except that the reduction of the metal ions is enabled via an oxidation reaction within the solution, at a catalytic surface, rather than by dissolution of the substrate. Generically, the process is represented by simultaneous anodic oxidation and cathodic reduction [6]:

Reducing Agent Metal z+ + ze

Reducing Agent z+ + ze Metal

(2.3) (2.4)

Formaldehyde is employed as the reducing agent in autocatalytic electroless Cu plating [7]. The reduction of Cu2+ has been shown to be diffusion limited and the oxidation of formaldehyde, to be electrochemically controlled [6]. The plating rate is therefore kinetically limited by the oxidation step, and variation of diffusion mechanisms (increasing the metal ion concentration or agitating, for example) will not change it. The catalytic nature of the substrate, however, does affect the decomposition of formaldehyde. It has been shown that Ni cannot be used as a catalyst for the oxidation of formaldehyde [6] so the deposition of Cu on Ni must proceed by another mechanism in these baths. A pure copper-formaldehyde-water bath needs to be operated below a pH of 6 [8]. Copper plating baths typically contain complexants, stabilizers and exaltants which stop the Cu ions precipitating in the bulk solution and change the initiation conditions. These often allow the bath to be operated at higher pH values. AEDs of Ni do not result in a pure Ni deposit on the catalytic surface but in an alloy with a composition that is dependent on the reducing agent. The use of sodium hypophosphite (NaH2 PO2 .H2 O) as the reducing agent, yields deposits of NiP alloys while deposits of NiB alloys can be obtained by using sodium borohydride (NaBH4 ) as the reducing agent [5], [49]. Both acid and alkali, Ni/NaH2 PO2 .H2 O plating baths can be employed [49], [48], but here the discussion is mostly conned to alkaline/Ni/NaH2 PO2 .H2 O baths. The resistivity of the a NiP alloy increases from 10 .cm to 120 .cm as the phosphorus content varies from 0 - 12 wt% (data from Enthone, Netherlands published in [37]). It has been shown that the P content of Ni AEDs varies from 4.7% to 3.3% as the pH was varied

14 from 8 to 12 [5]. In acid baths the same trend is observed but it is much more pronounced and the P content is generally higher than in alkali baths [48]. The phosphorus content of the deposit is also increased by increasing the plating temperature [62]. The plating rate is known to be directly proportional to the bath temperature and increasing the pH will also increase the plating rate [27], [48]. As with AEDs of Cu, AEDs of Ni are also kinetically limited by the oxidation step and therefore dependent on the hypophosphite concentration [49], but not the NiCl2 concentration [34]. The catalytic effect of the substrate also plays an important role in the AED of Ni. It was found that NiP lms plated from an alkaline, Ni-hypophosphate bath at 90 C onto n-type, 3-5 .cm samples were thicker on (100) surfaces than on (111) surfaces [9]. Differences in the Ni plating rates on n- and p-type surfaces have also been reported [34], [40]. One study found that this difference increased with increasing illumination but equal plating rates could be obtained by the addition of 6g/L of ethyl-diamine-tetra-acetic acid (EDTA) into the plating solution [34]. EDTA concentrations greater than this suppressed plating altogether on both substrate types. When plating DSBC solar cells, however, it was found that proprietary, alkalibased, Ni plating solutions containing EDTA were not able to plate the heavily boron diffused grooves but that EDTA-free solutions [21] and maintaining high pH values and temperatures [20] could overcome the problem. This was also found to be the case in this work.

2.3

Ni Silicidation
Ni silicide is used in IBBC solar cells for two reasons. The rst is to reduce the contact

resistance at the metal/semiconductor interface. The contact regions of a BC cell, however, are so heavily doped that the benet of forming a Ni silicide, in comparison to a Ni/Si interface on heavily doped Si, often does not outweigh the draw backs, such as the potential for shunting and the extra processing steps. The second reason for forming a silicide on IBBC solar cells is to promote adhesion of the subsequent, thick Cu layer. Cu can be plated directly to Si but it can not be heated to obtain good adhesion because of its high diffusion coefcient in Si and potential

15 to form traps. Ni, on the other hand, forms stable silicides when heated, which improves the adhesion of the existing Ni layer and of subsequent plated layers. In this section, a review of literature published on the theory and experimental results of Ni silicidation is presented, in order to better understand and control Ni silicidation in IBBC solar cells.

2.3.1

Silicidation of Pure Ni Deposits

Ni silicide is used extensively in CMOS devices because of its low sheet resistivity, low

silicon consumption and ability to form narrow line widths without compromising resistance (see [26], [28], and [54], for example). Silicide gates and interconnects in IC devices are generally formed by sputtering (see [26], [45], [38], [54] and [55], for example) or e-beam evaporation (see [16], [18], [39], [61] and [68], for example) at pressures of less than 106 Torr and the Ni silicide formed by rapid thermal processing (RTP). Ni is known to be the dominant mobile species in a Ni-Si system such that the growth of silicide is limited by the diffusivity of metal atoms through the silicide layer(s) to the Si interface (see [28], [50] and [60], for example). If the supply of Ni stops (if it is all consumed for instance or if the silicide layer becomes sufciently thick for the diffusion of Ni to the Si interface to become negligible) and energy is still supplied to the system then the phase of the silicide will change depending on the temperature, as shown in Figure 2.4. It is well established that for thin lms of pure Ni on Si substrates, the rst phase that forms is the Ni rich Ni2 Si phase which is stable up to 250-300 C (for examples see: [10], [28], [38], [55], [60]). For every micron of Ni consumed, 1.4 m of Ni2 Si will form [38]. As the temperature is raised and all the Ni is consumed the excess Ni in the Ni rich phase then diffuses to the Si interface forming NiSi in the temperature range 300-700 C (for examples see [10], [16], [28], [38], [39], [55], [60], [61]). For every micron of Ni2 Si reacted, 1.5 m of NiSi will form [58]. If the temperature of the system is raised high enough the epitaxial, Si rich, NiSi2 phase begins to form (for examples see [10], [18], [28], [39], [55], [61]). The NiSi2 phase is generally uneven in thickness and characterised by agglomeration of Si at the surface [39]. A summary of this is shown in Figure 2.4.

16 Table 2.1 presents a summary of sheet resistance measurements of Ni silicide layers found in the literature. It shows that, as a thin layer of Ni on a Si substrate is heated from room temperature to 900 C, the resistivity of the lm changes as the phase of the silicide changes. The Ni2 Si phase, which is formed below 300 C, is less conductive than the NiSi phase, which has sheet resistivity in the range 1.8 - 7 /sq. A 30 nm Ni lm can be completely converted to the low resistivity NiSi phase in the temperature range 400-700 C. Sintering at temperatures higher than this causes the sheet resistivity to increase, which is usually attributed to agglomeration of the lm during the NiSi to NiSi2 phase transformation. Similar sheet resistivities as those given in table 2.1 for Ni silicide lms were also observed in this work (see Sections 4.4.1 and 4.5.2). As shown in Table 2.1, the affect of temperature on Ni silicide phase transformation has been well characterised in the literature. While not as well characterised, dopant density at the substrate surface has also been found to affect the phase transitions during Ni silicide growth. One study found a signicant difference in the sheet resistivity of Ni silicide lms prepared on As and B ion implanted, (100) substrates [38]. The silicide lms were prepared by Ni sputtering and RTP. For sintering temperatures between 350 C and 550 C the sheet resistivity was the same on both polarity samples (7 /sq) but for sintering temperatures between 260 C and 330 C, the sheet resistivity on As implanted wafers was 30 /sq. while on B implanted wafers it was 70 /sq. This was attributed to a difference in the grain size which was found to be smaller on B implanted samples. The NiSi phase was found to form at a lower temperature on the B implanted samples because Ni diffusion through the Ni2 Si layer is faster with a higher density of grain boundaries. Another study observed the usual Ni2 Si-NiSi-NiSi2 phase transitions on 3-8 .cm, (100), n-type substrates but when they were BF2 + implanted, the order of the phase transformations was different, with the NiSi2 phase being found to form at much lower temperatures [10]. Stabilisation of the Ni2 Si phase and transition from Ni2 Si - NiSi2 without the formation of NiSi on samples with boron implanted through the Ni lms has also been reported [68]. Hence, the correlation between sheet resistivity and silicide phase that exists for undiffused samples is not the same for diffused samples. This factor has been taken into account in

17

Figure 2.4: A summary of the most commonly reported phases of Ni silicide and their temperatures of formation, [10], [16], [18], [28], [38], [39], [55], [58], [60], [61]. In general, x1 < x2 < x3 and the Si rich phase, formed at higher temperatures, tends to agglomerate.

Type N P N P P P N P P P

Doping (.cm) 3-8 20 - 30 3-8 20 - 30 1 - 10 20 - 30 3-8 20 - 30 1 - 10 20 - 30

Thickness of Ni (nm) 30 30 30 27 30 30 30 27 30 30

units are in .cm

Sintering Temperature ( C) 200 - 300 350 - 450 400 - 600 450 - 700 500 - 700 400 - 700 600 - 900 700 - 800 800 700 - 800

Phase Ni2 Si Ni2 Si NiSi NiSi NiSi NiSi NiSi + NiSi2 NiSi2 NiSi2 -

Sheet Resistivity (/sq.) 6 - 3.5 30 - 13 3.5 2.5 7 1.8 3.5 - 6 2.5 - 10 110 1.8 - 3.5

Source [10] [16] [10] [16] [18] [61] [10] [16] [18] [61]

Table 2.1: Summary of Ni silicide phase transitions and sheet resistivity results from various authors. All substrates are (100), c-Si

18 the experiments of this work. Crystal orientation of the substrate has been found to affect the silicidation growth rate. One study compared Ni silicide formation from 160 nm thick, vacuum evaporated Ni lms on 2-10 .cm, (100) and (111) substrates [60]. The lms were sintered in a vacuum in the temperature range 200 C - 325 C. The Ni2 Si phase (only) was formed on both substrate orientations, as expected at this temperature. The growth rate, however was found to be signicantly higher on (100) substrates than on (111) substrates. These ndings were conrmed by another study which found that the growth rates of both Ni2 Si and NiSi on 1-10 .cm, n-type substrates sintered in the temperature range 300 C-370 C was nearly double on (100) substrates compared to (111) substrates [50]. In this thesis silicide formation and the adhesion of subsequent AEDs is observed on planar, (100) samples. In a pit contact IBBC solar cell, however, the contacts are inverted pyramids with (111) facets. This means that when transferring the process from test structures to cells, longer sintering times may need to be employed in order to form the same thickness of silicide.

2.3.2

Silicidation of AEDs
It has been reported that there are considerable differences in the phase transformations

at low temperatures for AEDs of Ni compared to vacuum depositions. One author studied the Ni-silicide phase transformations of 30-40 nm AEDs from acidic, NiSO4 -NaH2 PO2 based baths at 70 C on n-type, (100) substrates, sintered at various temperatures for 1 hour [46]. The substrates were activated with either a seed layer of electron beam evaporated Ni (EB-Ni) or SnCl2 sensitized Pd. Another reports a similar study of AEDs of Ni on p-type, 1-10 .cm Si plated in alkaline, NiCl2 -NaH2 PO2 baths at 95 C, sintered at various temperatures for 1 hour [57]. Their ndings are summarised in Table 2.2. Table 2.2 shows that Pd activation tends to inhibit Ni silicide formation, a phenomenon also observed elsewhere [47] and in this thesis (see Section 4.4). Epitaxial NiSi2 , usually reported to form above 600 C, was found to form on the EB-Ni and Pd-activated samples at temperatures of 300 C and 400 C, respectively [46]. This was attributed, by the authors, to

19

Sintering Temperature As Deposited 200 C 300 C 400 C 500-700 C >800 C

Deposition 1 3 nm amorphous layer at AED-Ni interface 20 nm unreacted NiP, 15 nm epi-NiSi2 10 nm Ni3 P 10 nm NiSi 20 nm epi-NiSi2 NiSi only NiSi and poly-NiSi2

Deposition 2 1.5 nm amorphous layer at AED-Ni interface Ni3 P at surface, no reaction at interface 10 nm NiSi 20 nm, epi-NiSi2 NiSi only NiSi and poly-NiSi2

Deposition 3

Ni3 Si2 major NiSi traces

Ni3 Si2 major NiSi minor NiSi major Ni3 Si2 minor NiSi2 major NiSi minor Ni3 Si2 traces

Table 2.2: Phenomena observed for AEDs of Ni plated to (100) substrates and sintered at various temperatures. Deposition 1 refers to 30-40 nm of NiP plated on EB-Ni seed layers on n-type substrates [46], Deposition 2 refers to 30-40 nm of NiP plated to Pd activated, n-type substrates [46] and Deposition 3 refers to 800-3000 nm of NiP plated directly onto p-type 1-10cm substrates [57].

the presence of a Ni3 P layer at the surface, reducing the metal concentration at the interface and hence inhibiting the metal rich phase formation. It is possible that the presence of the Ni3 P layer is due to the presence of the amorphous interlayer (assumed to be oxide). Others, however, have not found impurity containing phases. For example, Ni2 B or NiBSi were not detected on samples where boron was implanted through a pure Ni lm [68] and the formation of a Ni3 P layer was not observed for Deposition 3 in Table 2.2. Instead, a Ni3 Si2 phase, which has not been previously reported, formed from AEDs of Ni varying in thickness from 800-3000 nm [57]. The formation of the NiSi phase, at temperatures as low as 275 C, has also been reported for AEDs of Ni [4]. This silicide layer was formed on the (111) facets of a textured, (100), p-type wafer with a 20-30 /sq. phosphorus diffusion. Sintering was carried out in a furnace in air ambient. Although the authors attribute the low temperature formation of the NiSi phase to the orientation of the plated surfaces, the preceding discussion indicates that the nature of the Ni layer (pure Ni or NiP), and the dopant level at the surface, are probably also contributing

20 factors in this case. Clearly, silicidation of AEDs of Ni is not as well characterised or as predictable as the silicidation of vacuum deposits of Ni. It is also clear that, impurities within the plated layer, substrate orientation and doping level, dopant type and Pd activation all play an important role in determining the characteristics of the resultant Ni silicide. Heavy doping levels, variable impurity levels in the Ni plate, Pd activation and plating of (111) surfaces formed in (100) wafers are all features of IBBC solar cells and should be taken into account during silicide formation.

2.4

Electroless Metallization of Silicon Solar Cells

The electroless metallization techniques described in Sections 2.2 and 2.3 have been

applied in various combinations to various types of c-Si solar cells. In order to plate metals in a contact pattern on the cell surfaces, the wafer must rst be masked and the contact pattern dened in the mask such that only the contact areas plate. Oxides or nitrides or a combination of the two are generally employed in c-Si solar cells as anti-reection coatings and for surface passivation and they can also be used as plating masks. These dielectrics can be patterned in various ways, the most common of which are photolithography and scribing. Patterning a dielectric layer by photolithography involves the deposition of a temporary, photosensitive layer onto the wafer surface and the patterning of this layer by exposure to light through a detachable mask. The contact pattern is then developed in the photosensitive layer which is resistant to certain etches that will dissolve the underlying dielectric. The contact pattern is formed in the dielectric layer by immersing the wafer in such an etching solution. The photosensitive layer is then removed. Photolithography can achieve ne line widths (on the order of a few microns) but it is slow, costly and involves many processing steps. For this reason it is generally used in conjunction with vacuum evaporated metals for high efciency, laboratory devices (see [74], for example). Contact openings can also be made through the eld dielectric by laser or mechanical

21 scribing. Scribing processes not only remove the dielectric mask in the contact areas but usually some of the underlying Si as well. Laser scribed contacts require alkaline etching prior to further processing, to remove loose, ablated Si from the contact areas [70]. Laser and mechanically scribed contacts are generally 30 m wide and 50 m deep [3], [37], and usually require an additional diffusion step. To make ohmic contact between a metal and a semiconductor, a minimum surface concentration of 1019 dopant atoms/cm2 is required at the interface [66]. For conventional furnace diffusions, this usually corresponds to sheet resistances lower than about 20 /sq. Doping an emitter to this level, to minimise contact resistance, would result in substantial recombination losses in the emitter. The ideal emitter sheet resistivity, that minimises both series resistance and shading losses, depends on the geometry and resistivity of the ngers [53]. In screen printed solar cells, emitter sheet resistances of 40 - 60 /sq. are used which results in adequate contact resistance to the wide, high resistivity printed pastes but substantial emitter recombination losses [59]. If contact resistance was not an issue, better cell performance could be achieved by going to higher emitter sheet resistivities and thinner, less resistive ngers. Such a cell can be realised by the use of a selective emitter. A selective emitter has light emitter doping (typically 100 /sq.) over most of the cell surface but heavy doping (less than 20 /sq.) in localised regions under the metal contacts. Figure 2.5 shows the various types of solar cell contacts that can be made using photolithographically dened or scribed contact openings. Planar contacts with either homogeneous or selective emitters (Figure 2.5 a) and b), respectively) can be made using photolithography. Three dimensional or buried contacts can be made using either photolithography in conjunction with etching or laser or mechanical scribing (Figure 2.5 c) and d), respectively). Emitters with buried contacts can be homogeneous but are usually selective, because a second diffusion is required. There are various studies reported in the literature which utilise the different techniques of fabricating electroless contacts in silicon solar cells. A discussion of the electrical and adhesion properties of such contacts are presented in Sections 2.4.1 and 2.4.2.

22

a)

b)

c)

d)

Figure 2.5: Schematic of various electroless plated contacts. Dotted lines indicate diffused Si, light grey areas indicate the dielectric and dark grey areas indicate the plated metal. Photolithographically dened contacts with a planar homogeneous emitter, a planar selective emitter, and a buried selective emitter are shown in a), b), and c), respectively. A scribed contact with a selective emitter is shown in d).

2.4.1

Planar AED Contacts

Several devices with electroless contacts plated to photolithographically dened open-

ings in the eld dielectric have been reported in the literature. A summary of the processing used in these is presented in Table 2.3. All the cells are p-type with homogeneous, phosphorus diffused emitters and all ADEs of Ni are in fact Ni-P. One study compared cells with Ni plated contacts sintered by two different methods to cells of the same structure with vacuum evaporated Ti-Pd-Ag contacts [47]. It found that the adhesion and series resistance of the Ni plated contacts was poorer than the Ti-Pd-Ag contacts. The Ni plated cells that were sintered by rapid thermal processing (RTP) had only marginally poorer IV characteristics than the Ti-Pd-Ag ones. Cells with furnace sintered, Ni plated contacts, however, exhibited IV characteristics consistent with a high concentration of recombination centres in the diode due to excessive Ni diffusion. Another study compared cells with plated contacts to the same cells with Al sputtered contacts and found the IV behaviour of both cell types to be the same [69]. The Ni sintering time at 270 C was varied and it was found that cells sintered for 40 minutes exhibited only

Cell Type Pd Type PdCl-HCl PdCl-HCl PdCl3 -HF 30 30 30 350 350 290 15 RTP 20 5 15 400 RTP 270 260 240-400 Ni Sinter Time (min) Ni Sinter Temp ( C)

Plated Surface

Planar 111 Planar 111 Planar 100 Textured 111 Planar 111 Electrolytic Cu was then solder dipped

Sheet Resistivity (/sq.) 30 30 30 20-30 14 Pd Sinter Time (min) Pd Sinter Temp ( C)

Ni Sinter Ambient N2 RTP Vacuum Air N2

Silicide Various Various NiSi NiSi N/A

Other Metal None None Cu + Sn Solder None

Source [47] [47] [69] [4] [3]

Table 2.3: Summary of processing parameters of various c-Si solar cells with planar, photolithographically dened, electrolessly plated contacts.

23

24 a small degradation in Voc while Voc was reduced by 20% in cells that were sintered for 60 minutes. The cells that were sintered for 20 minutes [69] and the cells with RTP Ni contacts [47] and the textured cells in Table 2.3 [4] all exhibit similar IV characteristics. This suggests that the non-optimal IV curves observed by Lue for the furnace sintered cells are the result of to high an sintering temperature (see Table 2.3). Table 2.3 illustrates that it is possible to plate adhesive AEDs of Ni to planar (as opposed to buried) surfaces and form a silicide at the Ni/Si interface on both (100) and (111) surfaces, with and without Pd activation. Only one of the authors reported the adhesion of Ni to be a problem on planar surfaces who observed that the Ni layer would ake off at a thickness of 1 m [3].

2.4.2

Buried AED Contacts

Table 2.4 lists the parameters of various types of electrolessly plated solar cells with

buried contacts and selective emitters. Cell No. 1 is an example of a buried contact produced by photolithography and reactive ion etching (RIE), Cell No. 2 is an example of a buried contact made by mechanical scribing and the rest are all laser scribed buried contacts. The RIEed contacts had a 5 m x 5 m square cross section [17]. The mechanically scribed and etched contacts were 40 m wide, 60 m deep and diamond shaped [3]. The laser scribed grooves of Cell No. 4 are of a similar shape but the dimensions are approximately 25 m x 25 m [37]. The grooves on Cell No. 8 and Cell No. 9 are the same depth as the mechanically scribed ones but only half as wide [15], [29]. One of the drawbacks of electroless plating of buried contacts is that the metals plate faster at the corners of the grooves than inside them resulting in the grooves being closed off before they can be lled [37]. This does not appear to be a problem for the small, square shaped grooves of Cell No. 1 which were able to be completely lled with an adhesive AED of Ni [17]. Mechanically scribed grooves plated with electrolytic Ag (Cell No. 2) and small laser scribed grooves plated with electroless Cu (Cell No. 4) or with non-optimised electrolytic Cu (Cell No. 5) all result in a thin layer if metal on the walls of the grooves and overplating at the groove

Cell No. Dopant As 14 Heavy Heavy Heavy <5 P < 5, 20 < B < 70 P < 5, B < 10 P < 5, B < 10 Ni Sinter Ambient Forming Gas N2 N2 N2 N2 N2 N2 Other Metal Thin AED Cu Electrolytic Ag AED Ni + Cu AED Ni (0.1 m) + Cu (5 m) AED Ni (2 m) + electrolytic Cu AED Ni + Cu (50m) AED Ni + Cu (50m) AED Ni + Cu (50m) AED Ni + Cu (50m) Heavy Chemical roughening PdCl2 -HCl-HF-NH4 OH PdCl2 -HCl-HF-NH4 OH Sheet Resistivity (/sq.) Activation

Cell Type

Contact

Etched

2 SSBC 3 EWT 4 SSBC 5 SSBC 6 SSBC 7 DSBC 8 DSBC 9 IBBC Cell Ni Height No. (m) 1 5 2 1 3 N/A 4 0.1 5 0.1 6 N/A 7 N/A 8 N/A 9 N/A The unreacted Ni was removed after sintering. P P P P P P&B P&B P&B Ni Sinter Temp ( C) 400-700 290 375 400 400 400 250

Photolithography and RIE Mechanically scribed Laser scribed Laser scribed Laser scribed Laser scribed Laser scribed Laser scribed Laser scribed Ni Sinter Time (min) N/A 15 10 N/A N/A 5 10

Source [17] [3] [44] [37] [37] [70] [20] [15] [29]

Table 2.4: Summary of processing parameters of various c-Si solar cells with buried, electrolessly plated contacts. 25

26 opening. The electrolytic Cu bath composition of Cell No. 5 was varied to achieve bottom up lling of the grooves with no overplating and the cell IV characteristics were compared to the electrolessly plated Cell No. 4. The contact resistance and ll factor were both slightly improved by switching to lled grooves [37]. Cells No. 4 and Cell No. 5 were plated using the technique of removing the unreacted Ni after silicide formation. This is the only application of this technique applied to solar cells that could be found in the literature. Cell No. 3 is an example of a laser scribed buried contact with a different structure an emitter wrap through (EWT) cell. In EWT cells the emitter contact busbar is on the rear side and is connected to the front grid through via holes, to reduce shading losses. Here Ni is electrolessly plated simultaneously to ngers (single laser scribe), large area busbars (many scribes etched together) and laser drilled holes [44]. In plating Cell No. 3, it was reported that it is much more difcult to obtain adhesive AEDs on the large area, heavily P diffused busbars than in the ngers and via-holes. Inhomogeneous Ni layers and blistering were found to be a problem during plating. Sintering the AEDs of Ni at too low a temperature also caused adhesion problems while sintering at too high a temperature or in oxygen was found to cause Ni spiking. EWT cells with AEDed contacts were found to have lower series resistances than the same cells with screen printed contacts, however screen printed contacts made a better rear surface reector [44]. As was the case with the furnace sintered cells in Section 2.4.1, the IV characteristics of Cell No. 3 did not t the 2-diode model which may also be due to the relatively high Ni sintering temperature of 400 C. A Ni annealing temperature of 400 C was employed for Cell No. 6, however, because the series resistance of these SSBC cells was reduced by annealing at higher temperatures [70]. The Ni annealing temperature for Cell No. 9 was reduced to 250 C to avoid shunting between the base contacts and the emitter [29]. IBBC cells with adhesive contacts and efciencies of 19.6% have been achieved with this sintering temperature [29]. The DSBC Cell No. 7 and Cell No. 8, with efciencies almost as high as that of the IBBC, have been achieved without sintering the Ni at all [15], [20]. This demonstrates that for a laser scribed, buried contact, a silicide does not need to be formed in order to make

27 ohmic contact to heavily diffused Si or for the contacts to be adhesive.

2.5

Summary
In this chapter, a review of the literature pertaining to the electroless metallisation of Si

solar cells has been presented. Examination of reports on Pd immersion activation reveals that this increases the nucleation density of susequent Ni deposits on p-type Si and thereby improves adhesion of the Ni layer. The plating rate, adhesion and resistivity of AEDs of Ni is reported to be related to the plating bath pH and plating temperature while the silicidation and adhesion of these deposits is reported to be related to the dopant density and orientation of the substrate. The dopant density in an electrolessly plated, NiP alloy was reported to affect the phase of the silicide formed and Pd activation of the substrate was reported to inhibit the formation of Ni silicide. Many different solar cell structures, with both planar and buried contacts have been reported to have been successfully metallized by various electroless plating sequences. The most commonly reported problem with electrolessly plated cells was increased recombination or shunting due Ni sintering temperatures that were too high. Adhesion was only reported to be an issue for some planar contacts and large area buried contacts.

Chapter 3 Research Methodology

3.1

Introduction
In this chapter, the method used to carry out the experiments of Chapter 4, is presented.

Section 3.2 provides some information about the types of contacts found in buried contact solar cells and their usual metallization sequences. Section 3.3 starts by discussing the test structures used in this thesis. Constituents of the plating solutions are given in Section 3.3.1. Section 3.3.2 discusses how Ni plated samples were sintered in this work. Section 3.3.3 and Section 3.3.4 demonstrate how a sulfuric peroxide mixture (SPM) is used in this thesis.

3.2
3.2.1

Background Information
Buried Contact Solar Cell Structures
The single sided buried contact (SSBC) solar cell was invented by Wenham and Green in

1985 [71], [70], and has been in commercial production ever since. A schematic of the SSBC is shown in Figure 3.1. It consists of a selective phosphorus emitter with laser scribed buried contacts on a p-type base. Contact to the base is achieved through an Al alloyed region over the whole of the rear surface. Modications to the SSBC that have the potential to signicantly improve cell efciency have been worked on extensively at the University of NSW. The double sided buried contact (DSBC) solar cell [15], [21], [52], and IBBC solar cell [29] utilise P and

29

Figure 3.1: Schematic of a SSBC solar cell showing 1) random pyramid textured, front surface, diffused with 100 /sq. phosphorus emitter and passivated with SiO2 , 2) laser scribed grooves, diffused to < 5 /sq with phosphorus, 3) random pyramid textured rear surface with an aluminium back surface eld, 4) Ni and Cu plating in the front surface grid and 5) Ni and Cu plated over the entire rear surface.

Figure 3.2: Schematic of a IBBC solar cell showing 1) random pyramid textured, front surface, diffused to 100 /sq. with phosphorus and passivated with SiO2 , 2) saw damage etched, rear surface, diffused with 100 /sq. boron emitter and passivated with SiO2 , 3) laser scribed grooves, diffused to < 5 /sq with phosphorus, 4) laser scribed grooves, diffused to < 10 /sq. with boron and 5) Pd, Ni and Cu plating in both rear grids.

30

Process Name Saw Damage Etch Texturing Front Surface Field Oxidation Rear Surface Prep Boron Emitter Oxidation Base Contact Scribing Base Contact Diffusion Base Contact Drive-In Base Contact Masking Emitter Contact Scribing Emitter Contact Diffusion Emitter Contact Drive-In

Process Description 25% NaOH Solution 2% KOH/10% IPA Solution 100 /sq P diffusion TCA dry oxide growth HF then 12% NaOH Solution 100 /sq B diffusion Dry/wet/dry oxide growth Base contact glass deposition Diffuse P to 3 /sq Dry oxide growth Emitter contact glass deposition Diffuse B to 10 /sq

Time 20 mins 20 mins 10 mins 60 mins 10 mins 20 mins 150 mins 60 mins 180 mins 60 mins 60 mins 180 mins

Temperature 85 C 90 C 850 C 1030 C 55 C 900 C 980 C-1030 C 940 C 1050 C 1000 C 940 C 1050 C

Table 3.1: IBBC solar cells processing sequence prior to metallization.

B diffused surfaces with thermal SiO2 coatings to reduce the high rear surface recombination velocity associated with the Al BSF in the SSBC structure. A schematic of the IBBC is shown in Figure 3.2. The DSBC has a different structure to the IBBC but the contacts are virtually identical. Both the DSBC and IBBC structures introduce heavily diffused boron grooves into the processing sequence in place of Al alloyed contact of the SSBC. The substrate of the standard SSBC is p-type and hence the selective emitter contact is achieved with a heavy phosphorus groove diffusion (PGD). P2 O5 glass is deposited in the grooves at 940 C for 45 - 60 minutes by solid source diffusion. The base contact is formed by alloying an Al layer to the rear surface. The Al alloying step also serves as the PGD drive in and in the laboratory is performed for 15 hours (overnight) at temperatures of around 1000 C. This results in a sheet resistivity of less than 3 /sq. It also leaves a phosphorus silicate glass (PSG) on the surfaces of the grooves which can be removed in about one minute in a NH4 F:HF (15:1) solution. The IBBC solar cell processing sequence is shown in Table 3.1. As can be seen from this and Figures 3.1 and 3.2, there are several key differences between the SSBC and the IBBC structures, that greatly effect the plating sequence. As previously shown [29], the requirements for deglazing the grooves on an IBBC cell are remarkably different from those on an SSBC

31 cell. This is because, in order to diffuse boron into the emitter contact, a masking oxide must be grown over the phosphorus diffusion in the base contact. The two groove diffusions result in the presence of a thick layer of boro-phospho-silicate glass (BPSG) in the phosphorus grooves and a boro-silicate glass (BSG) in the boron grooves. It has been shown , that the deglazing solution for the IBBC needs to be signicantly different to that used for SSBCs due to the different etch rates of the various glasses involved [30].

3.2.2

Plating Buried Contact Solar Cells

Electroless metallization of SSBCs was initially employed because SSBCs made with

screen printed pastes were unable to produce efciencies as high as those with Cu contacts [70]. The screen printed cells were fabricated by using a squeegee but no screen [1]. Paste was deposited in the grooves but wiped off the eld oxide with the squeegee. This method proved inferior to electroless copper plating because it was difcult to get the paste into the grooves and it left a residue on the surface which was particularly problematic in the case of textured wafers. Shrinkage and high bulk resistivity of the printed pastes also proved detrimental for the SSBC design and electroless plating was found by licensees of the technology to be so much more economical than screen printing that it offset the cost of the extra furnace diffusion associated with the selective emitter [51]. The metallization sequence for the original SSBC solar cell is reported as follows [70]: 1. Residual PSG, which is present in the front contacts after phosphorus groove diffusion, is removed with a 15:1 buffered HF solution. 2. A layer of Ni is plated conformally in the phosphorus diffused, front contact grooves from an acid based, proprietary, electroless plating bath (from chemical supplier Transene [22]). Ni also plates to the Si rich regions of the Al/Si alloyed rear surface. 3. The Ni layer is sintered in a resistively heated, quartz tube furnace at around 400 C to form a Ni silicide layer. The silicide layer is made to reduce contact resistance, improve adhesion and act as a diffusion barrier to the subsequent Cu layer.

32 4. Another Ni layer is then electrolessly deposited from the same Ni bath to ensure that the subsequent Cu layer will initiate. 5. A layer of Cu is electrolessly deposited in the phosphorus grooves and over the rear surface, from a proprietary electroless Cu solution (from Enthone [64]). Because the SSBC, DSBC and IBBCs have substantially different contacts, the plating sequence for the SSBC could not be used on the DSBC and IBBC solar cells. The metallization sequence for these cells, which was developed at UNSW, is reported as follows [29]: 1. The thick layers of BPSG from the phosphorus grooves and BSG from the boron grooves is simultaneously removed with a 1% HF, 1% NH4 F solution. 2. Both groove types are activated with an NH4 OH-based, Pd immersion solution. 3. A layer of Ni is plated conformally in the phosphorus and boron grooves. Ni is plated from an alkali based proprietary electroless plating bath (from chemical supplier Transene [22]) at 90-95 C. 4. The Ni layer is sintered in a resistively heated, quartz tube furnace at around 250 C to form a Ni silicide layer. The silicide layer is made to reduce contact resistance, improve adhesion and act as a diffusion barrier to the subsequent Cu layer. 5. Another Ni layer is then electrolessly deposited, to ensure that Cu will plate to the sintered Ni layer which may have become deactivated during the sintering process. 6. A layer of Cu is electrolessly deposited in the phosphorus and boron grooves from a proprietary electroless Cu solution (from Enthone [64]). The IBBC plating sequence is complicated by the requirement to plate Ni to both polarities of Si. The PGD sequence for IBBC solar cells consists of the same P2 O5 glass deposition with a shorter drive-in time at a higher temperature. There is also a masking oxide step and a B2 O3 deposition half way through the drive-in process. The sheet resistivity of this diffusion

33 sequence is generally lower than that of the SSBC sequence and it is likely that the surface concentration is also different (although it is unclear whether it is higher or lower). In an IBBC cell the phosphorus grooves are used as the base contact and hence there is also no p-n junction present between the PGD and the base. The two types of PGD are, however, usually thought to be similar enough to be plated in the same way. The switch to an alkali-based electroless Ni bath was made during the development of the DSBC because it was thought to initiate better on the heavily boron-diffused grooves [2]. Pd activation was incorporated into the IBBC plating sequence to further improve the Ni plate in the boron grooves [29]. This resulted in a signicant improvement in the series resistance of IBBC cells activated with Pd but also an signicant drop in the shunt resistance. The cells plated with Pd were 3% more efcient (in absolute terms) than ones plated without Pd activation. It was hypothesised that the reason for this was improved nucleation of Ni on the heavily diffused boron surfaces, which has been observed previously [42] and which is conrmed in Section 4.3 of this thesis. Several authors report, however, that over-plating of the eld dielectric became problematic when using Pd immersion activation [19], [29], [69], a phenomenon also observed in this work (see Section 4.3). This does not result in shading issues in back contact cells but it is a potential cause of shunting and is best avoided if possible. Another difference between the two structures that affects, particularly the Cu plating, is the total surface area to be plated. The entire rear surface of the SSBCs is covered in an Al/Si alloy, on which plates both Ni and Cu. This activates the solution such that plating is much more likely to initiate on other, smaller areas on the cell, such as the front surface grooves. The total area to be plated on an IBBC cell, however, is much smaller than on an SSBC cell and hence the metal plate does not always initiate. This is generally mitigated by adding something that is known to plate (eg: strips of Al, dummy wafers) into the bath as well [20].

34

3.3

Experimental Method
All IBBC solar cells processed for this thesis were fabricated according to the sequence

outlined in Table 3.1. Simpler test structures, consisting of 1 .cm, (100) p- and n- type wafers with various diffusions types over the entire surface were also fabricated for this work. These structures, which represent the three different groove types employed in buried contact cells, are outlined in Table 3.2, along with their usual plating sequences. Although this work focuses on plating IBBC cells, the SSBC groove structure was included to enable sheet resistivity measurements of metal layers on a phosphorus diffused surface. All planar test structures were deglazed until hydrophobic in a proprietary solution of 7:1 buffered HF (from chemical supplier J. T. Baker [35]) prior to electroless plating. Sheet resistivity measurements were carried out using a standard, equispaced four point probe station.

Cell Type SSBC IBBC IBBC

Substrate p-type n-type n-type

Groove Diffusion 60 min P deposition, 15 hour drive-in 60 min P deposition, 8 hour drive-in 20 min B deposition, 5 hour drive-in

Interface Plating Alkali-based electroless Ni NH4 OH-based Pd Immersion, Alkali-based electroless Ni NH4 OH-based Pd Immersion, Alkali-based electroless Ni

Table 3.2: Silicidation test structure types.

Although the diffusion proles on the test structures has been kept as close as possible to those found in buried contact cells, the orientation of the plated surface is different. As discussed in Section 2.3.2, this affects the silicide growth rate from pure Ni deposits and possibly the phase transformations from AEDs of Ni. This means that the silicide formation observed on these test structures is not necessarily the same as the silicide formation occurring on buried contacts scribed through the surface of a (100) wafers. There is, however, a strong correlation between the observations of metal plating and sintering on the pit contacts in Section 4.2.3 and Section 4.3 and the test structures in Section 4.4 and Section 4.5. This correlation could be tested by plating pit contact IBBC solar cells using the plating sequence developed in this thesis.

35

3.3.1

Electroless Plating
The deglazing solution used on all IBBC cells in this work is identical to the one reported

in [30], which consists of mostly deionised water with 1% HF and 1% NH4 F, by volume. The electroless Pd immersion solution employed on all structures is the NaOH-based bath (bath F) reported by Karmalkar et al. [40]. Autocatalyitic electroless NiP deposits were plated from the alkaline based proprietary electroless Ni solution from Transene [22]. Constituents of the bath are detailed in Table 3.3. All were Ni plated in 300 mL of solution which was stirred using a teon coated magnetic stirring rod and a stirring hot plate. Plating was carried out at 80 C 2 C or 93 C 2 C.

Ingredient Nickel Chloride Hexahydrate Sodium Hypophosphite Ammonium Citrate Ammonium Chloride Ammonium Hydroxide Ethylene Diammine Tetracetate Distilled Water

Chemical Name NiCl2 .6H2 O NaH2 PO2 .H2 O (NH4 )2 HC6 H5 O7 NH4 NH4 OH (EDTA) H2 O

Amount 1 - 5% 1 - 5% 5 - 10% 5 - 10% 5 - 10% < 1% Balance

Table 3.3: Bath constituents of an ammonia-based, proprietary electroless Ni plating solution from Transene [22].

Ingredient

Chemical Name

Amount

Enthone Cu704 A Copper(II) Sulfate CuSO4 Formaldehyde H2 CO Tetrakis-(hydroxypropyl) ethylenediamine (Quadrol) Enthone Cu704 B Tetrakis-(hydroxypropyl) ethylenediamine (Quadrol) Enthone Cu704 M Sodium Hydroxide Potassium Cyanide NaOH KCN

10-20% 10-20% 0-9.99% 30-35% 30-60% 0-0.01%

Table 3.4: Bath constituents of a proprietary electroless Cu plating solution from Enthone [64].

36 Autocatalytic electroless Cu, where applied, was deposited from a proprietary solution Cu704 from Enthone [64]. Constituents of this bath are detailed in Table 3.4. All Cu plating was carried out out at 46 C in a 300 mL bath made up of 6% Cu704A, 6% Cu704B, 2% Cu704M and 86% deionised water, by volume. One activation wafer was added to the Cu plating bath along with the samples in each plating run. Activation wafers were 4 cm x 4 cm and were roughened prior to plating such that both sides plated Cu over the entire surface.

3.3.2

Ni Sintering
All Ni sintering in this work was carried out in a 4, resistively heated, quartz tube

furnace tted with a quartz load lock known as an elephant. A schematic of an elephant is shown in Figure 3.3. It consists of a section of quartz furnace tube that is closed at one end except for a small hole to t a push rod through. The other end is anged such that it ts over the mouth of the furnace and there is a N2 inlet on the top. Wafers are loaded into a parallel-loading quartz boat and pulled into the elephant. The elephant is ushed with N2 before attaching the elephant to the mouth of the furnace. Wafers are then pushed into the centre-zone of the furnace where they are sintered in a high N2 ow rate with the elephant still attached to the mouth of the furnace. During this time N2 is kept owing through the inlet on the elephant to keep it as free of O2 as possible. After sintering, the wafers are pulled into the mouth of the elephant and cooled on the furnace side of the N2 inlet to the elephant for around 3 minutes, to ensure that they cool to below 150 C whilst still in N2 ambient. The N2 ow to the elephant is then turned down momentarily, so that the wafers can be pulled passed the N2 inlet without breaking. The N2 ow is then turned up high and the elephant disconnected from the furnace. The wafers are allowed to cool back to room temperature in the elephant for a further 5-10 minutes. An elephant is used during furnace sintering of Ni plated layers because Ni oxidises readily in air at temperatures above about 200 C. Figure 3.4 shows how oxygen entering a furnace during sintering can be detrimental to the plated layer. Sample (a) has been Ni plated but not sintered at all. Sample (b) was loaded into the furnace without the elephant, so that it saw a temperature of about 200 C, and was then unloaded into air. It looks fairly similar to

37

Figure 3.3: Schemaitic of an elephant.

sample (a) but slightly yellowed. Sample (c) was sintered in the same way as sample (b) except that it saw a temperature of about 400 C. The Ni has turned a dark gold colour. Sample (d) was sintered in the same way as sample (c) except the furnace N2 ow was greatly reduced. The Ni has gone an even darker gold colour and blue streaks have started to appear. Samples sintered at 500 C, with an elephant connected to the mouth of the furnace but the elephant N2 left off during unloading, have been observed to turn bright blue and sintering electroless plated Ni in a belt furnace (air ambient) at 400 C will result in a deep purple Ni coating. It is important that this does not happen during experiments as the effects of oxidation during silicide formation has not been studied. Prior to commencing this work, the furnace used for Ni silicidation was temperature proled with the elephant connected (the prole was found to to be considerably different with and without the elephant attached for the same furnace settings). Temperature/position proles for some of the sintering temperatures used in this work are shown in Figure 3.5. The thermocouple used to measure the temperature prole was only just long enough to just reach the at zone with the elephant connected. A parallel boat was used so that the wafers in a single experiment all see the same temperature gradient and the boat was positioned such that the wafers sat at a distance 80 and 85 cm into the furnace. The temperatures quoted in this work are those shown on this graph and hence the actual temperature encountered by the samples is likely to be 10-20
C

higher than stated.

38

a)

b)

c)

d)

Figure 3.4: The effects of O2 on electroless plated Ni when heated. The samples have been Ni plated and (a) no sintered, (b) sintered at 200 C without the use of an elephant, (c) sintered at 400 C without the use of an elephant, (d) sintered at 400 C without the use of an elephant and with the furnace N2 turned down.

Figure 3.5: Temperature prole of furnace used for Ni silicide formation

39

3.3.3

Ni Cleaning
Selective etching of unreacted metal from silicide contacts is commonly used in the IC

industry where a two stage sintering process is employed to avoid shallow junction shunting [38]. Vacuum depositions of Ni are sintered by RTP at low temperatures to form thin layers of Ni2 Si. The unreacted Ni is then removed and a second RTP is performed to convert the Ni2 Si phase to the low resistivity NiSi phase. Selective etching is also useful when studying the sheet resistance of the underlying silicide phase. Good etching selectivity between Ni and Ni silicide has been achieved in H2 SO4 :H2 O2 :H2 O (4:1:60), HNO3 :HCl:H2 O (1:5:10) and HCl:H2 O2 :H2 O (1:1:60) solutions [45]. It has been clearly shown that unreacted Ni is etched away and the silicide is left behind after etching in a H2 SO4 :H2 O2 (4:1) solution at 60 C for 10 minutes [16], [61]. This solution can also be utilised as a selective etch at room temperature [18]. The technique of selectively removing the unreacted Ni from the silicide contact in solar cells has also been reported [37]. In this case, HNO3 was used as the etchant. A proprietary, H2 SO4 -based cleaning agent, to remove copper oxide from electroless deposits prior to contact resistance measurements, was also reported [37]. Cleaning the surfaces of plated metals is standard practice in the electroplating industry, especially between different layers of metals, to promote adhesion. The American Standard for Testing and Materials (ASTM) for electroplating Ni to electroless Ni seed layers recommends various cleaning techniques. One of these is acid immersion etching in either 500 mL/L of 37% HCl or 150 mL/L of H2 SO4 to remove any Ni oxide that might have formed on the surface [25]. HF is also effective at etching Ni oxides, but is problematic for use on semiconductor devices as it will also etch SiO2 . In this study, an SPM cleaning solution is used to remove the unreacted Ni from sintered, Ni plated samples. The solution is 1:1 (v/v) H2 SO4 (98% ) and H2 O2 (30%). This gives a H2 SO4 :H2 O:H2 O2 ratio of approximately 4:2:1. The reaction between H2 O2 and H2 SO4 is exothermic, and the solution heats itself to more than 100 C. The wafers are immersed as soon as the solution is mixed and stirred for one minute, before overow rinsing.

40

a)

b)

c)

Figure 3.6: Three sections of a boron diffused sample that has been Ni plated. Section a) shows the Ni plate intact, b) shows the Ni plate removed with RCA2 and c) shows the Ni plate removed with SPM. Figure 3.6 shows a Si wafer that has been boron diffused to 100 /sq and then Pd activated for 5 minutes, Ni plated at 80 C for 4 minutes and sintered at 350 C for 10 minutes. The sample was then split into three sections. Section (a) shows the Ni layer after sintering, section (b) shows the sintered Ni after RCA2 cleaning and section (c) shows the sintered Ni after SPM cleaning. Section (b) is grey with swirls of roughened areas whereas section (c) is covered with smooth grey and bronze swirls. These bronze sections can not be removed by repeating the SPM process and are assumed to be Ni silicide. The grey areas are assumed to be the original surface of the wafer where silicide formation failed and the unreacted Ni was removed. The roughened swirls on section (b) are assumed to be areas where silicide formed but was then removed in the RCA2 etch. This selective SPM is utilised in the remainder of the experiments presented in this chapter, to examine the silicide formation on planar test structures.

3.3.4

Pd Cleaning
The Pd activation technique employed by Karmalkar et. al. [42] differs signicantly

from that used by Guo in the IBBC plating sequence [29], in that the Pd is sintered at 200 C for an hour and a black residue is removed by swabbing the surface with a cotton bud soaked in isopropyl alcohol (IPA). Obviously this cleaning technique is not at all applicable to grooves or pits on solar cells, so another cleaning technique was sought. A Si wafer with a light boron diffusion (100 /sq) was cleaned in the 4:2:1 SPM dis-

41

a)

b)

Figure 3.7: A boron diffused wafer a) after Pd activation and b) the same wafer after cleaning. The left side of b) has been swabbed with a cotton bud soaked in IPA and the right side has been SPM cleaned and then swabbed with a cotton bud soaked in IPA. cussed in Section 3.3.3. There was no visible reaction at the wafer surface. The same sample was HF dipped, rinsed and Pd activated for 5 minutes. A brown coating appeared on the wafer surface, as shown in Figure 3.7 (a). The wafer was split in half and one half was cleaned in the SPM. Bubbles evolved vigorously from the wafer surface. Both halves of the wafer were then swabbed with a cotton bud soaked in IPA. A black residue was removed from the Pd plated sample as shown in the left side of Figure 3.7 (b). No black residue was able to be removed from the half of the wafer that was Pd activated and then SPM cleaned and yet the brown coating is still visible on the wafer surface, as shown in the right half of Figure 3.7 (b). This indicates that the two processes (IPA swabbing and SPM cleaning) produce a similar result so the SPM Pd cleaning process was trialled in some of the experiments in Chapter 4.

3.4

Summary
This chapter presented a review of the contact structures on buried contact solar cells

and gave details the experimental methods used in the current work. Section 3.2 discussed the differences between contacts on SSBCs, DSBCs and IBBCs and showed why Pd is necessary in IBBCs even though it can result in some overplating of the eld oxide. Section 3.3 discussed

42 the use of samples in this thesis. Section 3.3.1 gave details of the plating solutions used and outlined how the plating processes were controlled. Section 3.3.2 discusses process control for Ni sintering in a quartz furnace. Section 3.3.3 demonstrates how Ni silicide was observed on test structures and Section 3.3.4 demonstrates how SPM cleaning of Pd activated samples has the same effect as swabbing the samples with IPA.

Chapter 4 Experimental Results and Discussion

4.1

Introduction
This chapter presents and discusses the experimental results of this thesis. Section 4.2.1

demonstrates how the volume of heavily diffused Si in a buried contact solar cell is reduced by changing the laser scribing code from grooves to pits. This is then conrmed experimentally in Section 4.2.2. Adhesion problems encountered when pit contact IBBC cells are metallized using the standard plating sequence is discussed in Section 4.2.3. The results of a series of experiments that examine the effect of Pd activation and Ni plating parameters on silicide formation for the case of heavily phosphorus and boron diffused Si is then presented. Section 4.3 examines the morphology of electrolessly plated Ni layers and the contact interface on a pit contact IBBC cell with and without Pd activation, with and without sintering. In Section 4.4 phosphorus and boron diffused test structures are used to determine the effect of three different surface treatments - no activation, Pd activation, and Pd activation with SPM cleaning - on Ni silicide formation. The effect of Pd sintering and Ni plating bath temperature on silicide formation are also investigated in this section. An improved Ni silicidation technique is developed from these experiments. The nal experiment, presented in Section 4.5, demonstrates that the improved silicidation technique also improves the adhesion of thick, electroless Cu layers on planar test structures.

44

4.2

Preliminary Experiments
The main contribution to Jo in crystalline silicon solar cells with good post-processing

bulk lifetimes is recombination in the heavily doped regions under the metal contacts. In order to reduce this contribution to the recombination current there needs to be fewer dopants in the diffused contact regions. It has been shown that replacing large areas of heavy diffusion with locally diffused ones has a signicant impact on solar cell performance [65], [74]. One way to achieve this in the buried contact structure is to reduce the strength of the groove diffusions, which may lead to resistance limited enhanced recombination [14]. Another way is to reduce the total area of the contacts, thereby reducing the total number of recombination sites without increasing the barrier height between the metal and the semiconductor.

4.2.1

Pits and Grooves: a Structural Comparison

The trench-like structure of the grid ngers, in all of the UNSW buried contact solar cell

structures, is formed by scribing a line of overlapping holes through the eld oxide on the wafer surface with a laser. When the laser damage is etched away, using a 12% NaOH solution, the holes join together to form a trench. The geometry of the grooves does not allow them to be lled by the electroless plating sequence, as shown in Figure 4.1. To achieve a large enough volume of Cu in the grooves, so as not to incur signicant series resistance losses, the Cu ngers are generally plated to a width of about 50 m across the wafer surface. This is a thinner nger width than most screen printing processes achieve [71] but does not fully utilise the buried nature of the contact, which is only 25 m wide and extends 50 m into the substrate. Running a Q-switched, Nd:YAG laser in external mode causes the laser pulse to be triggered based on the position of the stage. This allows for precise control over the spacing between laser ablated holes on the wafer surface. By utilising this feature of the laser, a solar cell grid pattern can be formed in a similar manner to a standard buried contact grid pattern except that instead of the ngers consisting of trenches they will consist of a line of small holes, or pits, with a regular spacing. The spacing between pits is controlled by the laser software. If the laser

45 is operated with wavelength of 1064 nm, the pits formed (after the usual NaOH groove etch) are inverted, square-based pyramids with a 20 20 m2 base as shown in Figure 4.2 (the pyramids are inverted so the base is on the surface of the wafer). If the laser is operated at 532 nm, the pits formed will have a similar shape but will be 10 10 m2 on the base. The apex angle (the angle between the normal to the base through the apex and the facet) of a square based pyramid is 35.26 . Hence the height of each facet of a pyramid with base length 20 m is around 17 m and the total surface area of a pit of this size is around 700 m2 . This will be the total surface area of heavy diffusion per pit spacing. For pits with 10 m square bases the total surface area is a quarter of this. The total area contribution for a standard tench-shaped nger can be approximated by the depth of the groove multiplied by the length of the trench multiplied by two (ie: two sides of the trench). Hence, a 50 m long section of a 50 m deep trench will have a total surface area of 5000 m2 . Therefore, a grid made up of square-based pyramids with a base length of 20 m and a spacing of 50 m will have 7 times less surface area within the substrate than the same shaped grid made up of 50 m deep grooves. When cells with pit contacts are plated with the standard buried contact electroless metallization scheme, plating will nucleate in the pits, grow out of the pits, over the oxide and join together in the middle. If the pits are spaced 50 m apart and plated until they join together then the nger width will be 50m. Hence the volume of metal carrying the current will be the same as in the standard grid structure but the total area of heavy diffusion within the cell will be signicantly reduced.

4.2.2

Pits and Grooves: a Photoconductance Comparison

An experiment was conducted to investigate the effect of reducing the volume of the

total heavily-diffused Si in a well passivated, buried contact device. A batch of n-type, oat zoned, 1 cm wafers were lightly diffused with phosphorus (to 100 /sq) and a thick (3500A) thermal oxide was grown to passivate the surfaces. Two interdigitated grids were then scribed on all wafers except one control wafer which had no grid pattern scribed on it. Two samples were each scribed with pit spacings of 50 m, 75 m and 100 m and two were scribed with

46

Figure 4.1: Ni and Cu plated 50 m deep groove on an IBBC solar cell showing the void at the centre of the trench and 50 m of overplating.

a)

b)

Figure 4.2: SEM micrograph of (a) the plane view and b) the cross section of etched pits. The pits were scribed with a laser wavelength of 1064 nm and hence end up being 20 m across. The pits are spaced 50 m apart and hence the adjacent pits are out of the frame of this image. Note the oxide overhang in the plane view and the Si overhang in the cross section. The border with rounded corners in the plane view corresponds to the Si overhang and there is no oxide overhang in the cross section because the oxide was thinner to begin with and hence got etched back to the edges.

47 trench contacts. A laser wavelength of 1064 nm was used for all samples. Laser damage was removed with a weak NaOH etch and a heavy phosphorus groove diffusion ( 5 /sq.) was then performed. The P2 O5 deposition time was 60 minutes at 940 C and the drive in time was 3 hours at 1050 C in N2 ambient. The contact surfaces were then passivated with an oxide grown for 60 minutes at 1000 C. After diffusion of the scribed samples, the transient and quasi-steady-state photoconductance decay (PCD) methods [63] were used to measure the injection-level dependent, effective minority carrier lifetime curves. The lifetime of the sample, at any carrier density, can be converted into an implied open circuit voltage (I-Voc ), by the method outlined in [63]. By tting the lifetime curves at the high injection end, the saturation current contribution of the diffused regions, Jo , can be extracted. The I-Voc of each sample, at a carrier density corresponding to one-sun illumination and the Jo value of each sample, obtained by curve tting, are plotted in Figures 4.3 and 4.4, respectively. These shows that a 25-35% reduction in Jo can be gained by replacing grooves with pits spaced 50 - 100 m apart. This corresponds to an increase in I-Voc of approximately 10 mV. It was envisaged that this 10 mV gain could be incorporated in to the IBBC structure by simply rewriting the laser code (ie: for no additional cost). All other processing would be identical to the standard IBBC, including the plating, if the pits are spaced 50 m apart.

4.2.3

Metal Adhesion Problems of Pit Contacts

The main problem that could potentially arise from replacing groove contacts with pit

contacts is series resistance. It is not unreasonable to think that the main cause of increased series resistance in a pit-contact IBBC cell would be due to the same current being conducted into the contacts through a smaller area. In order to measure the effect of this, however, a split batch of the two types of cells would have to be manufactured. Several attempts at this were made before it became clear that the main cause of series resistance in pit contact IBBCs is a lack of redundancy. To achieve high efciencies with cells of this design, every pit must plate and join to the adjacent pits. If just one pit fails, part or all of a nger will become disconnected

48

Figure 4.3: Injection-level dependence lifetime curves of the various contact types.

Figure 4.4: Saturation current contribution from the diffused regions as a function of contact type.

49

Figure 4.5: SEM micrograph of poorly adhesive electroless Ni and Cu plated on the pits of several ngers of an IBBC cell. The rst and third ngers are phosphorus diffused and the second and fourth ngers are boron diffused.

from the contact grid, which negates the potential benet of having the pits in the rst place. Several split batches of IBBC cells, half with pit contacts and half with groove contacts, were fabricated (see Table 3.1 for processing details) and plated using the standard IBBC metallization sequence (see Section 3.2.2). The cells with groove contacts were plated until the nger width was 50 m and cell efciencies greater than 19% were measured. Efciencies of the pit contact cells were unable to be measured, however, because the plating was unreliable, as shown in Figure 4.5. The rst and third ngers (from left to right) have a heavy phosphorus diffusion in the pits. Only one in ve pits on each phosphorus diffused nger is copper plated. The second and fourth ngers have a heavy boron diffusion in the pits. There are at least ve pits on each boron diffused nger that have no metal in them. Figure 4.6 a) is an SEI of a busbar and part of a nger on a pit IBBC cell. Some of the pits in this image are over lled with Cu (arrow 1), some are half lled (arrow 2) and others appear to be empty (arrow 3). Arrow 4 points to three pieces of Cu with rounded tops and pyramid-shaped bottoms. Their shape indicates that they were plated in three adjacent pits and then came detached from the cell at some stage during the plating process. Figure 4.7 shows one of the ngers on another Cu plated cell, at the point of adhesion failure.

50

a)

b)

Figure 4.6: a) A busbar on a pit IBBC cell showing how the Cu plating has fallen out of the pits and b) a close-up of the top left hand corner of the same busbar. The numbers refer to the pit to the right of the number.

Figure 4.6 b) is a close-up of the top left corner of the image shown in Figure 4.6 a). There are, in fact, three different types of pits on this sample (labeled 1, 2 and 3 in the image): Pit 1. pits with no metal in them, Pit 2. pits with Cu in them and Pit 3. pits with Ni in them. To ascertain that this is actually the case, an EDS map was made of the each of these pits (see appendix A for a discussion of SEM and EDS). An SEI of the mapped area and EDS maps of the Si, Cu and Ni signals for each pit are shown in Figure 4.8. It is clear from these images that Pit 1 has no Ni plated in it and only a small amount of Cu plated around the top corners. Pit 2 has a layer of Cu plated in it which is so thick that the electron beam cant penetrate to the substrate (ie: there is no Si signal in the pit). This is also the case for Pit 3 except this time the Si signal is blocked by a layer of Ni. There are many points in the plating sequence that could be the source of metallization failure. The following discussion refers to the labeled arrows and pits in Figure 4.6. Arrows 1 and 2 point out that pits with Cu in them do not all have the same amount of Cu. There could be two reasons for this; 1) Cu initiates in the pits at different times during the plating sequence and 2) the Cu plated in some pits falls out at some stage during the plating process and then reinitiates. Arrow 4 points to evidence of this as does Figure 4.7. Arrow 3 and Pit 1 demonstrate that some pits have no metal plated in them. There could be several reasons for this; 1) neither the Ni nor the Cu plated in the rst place, 2) the Ni plated

51

Figure 4.7: A nger on a pit IBBC cell showing the Cu plate detaching from the Ni plate in the pit.

Pit 1. No Plating

Pit 2. Cu Plated

Pit 3. Ni Plated

SEI

Si Map

Cu Map

Ni Map

Figure 4.8: SEIs and EDS maps of the pits labeled Pit 1, Pit 2 and Pit 3 in Figure 4.6 b).

52 and then fell out of the pit or 3) the Ni and the Cu plated and then both fell out together. The rst is unlikely as the Ni deposit on this sample was observed with an optical microscope before proceeding to the next step in the process. Not all the pits were examined but, of a random sample of pits across the wafer (including both contact pads), all were found to have Ni plated to them. It will be shown in Section 4.4.4 that the Ni sintering process can cause the unreacted Ni to peel away from the substrate. Therefore the second reason can not be discounted as the failure point. It will be shown in Section 4.5 that when Cu is plated to an unsintered layer of Ni, both layers of metal peel away from the substrate. Therefore the third reason can also not be discounted. Pit 2 shows that there are some pits that have Ni plated in them but not Cu. This could be because: 1) the Cu failed to initiate or 2) the Cu plated to the Ni and then adhesion failed at the Cu/Ni interface. Cu could fail to initiate on the Ni in a given pit if the surface of the Ni has become oxidised. This could happen after the rst layer of Ni is sintered, thereby causing the second not to plate. It could also happen after the second layer of Ni is plated but before the Cu initiates. In Figure 4.7 the Cu that has come away from the substrate is still attached to the Cu in the adjacent pit. It appears that there is a layer of Ni left behind in the pit it has fallen out of, however, the geometry of the sample does not allow for this to be conrmed by EDS analysis. It is unlikely that the adhesion failed at the Ni/Cu interface, however, because, as will be shown in Section 4.5, the bond between Ni and Cu is quite strong. What is quite clear from this, is that the Cu is plating to many of the pits for a considerable length of time and then falling out. This is also quite surprising, given that the deposit from the same plating sequence applied to the standard groove contacts is always adherent, regardless of whether the Ni is sintered or not. This is most likely due to the way only a thin layer of metal plates on the walls of the grooves before the top is closed off, thereby physically holding the metal in place (see Figure 4.1). The geometry of the pits, on the other hand, allows the metal to fall out if the adhesion at any of the interfaces is poor. Determining which interfaces are poorly

53 adhesive is the subject of the rest of this thesis.

4.3

Metallization of Pit Contacts

This section shows the results of an investigation of electroless Ni plating of pit contacts

IBBC solar cells. The aim of the investigation was to determine whether or not the standard IBBC electroless Ni metallization and sintering sequence resulted in the formation of a silicide at the contact interface of pit contact IBBC cells. Pit contact IBBC cells were fabricated and metallized in the manner outlined in Section 3.3. Various parameters in the metallization sequence were varied and a Cambridge 360 scanning electron microscope (SEM) was used to make secondary electron images (SEI) of the topography of the Ni plate. Energy dispersive spectroscopy (EDS) on the same microscope was used to conrm the presence or absence of Ni in the pits. A discussion of SEM and EDS can be found in Appendix A. The results of this investigation show that Ni has a low nucleation density on heavily boron diffused pits. This causes extreme roughening of the contact interface after sintering which has the potential to cause shunting problems in nished devices. Section 4.3.3 shows that this problem can be mitigated by Pd activation.

4.3.1

Ni Plated Pits
Ni silicide formation has been shown to be inhibited by the presence of thin oxides at

the Ni/Si interface [45]. Hence, the rst step in a metallization scheme that employs silicide contacts, is proper deglazing of the contact surfaces. To determine roughly how long cell contacts should be deglazed for, phosphorus and boron groove diffusion test structures - that had been subjected to the same groove diffusion sequence as the cells - were deglazed in the cell deglazing solution. The phosphorus test structure took twice as long to go hydrophobic as the boron test structure. This means that, if the phosphorus diffused pits are properly deglazed, the boron diffused pits must be also. Figure 4.9 shows Ni plated to a boron and a phosphorus diffused pit on a pit contact IBBC

54 solar cell. This cell was Ni plated at 90-95 C for 10 minutes after being deglazed for 9 minutes (with agitation). The Ni plate is not conformal on either pit type and much of the Si in the pits is still exposed. Another cell was deglazed for 12 minutes (with agitation) and subjected to the same Ni plating process. The Ni layer was totally conformal on the phosphorus contacts on this cell. A typical example is shown in Figure 4.10 a). The AED on the boron diffused pits, however, still suffers from low nucleation density of the Ni plate. A typical example of this is shown in Figure 4.10 b). It is clear that the phosphorus diffused pit has been adequately deglazed which means the boron diffused pit must be also. Therefore, the low Ni nucleation density seen here must be a feature of the heavily boron diffused Si. a) b)

Figure 4.9: An example of badly deglazed a) phosphorus and b) a boron diffused pits, plated with electroless Ni.

a)

b)

Figure 4.10: An example of well deglazed a) phosphorus and b) a boron diffused pits, plated with electroless Ni.

55

4.3.2

Ni Sintered Pits
To examine the interaction of Ni and Si at the contact interface after silicidation, a pit

contact IBBC solar cell was split into three sections and two of the sections were plated with Ni at 90-95 C. One of the plated sections was sintered at 350 C for 10 minutes, to form a Ni silicide on the walls of the pits. The third section was not plated at all. The two plated samples appeared identical to the pits shown in Figure 4.10. Ni plating on the phosphorus diffused pits was conformal but on the boron diffused pits it was lumpy. Sintering did not change the appearance of the Ni plate; the sintered and the unsintered sample were practically identical. The plated samples were then etched in a standard RCA2 metal etch to remove the unreacted Ni. Figure 4.11 a) shows a pit on the sample that was not plated and Figure 4.11 b) shows a pit on the sample that was plated but not sintered. The Ni plate has all been removed in by the RCA2 process and the two pits appear almost identical. This indicates that there is not much interaction between the plated metal and the Si substrate, either during plating or removal of the metal in RCA2. This result was the same on both phosphorus and boron diffused pits. Figure 4.12 a) shows one of the phosphorus diffused pits on the sintered sample after removal of the Ni with RCA2. The Ni is now absent from this pit also and there has been some roughening of the pit walls in comparison to Figure 4.11 b). A Ni signal was not detected by EDS on any of the phosphorus pits. A boron diffused pit on the same sample is shown in Figure 4.12 b). A signicant Ni signal was unable to be detected by EDS in any of the boron pits either. As discussed Appendix A, this could mean there is no Ni present or that the amount of Ni present is too small to be detected by the microscope. It was shown in Section 3.3.3 however, that the etching selectivity of this process is low, which has most likely resulted in all the Ni being removed from the pits. Hence, Figure 4.12 shows that sintering the conformal Ni plated to phosphorus diffused pits - Figure 4.10 - causes minimal changes to the Ni/Si interface but sintering the uneven plating on boron diffused pits - Figure 4.10 b) - causes extreme migration of the Ni/Si interface. The mechanism behind this is not known and an investigation into its

56 causes has not been attempted here. It is likely to cause shunting, however and should be avoided. The next section shows how this effect can be avoided by increasing the nucleation density of the Ni plate on heavily boron diffused pits. This is achieved by Pd activation. a) b)

Figure 4.11: Pit contacts that have a) had no plating at all and b) been Ni plated at 90-95 C and the Ni removed in a standard RCA2 etch (no sintering).

a)

b)

Figure 4.12: An a) phosphorus diffused and b) a boron diffused pit that has been Ni plated at 90-95 C after sintering at 350 C and removal of the excess Ni in RCA2 solution.

4.3.3

Pd Activated Pits
It is hypothesised here, that rough plating in boron pits is a result of low nucleation

density of Ni on heavily diffused, p-type surfaces. To determine whether this is the case, another pit contact IBBC cell was properly deglazed and activated with Pd for 2 minutes (with agitation), rinsed with DI-water and then immediately plated with electroless Ni. The Ni plating used here was reduced to 80 C to avoid spurious overplating of the eld oxide, an example of which is shown in Figure 4.13. It was found previously, that overplating of the eld oxide was able to be

57 eliminated by reducing the Ni plating temperature from 95 C to 90 C for Pd activated, IBBCs with grooves [30]. It was found in this work, however, that spurious overplating was an issue for pit contact IBBCs for Ni bath temperatures above 83 C. A higher Ni plating temperature was employed in Sections 4.3.1 and 4.3.2 because heavily boron diffused pits are unable to be plated in the Transene Ni solution at 80 C without Pd activation. It should be noted that Pd activated, pit contact IBBC cells plated with Ni at 93 C suffered the same adhesion problems as those plated at 80 C. The Pd activated, Ni plated sample was split in half and one half was sintered at 350 C for 10 minutes. Figure 4.14 shows Ni plating on two of the pits on the unsintered sample and Figure 4.15 shows two of the pits on the sintered sample after the Ni has been removed in RCA2. The Ni plate in the boron diffused pits is much more conformal than when no Pd was used, indicating that the nucleation density has increased signicantly. Migration of the Ni/Si interface is now much more moderate. The interaction between the Ni and the phosphorus diffused surface, however, is also a lot more moderate than on the unactivated samples.

4.3.4

Conclusions
The main conclusion of the experiments presented in Section 4.3 is that the nucleation

density of AEDs of Ni, from the alkaline based bath outlined in Section 3.3 onto heavily boron diffused Si, is quite low. This causes extreme migration of the Ni/Si interface upon sintering, that may lead to junction shunting. The nucleation density on heavily boron diffused contact regions can be increased by Pd activation. Pd activation promotes a more conformal AED of Ni and moderates the interface migration. Table 4.1 shows a summary of these results.

4.4

Ni Silicidation
Section 4.3 showed that the interaction of Ni and Si at the interface of sintered, pit con-

tact IBBCs becomes more moderate with Pd activation. It is possible then, that poor silicide

58

Figure 4.13: Ni plated onto the eld oxide. The bottom left pit is plated with Cu but all other pits and the areas between them were determined to be Ni by EDS mapping.

a)

b)

Figure 4.14: A well deglazed, Pd activated a) phosphorus and b) boron diffused pit, with Pd activation and electroless Ni plating at 80 C.

a)

b)

Figure 4.15: The Pd activated a) phosphorus and b) boron diffused pits after sintering and RCA2 to remove the unreacted Ni.

59

Pit Type Phosphorus Phosphorus Phosphorus Boron Boron Boron

Pd

Ni Smooth Smooth Smooth Lumpy Lumpy Smooth

Sinter

Interface Smooth Uniform roughening Less roughening Smooth Extreme roughening Uniform roughening

Table 4.1: Summary of results from Section 4.3

formation may be one of the causes of low adhesion on pit contact IBBC solar cells. In order to study silicide formation, the interface conditions of the three planar test structure types (outlined in Section 3.3) were varied prior to electroless Ni plating. Three different surface preparations were tried: 1. Deglazing only (as found on SSBC grooves). 2. Deglazing followed by NH4 OH-based Pd activation (as found on IBBC grooves). 3. Deglazing followed by NH4 OH-based Pd activation followed by SPM cleaning. Surface preparation Number 3 was introduced to mimic the process reported by Karmalkar et al. [42] (as discussed in Section 3.3.4). Silicidation was carried out by furnace sintering as described in Section 3.3.2. The wafers were then SPM cleaned using the method discussed in Section 3.3.3 to remove any unreacted Ni, so that the Ni silicide formation could be observed.

4.4.1

Effect of Surface Activation

This section describes an experiment designed to test the effect of sintering temperature

and surface preparation on silicide formation. As discussed in Section 2.3, different phases of Ni silicide form at different temperatures above about 200 C and each phase has a different resistivity. It is hypothesised here that the low sintering temperature of 250 C, employed in the standard IBBC and/or the Pd activation may be inhibiting the silicide formation and contributing to adhesion failure on the pit contact IBBC cells.

60 Three SSBC (phosphorus diffused) test structures were HF dipped until hydrophobic and two of them were then Pd activated for 2 minutes until hydrophilic. One of these samples was SPM cleaned and then all three samples were HF dipped again. The sample without Pd became totally hydrophobic and the Pd-activated sample remained hydrophilic. The SPM-cleaned sample became partially hydrophobic; water clung to the surface for a few seconds before dispersing to leave the wafer hydrophobic. After surface preparation, the samples were plated with Ni at 80 C for 4 minutes. The Ni plated samples were then sintered for 12 minutes and the unreacted Ni removed by SPM cleaning. Four sets of three samples were prepared in this way and the sintering temperature varied from 250 C to 450 C in 50 C intervals. After Ni sintering, all samples were SPM cleaned to remove the unreacted Ni. A summary of this procedure is shown in Table 4.2. Without Pd HF dip Pd Activation SPM HF Dip Ni plating Sinter SPM With Pd With Pd and SPM

Table 4.2: Summary of the experiment. The results are shown in Figure 4.16.

The appearance of the Ni plate was quite repeatable for all four runs. All SPM-cleaned samples and samples without Pd plated uniformly bronze and all Pd-activated samples plated cloudy (grey). The surface of the wafers after the nal SPM clean (to remove the unreacted Ni) are shown in Figure 4.16. These images show that the SPM-cleaned samples are all mostly bronze in colour but the samples with and without Pd appear the same colour as they did before the Ni processing. The samples with Pd have some small bronze areas but the samples without Pd exhibit virtually no bronzed areas at all. The sheet resistivity of the SPM-cleaned samples was measured before and after the whole plating/silicidation process. The average sheet resistivity across each sample is shown in Table 4.3. Before is therefore the sheet resistivity of the heavy phosphorus diffusion and After

61 250 C 3.2 /sq 2.7 /sq 300 C 3.2 /sq 2.3 /sq 400 C 2.3 /sq 0.6 /sq 450 C 2.3 /sq 0.5 /sq

Before After

Table 4.3: Sheet resistivity variation with Ni sintering temperature. Measurements were taken before the plating sequence (ie: this is the sheet resistivity of the phosphorus diffusion), and after the unreacted Ni had been removed (ie: this is the resistivity of the phosphorus diffusion and the Ni silicide in parallel).

is the sheet resistivity of the Ni silicide layer and the heavy phosphorus diffusion in series. On all samples, the sheet resistivity decreased, indicating that the surface has changed. It is beyond the scope of this thesis to perform more precise qualitative analysis (Auger spectroscopy, for instance) of the surface, but three factors - bronzed areas on the wafer surface that are visible to the naked eye, inability of the bronzed areas to be etched by SPM cleaning and a lowering of the sheet resistivity in the bronzed areas but not in the grey areas - indicate that these bronzed areas are Ni silicide. Figure 4.16 shows that in order to get reasonable silicide coverage with these plating and sintering conditions, the Si surface rst needs to be Pd activated and SPM cleaned. None of the samples without Pd formed a silicide at all and silicide formation on samples that were Pd activated was minimal, patchy and independent of silicidation temperature. On the samples that were Pd activated and SPM-cleaned, however, a fairly uniform silicide formed over most of the surface and coverage exhibited a slight temperature dependence. Based on Table 4.16 it was concluded that a reasonable coverage of silicide can be obtained on phosphorus diffused surfaces at temperatures above 300 C, if the surface is Pd activated and SPM cleaned. Silicide formation for these conditions was then investigated on boron diffused surfaces. Three boron diffused test structures were prepared in the same manner as the SSBC samples. Both the Pd-cleaned sample and the sample without Pd failed to plate. The Pd activated sample plated well and a silicide formed over the entire surface. These results show that for these plating and sintering conditions it is not possible to form a silicide at the contact interface on both heavily phosphorus and boron diffused planar <100> surfaces at the same time. Boron diffused surfaces require Pd activation without SPM cleaning

62

Without Pd

With Pd

With Pd and SPM

250 C

300 C

400 C

450 C

Figure 4.16: P-type substrates with SSBC PGD of 3 /sq. across the whole surface. The samples had different Pd treatments prior to electroless Ni plating at 80 C for 4 minutes. The samples were sintered for 10 minutes at the temperatures indicated and the unreacted Ni removed in a 50% SPM.

63 in order to plate and the phosphorus diffused pits require Pd activation and SPM cleaning for a silicide to form.

4.4.2

Effect of Pd Sintering
In their studies, Karmalkar et. al., [40] - [43], sintered their Pd seed layers prior to Ni

deposition and then cleaned the remaining residue from the sample by swabbing. This section describes an experiment conducted to determine whether the formation of a Pd silicide prior to Ni silicidation, improves the formation of a Ni silicide on heavily phosphorus diffused samples. Six boron groove diffusion test structures were deglazed until hydrophobic and then Pd activated until hydrophilic (4 mins). Each sample was sintered with different time and temperature parameters, as shown in Table 4.4. The samples were then SPM-cleaned and a vigorous reaction was observed on all samples. The samples were plated with Ni at 93 C for 4 minutes and sintered at 300 C for 10 minutes to form a Ni silicide. The unreacted Ni was again removed by SPM cleaning so that the silicide formation could be observed. The higher plating temperature was used here because it was found that cells plated in this manner did not suffer from spurious overplating. It should be noted that boron test structures were not able to be plated at either Ni plating temperature without Pd activation. All boron test structures prepared with sintered Pd were able to be plated, however, suggesting that Pd was still present on the sample surface. Table 4.4 shows that Pd sintering enables subsequent Ni silicidation on boron diffused test structures even after SPM cleaning. It also demonstrates the importance of a nitrogen ambient during sintering. It would appear that Pd silicidation was successful at temperatures as low as 200 C and that a longer sintering time results in a more uniform Ni silicide at any temperature since the same swirly patterns that were visible in the Pd plate were also visible in the Ni silicide. Examples of uniform and non-uniform Ni silicide on Pd sintered samples are shown in Figure 4.17. Based on Table 4.4 a Pd sintering time and temperature of 20 minutes at 250 C was chosen to test both IBBC diffusion types, because it resulted in the formation of a uniform

64

Sample 1 2 3 4 5 6

Temperature 200 C 200 C 200 C 250 C 250 C 300 C

Time 20 min 20 min 40 min 10 min 20 min 10 min

Ambient AIR N2 N2 N2 N2 N2

Pd Silicide Swirly Swirly Swirly Swirly Swirly Swirly

Ni Silicide None Swirly Uniform Swirly Uniform Swirly

Table 4.4: Pd sintering on boron diffused test structures. a) b)

Figure 4.17: Boron groove diffused samples that have been Pd activated and the Pd sintered for a) 10 minutes at 250 C and b) 40 minutes at 200 C. Both samples then underwent SPM cleaning prior to Ni plating and at 300 C. Finally, the unreacted Ni was removed in SPM.

Ni silicide in a reasonable time. One test structure of each diffusion type was deglazed and activated with Pd for 3 minutes (until both samples became hydrophilic). The Pd was sintered at the chosen conditions and the two samples were SPM cleaned. The samples were then HF dipped and plated with Ni at 93 C for 4 minutes and the Ni sintered at 300 C for 10 minutes. The unreacted Ni was removed with SPM. Figure 4.18 shows images of the silicide formed by this process. A uniform silicide formed across the surface of the boron diffused sample, as before. Ni silicidation again failed on the phosphorus diffused sample. This and the fact that the boron diffused samples do not plate without Pd and that a silicide does not form on the phosphorus diffused samples with Pd suggests that the black residue removed in the SPM cleaning process after Pd activation, is in fact removing the Pd.

4.4.3

Effect of Ni Plating Temperature

Section 4.4.1 showed that in order to form a silicide on heavily phosphorus diffused

samples it was necessary to rst activate with Pd and then clean off the black residue with SPM. It was found that if this cleaning step is included, a Ni plating temperature of 90 C - 95 C can

65

a)

b)

Figure 4.18: Silicide formation on an a) IBBC phosphorus and b) boron test structure that was Pd activated and the Pd sintered at 250 C for 20 minutes. be used, without overplating the eld oxide (in a cell). It is desirable to use a higher plating temperature if possible because the resistivity of the NiP alloy will be lower due to a lowering of the phosphorus content (see Section 2.2.2). An experiment was carried out to determine the effect of higher plating temperature on Ni silicidation on each of the three test structures. One sample of each test structure type was prepared with one of the three surface preparations (no Pd, Pd, Pd and SPM). Pd activation was carried out for 3 minutes and Ni plating was done for 4 minutes at 93 C on all samples. The samples were sintered at 350 C for 5 minutes and the unreacted Ni removed with SPM. The resultant silicide is shown in Figure 4.19. Two major differences in silicide formation were observed on samples plated at 93 C compared to those plated at 80 C. The rst is that a silicide now forms on the SSBC PGD sample without Pd activation and the second is that the Pd activated/SPM cleaned, IBBC BGD sample now plates and a good coverage of silicide is obtained. Both Pd activated, phosphorus diffused test structures still fail to form a silicide. The experiment was repeated on IBBC phosphorus and boron diffused test structures but with a lower Ni sintering temperature of 300 C for a longer time (10 minutes). The same result was observed on both sample types. The boron test structure with no Pd failed to plate but all other samples plated. A silicide formed on both Pd activated, boron samples, with and with out SPM cleaning and on both the unactivated and SPM cleaned phosphorus sample but not on the phosphorus sample that was Pd activated. Silicide formation on the phosphorus samples is shown in Figure 4.20. The coverage is more uniform for the longer sintering time. Silicide

66

Without Pd

With Pd

With Pd and SPM

Boron

NO PLATE

SSBC Phos

IBBC Phos

NOT TESTED

Figure 4.19: The three different test structures with three different surface treatments prior to electroless Ni plating at 90-92 C for 4 minutes. The samples were sintered at 350 C for 5 minutes and the unreacted Ni removed in a SPM. Without Pd With Pd With Pd and SPM

IBBC Phos

Figure 4.20: IBBC phosphorus diffused test structures with three different surface treatments prior to electroless Ni plating at 90-92 C for 4 minutes. The samples were sintered at 300 C for 5 minutes and the unreacted Ni removed in a SPM. coverage on both the boron samples that plated was also uniform.

4.4.4

Unreacted Ni
During the course of these experiments on planar test structures, a previously unreported

phenomenon was observed. The unreacted Ni spontaneously peeled away from the surface of the test structures upon removal from the elephant when cooled. Figure 4.21 shows a wafer that was diffused to 100 /sq with boron, Pd activated, SPM cleaned and plated with Ni at 90 C. The sample was then sintered at 300 C for 7 minutes. The picture has been taken at an angle and the semi-circular patterns are layers of Ni that are peeling away from the surface as the

67

Figure 4.21: A photograph of Ni aking off a test structure after sintering at 300 C for 7 minutes. picture is being taken. Once all the Ni has aked off, a uniform coating of Ni silicide can be observed on all areas where aking occurred. This was conrmed by SPM cleaning and sheet resistance measurements. This phenomenon typically happens on heavily phosphorus diffused samples and it only happens in areas where silicidation has been successful. The Ni was observed to curl up from the surface of the sample for at least ten minutes after being removed from the elephant after being cooled in the manner described in Section 3.3.2. The cause of the aking Ni in not known but quite clearly such behaviour could lead to poor adhesion of subsequent plated metal layers. It is difcult to observe Ni aking off 10 x 10 m2 pits, so chemically removing any unreacted Ni after sintering and prior to further metal deposition may need to be incorporated into the pit plating sequence.

4.4.5

Conclusions
Section 4.4 has examined the conditions required to form a Ni silicide on heavily phos-

phorus and boron diffused, <100> surfaces. The plating and sintering results of this investigation (from Sections 4.4.1 and 4.4.3) are summarised in Table 4.5. It is concluded that Pd activation in conjunction with SPM cleaning and high temperature Ni plating is the only surface preparation and plating sequence that will lead to Ni silicide formation on both heavily boron and phosphorus diffused surfaces simultaneously. This is the main nding of this thesis. Additionally, it has been observed during this work that one potential source of adhesion failure of electroless plated layers is Ni aking after sintering and that adhesion on pit contact IBBC cells might be improved by removal of the unreacted Ni after silicide formation.

68

Diffusion

Plating Temp 80 C 90 C 80 C 90 C 80 C 90 C 80 C 90 C

Without Pd

With Pd

Pd and SPM

Appearance of the Ni Plate Phosphorus Phosphorus Boron Boron Bronze Bronze None None Cloudy Cloudy Cloudy Cloudy Bronze Bronze None Bronze

Coverage of Ni Silicide Phosphorus Phosphorus Boron Boron 10% 80% N/A N/A 10% 10% 100% 100% 100% 100% N/A 100%

Table 4.5: Summary of results from Sections 4.4.1 and 4.4.3

4.5

Cu Plated Layers
Many of the Ni plated test structures that were made during this work were subsequently

Cu plated, so that the adhesion of the metal layers could be observed. The Cu plating method used is described in Section 3.3.1. Adhesion of plated layers was observed by conducting a tape test. A piece of commercially available, clear scotch tape is stuck to the plated surface and smoothed down to remove any air bubbles. The free end of the tape is then doubled back over the wafer and pulled off again parallel to the wafer surface. If the metal/silicon interface is more adhesive than metal/tape interface the metal will remain on the wafer. If not it will come away on the tape. This method of adhesion testing is not as rigorous as the industry standard pull test, which involves soldering a tab onto the contact and measuring the force required to pull it away from the cell. It does, however, demonstrate the relative adhesion strengths between samples, as will be shown in Section. Previous studies [5] have shown that high stresses can be encountered within AEDs and that bath additives can reduce this stress (for the case of Ni pyrophosphate baths). In the current work it was found that the adhesion of Cu layers plated to Ni layers on Si could be improved by Ni silicidation. It was also found that the Cu/Ni bond is strong but that the stress within the

69 Cu layer during deposition is so great that both the Cu and the Ni layer will spontaneously peel away from the substrate unless the Ni layer is anchored to it by the formation of a silicide at the interface.

4.5.1

Without Ni Silicide
When the test structures used in this work were plated with thin layers of Ni, the as-

plated (ie: not sintered) Ni layer was unable to be peeled away in a tape test. This was true of samples that were Ni plated with and without Pd activation and SPM cleaning steps. When Cu was plated to the thin Ni layer, however, both metal layers spontaneously peeled off the substrate surface (ie: came away from the surface and fell off without the use of any external force such as tape or drying in a stream of nitrogen). a) b)

Figure 4.22: Cu plated layers on phosphorus diffused IBBC test structures that were rst plated with Ni at a) 80 C and b) 90 C.

Figure 4.22 shows two IBBC PGD test structures that were Pd activated for 3 minutes, SPM cleaned, HF dipped and plated with Ni - sample a) at 80 C for 4 minutes and sample b) at 90 C for 3 minutes. The samples were then Cu plated at 46 C for 1 hour. The Cu layer is not at all adherent to the sample surface regardless of the plating temperature of the initial Ni layer. When tape tested, the Cu layer came away from the sample easily, with the Ni layer clearly attached to the other side of it (the Cu and the Ni are different colours). The tape tested layer was itself tape tested to see if the two layers of metal could be pulled apart, which they could not. It was concluded from this that the Ni/Cu interface is more adhesive than the Ni/Si interface. As the Cu layer becomes thicker, the internal stress is greater than the strength of the

70 Ni/Si bond and so the plated layer fails at the Ni/Si interface.

4.5.2

With Ni Silicide
To test the effect of Ni silicidation on the adhesion of subsequent AEDs of Ni and Cu,

three SSBC PGD test structures were made. One wafer was diffused between each pair of solid sources so that the diffusion would be the same on both sides of the wafer. Instead of deglazing the entire surface, however, the masking oxide was patterned photolithographically, as shown in Figure 4.23.

Figure 4.23: Cross sectional schematic of the photolithographically dened pattern used in Section 4.5.2.

An interdigitated grid pattern was formed on one side of each wafer which had a line width of 400 m with a 200 m spacing between ngers. A different pattern was formed on the other side of each wafer which consisted of 10 evenly spaced ngers with a line width 120 m and a spacing of 31 mm. Each line was 25 mm long. Photolithographically patterned IBBC BGD test structures were also made but these were not able to be Ni plated either with or without SPM cleaning after Pd activation. It is believed that this was the result of a non-optimal boron diffusion. The three, patterned, SSBC PGD samples were plated as described in Table 4.6.

The two samples that were SPM cleaned after Pd activation had to be Ni plated three times before Ni initiated on the surface. This was eventually achieved by adding NaOH and an activating dummy wafer to the Ni plating bath. With an activating dummy in the bath, other

71 samples from the same batch plated on the rst run. This illustrates the unreliable nature of electroless plating. Sheet resistance measurements were made on the grid pattern of Samples 2 and 3 at three stages during the metallization process: after oxide removal, after Ni plating and after SPM cleaning of the sintered contact. The results are shown in Table 4.7.

a)

b)

c)

Figure 4.24: Plan view of two SSBC PGD test structures that were photolithographically patterned and metallized. After the initial Ni deposition, both samples were sintered at 300 C for 10 minutes and the unreacted Ni was a) left on and b) removed in an SPM before further processing.

The sheet resistivity of the diffused layer was the same on both samples. The sheet resistivity of the Ni plated and sintered layer in series with the diffused layer was lower than Sample 1 2 3 Pd 3 mins 3 mins 3 mins SPM HF Ni 4 mins 4 mins 4 mins Sinter Temp 300 C 300 C 400 C SPM + HF

Table 4.6: Ni plating and sintering parameters for three SSBC PGD test structures with photolithographically dened contacts.

72 that of the diffused layer, indicating that Ni was indeed present. A difference in the resistivity of the silicide layer formed at each sintering temperature was not signicant in comparison to the total resistivity of the stack. A difference in the sheet resistivity was found however after removal of the unreacted Ni. This is either due to a difference in the thickness of the silicide layers or difference in the phase of the silicide or both. The sheet resistivity is different to that of both the diffused layer and the Ni layer before the SPM cleaning process. This conrms that a silicide has been formed and that the SPM cleaning process has removed the unreacted Ni. After SPM cleaning Samples 2 and 3, all three samples were Ni plated at 93 C for 2 mins and Cu plated for 4 hours. Figure 4.24 shows plan and tilted views of the resultant AEDs of Cu on a) Sample 1 and b) Sample 2. Sample 2 was dried with a nitrogen gun and tape tested prior to imaging. The bottom left hand corner of the grid and all of the thinner gridlines on the other side of the sample came away in the tape test. Sample 3 had the same appearance as Sample 2. Less metal was able to be removed in the tape tests on Sample 3 than on Sample 2. Sample 1 was not dried with the nitrogen gun as the metal is obviously not adherent to the surface. No tape test was needed for this sample because the entire grid came away during handling revealing that there was no silicide present on the wafer surface.

4.5.3

Conclusions
Plating thick, adhesive layers of electroless Cu is problematic. This is probably due

to stresses encountered within the plating layer. It can be concluded from the experiments in Section 4.5 that the Cu/Ni bond is stronger than the Ni/Si bond (where the Si <100> and heavily doped). Stress in the electroless Cu lm during plating causes adhesion failure at the Sheet Resistivity (/sq.) Sample 2 Sample 3 2.94 2.94 1.13 1.13 1.45 0.77

PGD

Ni

Silicide

Table 4.7: Sheet resistivity measurements of the various layers formed on photolithographically dened contacts. Sample 2 was sintered at 300 C and Sample 3 was sintered at 400 C.

73 Ni/Si interface. With the right processing parameters, silicidation of the Ni layer can improve the adhesion of the Cu layer to the point where it is still adherent after 4 hours of plating at 46 C. These Cu plating bath parameters are known to provide sufcient Cu deposition for the pits on a pit contact IBBC solar cell, with a spacing of 50 m, to plate together to form a contact grid.

4.6

Summary
Design of a new contact grid structure for IBBC solar cells was presented in Section

4.2.1. The potential benets of this design were presented in Section 4.2.2. It was shown that IBBC cells with a pit contact grid pattern should have a higher open circuit voltage than those with the standard grooves. Problems encountered during the electroless metallization of cells with the new grid design were presented in Section 4.2.3. The cause of the adhesion problem is identied and a possible solution developed in Section 4.3 to Section 4.5. Section 4.3 shows that Ni plated to heavily boron diffused pits without Pd can cause excessive Si migration during sintering. The use of Pd, however, results in overplating of the eld oxide. For pit contact IBBCs it was found that this could be mitigated by lower the Ni plating temperature to less than 83 . Section 4.4 shows that lowering the Ni plating temperature, however, causes Ni to fail to plate to BGD test structures and Ni silicide to fail to form on PGD test structures that are not Pd activated. On Pd activated samples, Ni will plate to either type at low and high Ni plating temperatures and a silicide will form on BGD samples but not on PGD samples. If the samples are plated with Pd and then SPM cleaned prior to Ni plating, however, both types of samples with plate and Ni silicide will form on both. Section 4.5 shows that when Cu is plated to a Ni layer where a silicide has not been formed or silicidation has not been successful, both metal layers peel away from the substrate. This shows that a lack of silicide in the phosphorus contacts may be the cause of adhesion problems in pit contact IBBCs. It does not however, explain the adhesion problems with the boron contacts. Section 4.4.4 shows that when the unreacted Ni is left in the contact after silicidation, there is a potential for it to ake

74 off, which could be causing adhesion problems on both contacts. Adding two SPM cleaning steps - one after Pd plating and one after Ni sintering - should improve the adhesion of the electroless metal layers on pit contact IBBC solar cells.

Chapter 5 Conclusion and Future Work

In this study, a new contact design for IBBC solar cells is introduced and examined. The purpose of the new design is to reduce the volume of heavily diffused material within the cell, thereby reducing its contribution to Jo . A signicant reduction in the volume of heavily diffused material can be achieved by replacing the trench-shaped grooves of an IBBC solar cell with lines of inverted pyramids, otherwise known as pits. It is shown here that this modication to the existing contact design could potentially lead to a 25-35% reduction in Jo and a 10 mV increase in open circuit voltage. It is also shown in this work that it is difcult to metallize pit contact IBBC solar cells with the standard IBBC electroless metallization scheme. This is because pit contacts suffer from initiation and adhesion problems that do not affect cells with laser scribed grooves. Initiation problems are probably due to the reduced area of the plating surface. This aspect of the metallization scheme was not examined in this work. This thesis shows that poor silicidation is the main factor affecting adhesion. In order to form an electroless Ni silicide on the heavily boron and phosphorus diffused Si present in an IBBC device, Ni plating must rst be initiated on the diffused surfaces. The factors effecting Ni initiation were found, experimentally, to be: The type of the dopant atoms at the substrate surface - Ni was found to have a lower nucleation density on boron diffused samples than on phosphorus diffused samples.

76 This can lead to lumpy Ni deposits or no deposits at all, depending on the plating temperature. Pd activation - the nucleation density on p-type surfaces increases with activation leading to more uniform Ni deposits and deposits forming on p-type material at lower plating temperatures. Once the surface is plated, several factors may still inuence the silicide formation. In the temperature range 250o C - 450o C the main factors effecting the silicide formation on p- and n- diffused surfaces were found to be: Morphology of the Ni Plate - deposits with a low nucleation density were found to change the morphology of the Ni/Si interface when sintered. Pd Activation - this was found to inhibit silicidation on n-type surfaces but not on p-type surfaces, regardless of the plating temperature. The Ni Plating Bath Temperature - a silicide was unable to be formed on unactivated n-type surfaces that were plated at 80o C even though Ni was deposited on the surface. A silicide was found to form on unactivated n-type surfaces when the Ni plating bath temperature was increased to 90o C. Pd Cleaning - inclusion of a SPM cleaning step after Pd activation resulted in silicide formation on both p- and n-type surfaces for a Ni plating temperature of 90o C. Pd Sintering - if the Pd is sintered prior to this cleaning step, silicide coverage is greatly reduced on the n-type surfaces. It was also found that it is possible for the unreacted Ni to spontaneously ake off planar samples after Ni silicidation. It is possible that this potential adhesion problem only affects planar samples and does not occur on pit contacts but this would be difcult to verify. This phenomenon was not observed on all samples and its cause is unknown. It was only observed to occur on areas where Ni silicidation had been successful however, so SPM cleaning prior to

77 the second Ni plate would negate its effect whilst still retaining the Ni silicide layer. Including such a step in the metallization sequence, however, means that adhesion between the second Ni layer and the silicide needs to high. Adhesion of the plated layers in this work was studied by electroless Cu plating. It was shown that the adhesion of the second Ni plated layer is signicantly improved by rst forming a silicide at the Ni/Si interface. The properties, not just the presence, of the underlying silicide also affected the adhesion of the plated layers. Adequate adhesion of the second Ni plated layer, and hence of the Cu layer, were able to be obtained for a Ni sintering time and temperature of 10 minutes and 350o C, respectively. This thesis has shown that electroless metallization of pit contacts IBBCs is problematic. Many issues pertaining to Ni silicide formation were identied and the rectication of these issues was shown to improve adhesion of Ni and Cu plated layers on test structures. It was shown that a metallization scheme that might be able to successfully plate pit contact IBBC solar cells is the same as the standard scheme but it includes two SPM cleans. The rst clean follows Pd activation to allow the formation of Ni silicide on both p- and n- type contacts. The second clean follows Ni silicidation to remove any unreacted Ni that may be spontaneously peeling from the silicide surface. The next step of this investigation would be to implement the new metallization scheme on pit contact IBBC cells. If such cells can be fabricated by electroless plating, the most likely problem to arise is shunting of the base grooves to the emitter due to the increased silicidation temperature. Hence, a study of Ni silicidation times and temperatures could be conducted to determine the minimum temperature required for adequate adhesion. Contact resistance may also be an issue in pit contact cells due to the reduced contact area. A comparison of the contact resistance of plated pit and groove type contacts would also make an interesting study. It might be instructive to analyse the deposition from the Pd immersion solution on heavily diffused n-type and p-type Si. It is possible that the different surface dopant concentrations result in Pd layers with differing compositions. Determining the composition at the surface

78 before and after the SPM clean (after the activation step) may provide insight into why Ni silicide does not form on Pd activated, heavily phosphorus diffused Si but is enhanced after Pd activation and SPM cleaning. It is clear from the literature that the formation of Ni silicide from AEDs of Ni has not been well studied. There is much scope for XRD analysis and correlation of sheet and contact resistances of Ni silicides formed in this way. Such a study could also incorporate an investigation of the selectivity of various etchants on the phases of the silicides formed.

Appendix A SEM and EDS

The pit contact solar cells plated in Section 4.3 were imaged using a scanning electron microscope (SEM) and analysed by energy dispersive spectroscopy (EDS). Figure A.1 shows typical X-ray energy spectrums for a typical AED of Ni deposited from a Ni bath at 80o C. The black spectrum was measured at a lower magnication than the grey one, which yields a large Si signal and a small Ni and P signal. A larger signal can be generated from the smaller peaks by reducing the scanned area (increasing the magnication). This shows that it is not easy to use EDS for quantitative measurements. It is a useful qualitative technique, however, for conrming the presence or absence of different materials. The SEM/EDS system can also be used to make qualitative X-ray energy maps. Maps were made of Ni plated to pits on a pit contact IBBC cell. A secondary electron image (SEI) showing the topography of the mapped area is shown in Figure A.2 a). The Si, Ni and P maps are shown in Figures A.2 b), c) and d), respectively. Maps of pits on the same sample are shown in Figure A.3 after sintering and RCA2 cleaning. It would appear from this measurement that all the Ni has been removed by the RCA2 solution. It is possible, however, that the Ni silicide layer makes up such a small proportion of the interaction volume of the beam in the sample that it can not be detected by this technique.

80

Figure A.1: X-ray spectrum generated on a Ni plated pit at low magnication (black spectrum) and at high magnication (grey spectrum).

a)

b)

c)

d)

Figure A.2: X-ray maps of a Ni plated pit; a) the SEI image of the mapped area, b) the Si signal, c) the Ni signal and d) the phosphorus signal.

a)

b)

c)

d)

Figure A.3: X-ray maps of a pit where the Ni has been sintered and the unreacted Ni removed with RCA2; a) the SEI image of the mapped area, b) the Si signal, c) the Ni signal and d) the phosphorus signal.

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