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Energy Procedia 33 (2013) 70 – 75

PV Asia Pacific Conference 2012

Lightly Doped Emitters for High Efficiency Silicon Wafer

Solar Cells
Kishan Devappa Shettya,*, Matthew B. Borelanda, Vinodh Shanmugama,b,
Jessen Cunnusamya, Chun-Kwei Wuc, Scott Iggoc, Homer Antoniadisc
a
Solar Energy Research Institute of Singapore, National University of Singapore, 7 Engineering Drive 1, Block E3A,
Singapore 117574, Singapore
b
Department of Electrical and Computer Engineering, National University of Singapore, 4 Engineering Drive 3, Block E4,
Singapore 117576, Singapore
c
MicroCircuit Materials, DuPont Electronics and Communications.

Abstract

Tube diffusion is the de facto industry standard for emitter formation for silicon wafer solar cells. In this paper, we
report on optimised dopant profiles to produce a lightly doped emitter (LDE) with a lower surface dopant
concentration. Solar cells are fabricated with a LDE and achieve a significant gain in open-circuit voltage (Voc) due to
a reduced front surface and emitter recombination. The POCl3 tube diffusion process is optimised by introducing a
pre-oxidation and multi-plateau drive-in during the diffusion process. Using the optimised process, the surface dopant
concentration of our tube diffused n+ emitter is reduced from 4.5×1020 to 2.5×1020 atoms/cm3 for a ~70 Ohms/sq
emitter. An increase of 4 mV in Voc, 0.2 mA/cm2 in short-circuit current Jsc and 0.2% absolute increase in efficiency
is achieved for solar cells using a LDE compared to solar cells with our standard emitter profile. The average fill
factors for the standard and LDE batches are above 79%, suggesting the Ag paste (DuPont Solamet PV17F) used in
this work had no issues in contacting the lower surface concentration of the LDE.

© 2013
© 2013ThePublished by Elsevier
Authors. Published Ltd. Selection
by Elsevier and/or
Ltd. Open access peer-review
under CC BY-NC-ND under responsibility of Solar Energy
license.
Researchand
Selection Institute of Singapore
peer-review (SERIS) ofNational
under responsibility University
Solar Energy ofInstitute
Research Singapore (NUS). The
of Singapore PV Asia
(SERIS) Pacific
– National
University
Conference of Singapore
2012 was(NUS). Theorganised
jointly PV Asia Pacifi
by cSERIS
Conference
and 2012
the was jointly
Asian organised byIndustry
Photovoltaic SERIS and the Asian
Association
Photovoltaic
(APVIA). Industry Association (APVIA)

Keywords: Lightly doped emitters (LDE); POCl3 diffusion; diffusion barrier; phosphorus silicate glass (PSG).
________________________________________________________________________________________________________

* Corresponding author. Tel: +65 6516 1544; fax: +65 6775 1943
E-mail address: kishan.shetty@nus.edu.sg

1876-6102 © 2013 The Authors. Published by Elsevier Ltd. Open access under CC BY-NC-ND license.
Selection and peer-review under responsibility of Solar Energy Research Institute of Singapore (SERIS) – National University of Singapore
(NUS). The PV Asia Pacific Conference 2012 was jointly organised by SERIS and the Asian Photovoltaic Industry Association (APVIA)
doi:10.1016/j.egypro.2013.05.041
 Kishan Devappa Shetty et al. / Energy Procedia 33 (2013) 70 – 75 71

1. Introduction

Lightly doped emitters (LDE) are an important aspect to improve the efficiency of silicon wafer solar
cells because a highly phosphorus doped region introduces crystalline defect states that increase the
electron-hole recombination thereby decreasing the s blue response (i.e., the short-circuit current
density Jsc) as well as the open-circuit voltage Voc. Another unwanted effect is the increase in photon
absorption near the front surface due to band-gap narrowing [1]. On the other hand, a lightly doped
emitter has a lower phosphorus dopant concentration near the cell's front surface which can be well
passivated, reducing the surface recombination and thus improving the Voc and Jsc [2, 3].

2. Experimental details

The complete cell fabrication process flow is shown in Fig. 1. Six inch wide pseudo-square <100> p-
type Cz mono-Si wafers with a bulk resistivity of 0.5- and a thickness of 150-1 as
substrates. The main variation between the three process flows was the emitter formation method. All the
other processes were identical, apart from some process optimisation for the co-firing step. After a
standard saw damage removal and texturing process, the wafers were diffused in different batches in a
standard industrial tube diffusion furnace (Tempress, TS81004). After phosphorus silicate glass (PSG)
removal using dilute HF, a 70 nm SiNx layer was deposited on the emitter surface at 450ºC in an inline
plasma reactor (Roth & Rau, SiNA-XS) for front side surface passivation and anti-reflection coating
(ARC). A standard industrial screen printing process was applied using silver paste for the front contact
(DuPont, PV17F) and Al paste for the rear contact (Cermet Solus 6214), on a standard screen print line
(DEK, PVP1200). Finally the samples were co-fired in an industrial inline fast firing furnace (Despatch,
UltraFlex). One-Sun I-V measurements under standard testing conditions (Aescusoft, SolSim-210) were
used to extract the one-Sun I-V parameters of all finished solar cells.

RCA1 clean

Saw damage removal

KOH with IPA texturing

RCA2 and HF clean

Standard diffusion LDE-1 diffusion LDE-2 diffusion

PSG removal (HF)

Dry oxidation

PSG removal (HF) SiO2 removal (HF)

Laser edge isolation

SiN deposition (Front ARC)

Screen printing: front Ag & rear Al (no bus bars)

Co-firing

Fig. 1. Process flow for the standard emitter and LDE diffusion batches. The dashed boxes highlight the steps that were different in
the three process flows.

The effective minority carrier lifetime ( eff), emitter saturation current density (J0e) and implied voltage
(Voc) were measured on one selected sample from each diffusion batch. The samples had a n+pn+ structure
passivated on each side by a SiNx film and fired using the same firing profile as used for the solar cell
processing. The results are summarised in Table 1. Low recombination emitters are especially relevant in
high-efficiency Cz Si solar cells where high Voc is required [4]. To obtain high Voc, the emitter saturation
current density J0e should be as small as possible [5]. As can be seen in Table 1, the J0e for the LDEs were
72 Kishan Devappa Shetty et al. / Energy Procedia 33 (2013) 70 – 75

lower due to better surface passivation and reduced surface dopant concentration when compared to the
standard emitter.

Table 1. Results of carrier lifetime and saturation current density for selected wafers of each emitter type.
Sample name Diffusion recipe Effective carrier lifetime Emitter saturation current Implied voltage Voc
eff (μs) density J0e (fA/cm2) (mV)
Cell 6 Standard emitter 38 403 619
Cell 28 LDE-1 50 266 624
Cell 8 LDE-2 55 193 627

3. Results and discussion

A lightly doped emitter was achieved by fine-tuning the diffusion process to result in a lower surface
dopant concentration. In this work, a pre-oxidation before phosphorus silicate glass (PSG) deposition was
combined with a multi-plateau drive-in, using limited source diffusion techniques to reduce the surface
dopant concentration with minimal impact on the sheet resistance. Our standard diffusion recipe achieved
a sheet resistance of 70 Ohms/sq using a PSG deposition at 810°C and subsequent drive-in at 830°C. The
first LDE approach (LDE-1) added an in-situ pre-oxidation before the PSG deposition step, and a multi-
level drive-in plateau. This oxide layer acts as a diffusion barrier [6], minimising the amount of
phosphorus diffusion into silicon. In addition, the oxidation creates self-interstitials at the surface of the
silicon to reduce the diffusion rate of phosphorus [7]. For the second LDE approach (LDE-2), two
separate thermal processes were used: an initial diffusion to produce a 120 Ohms/sq emitter, followed by
a separate oxidation/drive-in after PSG removal. The active dopant profiles for standard emitter, LDE-1
and LDE-2 are shown in Fig. 2. It can be seen that the peak dopant concentration for the SERIS standard
PL-70 recipe is 4.5×1020 cm-3. The LDE approaches reduced the surface concentration to 2.5×1020 cm-3
for the LDE-1 method and 1.8×1020 cm-3 for the LDE-2 method. One-Sun I-V parameters of the solar cells
processed using standard and LDEs are shown in Fig. 4. The batch average efficiency for LDE-1 batch
increased by 0.2% absolute compared to the batch average efficiency for the standard emitter solar cells.
The main contribution for efficiency improvement comes from the gain in Voc, which increased by 4 mV,
and the gain in Jsc, which increased by 0.2 mA/cm2 for the LDE-1 batch. The Voc increase can be
attributed to a reduced emitter saturation current density (J0e) resulting from the different active dopant
profile and a better surface passivation enabled by the lower surface dopant concentration. The average
fill factors for the standard and LDE-1 batches were above 79%, indicating that the Ag paste had no
issues in contacting the lower surface concentration of the LDE. For the LDE-2 batch, the voltage
improvements were similar to the LDE-1 batch and only a small drop in FF was observed mainly due to
the relatively lower surface concentration. In addition, there was a drop in Jsc, which is thought to be due
to the deeper junction for LDE-2 (see Fig. 2) resulting from the oxidation drive-in [8]. The junction
depths of standard emitter and LDE-1 diffusion profiles were about 0.25 μm whereas it is more than 0.4
μm for the LDE-2 profile, which explains the lower current. The champion cell result from each batch is
shown in Table 2. In Fig. 5, the internal quantum efficiency (IQE) of a typical solar cell from each batch
is shown. As seen, the LDE-1 approach using the LDE-1 diffusion recipe has an improved IQE across the
majority of the wavelength range, especially in the shorter wavelength region, demonstrating both surface
and bulk improvements due to reduced surface dopant concentration. The final sheet resistances for all
the emitters were in the range of 70-75 Ohms/sq, as shown in Fig. 3.
 Kishan Devappa Shetty et al. / Energy Procedia 33 (2013) 70 – 75 73

21
10
Standard emitter
LDE-1
20
10 LDE-2

[atoms/cm ]
3
19
10

18

D
10

17
10
0.0 0.1 0.2 0.3 0.4 0.5
Junction depth [μm]
Fig. 2. Active dopant profiles for the standard and LDE diffusion process, as determined by electrochemical capacitance voltage
(ECV) profiling.

0 59.0
0 59.0 330 30 59.0 0
62.0 62.0 330 30 62.0
330 30 65.0
65.0 65.0 68.0
68.0 300 60 68.0 71.0
300 60 71.0 71.0 300 60
74.0 74.0
74.0 77.0
77.0 77.0 80.0
80.0 270 90 80.0 270 90
270 90
Units: Ohms/sq Units: Ohms/sq
Units: Ohms/sq
240 120
240 120 Min 240 120
72.3 Min 58.2 Min 67.1
Max 79.1 210 150 Max 72.0 Max 76.3
210 150 180 210 150 Ave 71.6
Ave 75.5 Ave 68.1 180
180 Std dev 2.0 Std dev 3.3 Std dev 2.1
(a) Standard emitter (b) LDE-1 (c) LDE-2

Fig. 3. Sheet resistance of standard and LDE for various diffusion batches.

640 Standard Standard

LDE-1 39 LDE-1
[mA/cm ]

LDE-2 LDE-2
2

636
[mV]

38

632
oc

36
sc

628 35
Standard LDE-1 LDE-2 Standard LDE-1 LDE-2

Standard 18.8 Standard

81 LDE-1 LDE-1
LDE-2 18.4 LDE-2
80

78 18.0

77 17.6
Standard LDE-1 LDE-2 Standard LDE-1 LDE-2

Fig. 4. One-Sun I-
I V parameters for the standard and LDE batches.
74 Kishan Devappa Shetty et al. / Energy Procedia 33 (2013) 70 – 75

Table 2. Summary of batch average solar cell results for the two SERIS LDE approaches compared to the SERIS standard process.
Diffusion recipe Jsc (mA/cm2) Voc (mV) FF (%) Efficiency (%)
Standard emitter 36.3 628 79.2 18.1
LDE-1 36.5 632 79.1 18.3
LDE-2 35.8 632 78.5 17.8

100
90
IQE, Reflectance [%] 80
70
IQE (Standard)
60
IQE (LDE-1)
50
IQE (LDE-2)
40
Reflectance (Standard)
30
20
10
0
400 600 800 1000
Wavelength [nm]
Fig. 5. IQE results for the standard emitter and LDE batches

4. Conclusion

A lightly doped emitter (LDE) was achieved using the POCl 3 diffusion process and significant
improvements in Voc and Jsc were observed leading to increased solar cell efficiency for LDE when
compared to the standard emitter. These gains are realised by a simple modification of the diffusion
recipe without the need to use additional processes typically applied to achieve similar results on tube
diffused emitters. An absolute increase of 0.2% in cell efficiency was made possible with a gain of 0.4
mV in Voc and 0.2 mA/cm2 in Jsc. This was achieved due to the increase in overall blue response and
better surface passivation for the LDE-1 approach. The LDE-2 approach also demonstrated a Voc gain, but
had a current drop of 0.6 mA/cm2 which was attributed to the deeper emitter formed by the separate
oxidation drive-in process used for this approach. It is expected that further optimisation of the LDE-1
approach should provide additional improvements in the solar cell efficiency.

Acknowledgements

The authors would like to thank their colleagues from the Silicon Photovoltaics Cluster of the Solar
Energy Research Institute of Singapore (SERIS) for their assistance in sample processing and
measurements. SERIS is sponsored by the National University of Singapore (NUS)
National Research Foundation (NRF) through the Singapore Economic Development Board (EDB).

References

[1] Brammer T, Zastrow U, Stiebig H. Analysis of phosphorus doped emitter profiles of multi-crystalline silicon solar cells.
Proc. 17th European Photovoltaic Solar Energy Conf., Munich, Germany; 2001, pp. 22-26.
 Kishan Devappa Shetty et al. / Energy Procedia 33 (2013) 70 – 75 75

[2] photovoltaic metallization for lightly doped emitter solar cells Technical Data Sheet, February
2012.
[3] Mikeska KR, Carroll AF, Hanna LG, Lewittes ME, Li Z, Liang L, Meisel A, Scardera G, Subramoney S, VerNooy PD. Thick
film pastes for contacting homogeneous lightly doped n-type emitters enabling high blue right response. Proc. 27th European
Photovoltaic Solar Energy Conf., Messe Frankfurt, Germany; 2012, pp. 1717-1721.
[4] Komatsu Y, Galbiati G, Lamers M, Venema P, Harris M, Stassen AF, Meyer C, van den Donker M, Weeber A. Innovative
diffusion processes for improved efficiency on industrial solar cells by doping profile manipulation. Proc. 24th European
Photovoltaic Solar Energy Conf., Hamburg, Germany; 2009, pp. 1063-1067.
[5] Vázquez C, Alonso J, Vázquez MA, Caballero LJ, Romero R, Ramos-Barrado JR. Efficiency of commercial Cz-Si solar cell
with a shallow emitter. Materials Science and Engineering B 2010; 172(1): 43-9.
[6] Ferrada P, Harney R, Wefringhaus E, Lossen J, Meyer K. Micro selective emitters. Proc. 24th European Photovoltaic Solar
Energy Conf., Hamburg, Germany; 2009, pp. 133-136.
[7] Hu SM. Kinetics of interstitial supersaturation and enhanced diffusion in short - time/low - temperature oxidation of silicon.
J. Appl. Phys. 1985; 57:4527.
[8] Prajapati V, Horzel J, Choulat P, Janssens T, Poortmans J, Mertens R. Oxidation enhanced diffusion for screen printed silicon
solar cells. Proc. 38th IEEE Photovoltaic Specialists Conf., Austin, Texas, USA; 2012, pp. 1089-1093.