Applied Surface Science 266 (2013) 1–4

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Crystalline silicon solar cells with micro/nano texture

Dimitre Z. Dimitrov a,∗ , Chen-Hsun Du a,b
a
Green Energy & Environment Research Labs, Industrial Technology Research Institute (ITRI), Chutung, Hsinchu, Taiwan
b
National Tsing Hua University (NTHU), Institute of NanoEngineering and MicroSystems, Hsinchu, Taiwan

a r t i c l e i n f o a b s t r a c t

Article history: Crystalline silicon solar cells with two-scale texture consisting of random upright pyramids and surface
Received 26 April 2012 nanotextured layer directly onto the pyramids are prepared and reflectance properties and I–V charac-
Received in revised form 12 October 2012 teristics measured. Random pyramids texture is produced by etching in an alkaline solution. On top of
Accepted 15 October 2012
the pyramids texture, a nanotexture is developed using an electroless oxidation/etching process. Solar
Available online 23 October 2012
cells with two-scale surface texturization are prepared following the standard screen-printing technol-
ogy sequence. The micro/nano surface is found to lower considerably the light reflectance of silicon. The
Keywords:
short wavelengths spectral response (blue response) improvement is observed in micro/nano textured
Crystalline silicon solar cell
Texturization
solar cells compared to standard upright pyramids textured cells. An efficiency of 17.5% is measured for
Nano structure the best micro/nano textured c-Si solar cell. The efficiency improvement is found to be due to the gain in
Antireflection both Jsc and Voc .
© 2012 Published by Elsevier B.V.

1. Introduction could be also incorporated on microtextured silicon surfaces (for

The silicon surfaces functionality increasing is of high impor-
tance for various applications. One particular approach for
implementing multifunctionality is the formation of two-scale
structured surfaces, as for instance micron-scale structured sur-
faces that also possess nanoscale roughness. These surfaces have
superhydrophobic self-cleaning (after an additional surface fluo-
rination), photoluminescence and antireflection properties. There
are several methods for preparation of two scale micro/nano sur-
face structures, the metal-assisted etching [1] being one of the
simplest and effective. Superhydrophobic surface was obtained by
two-scale roughness prepared by this simple silicon etching tech-
niques as described in [2]. Micron-scaled pyramid structure was
obtained by anisotropic KOH etching and nanostructure onto these
pyramids by metal-assisted etching in HF/H2 O2 aqueous solution.
Furthermore [3] the potential application of these two-scale rough
surfaces formed by the metal-assisted etching of micron-sizes
pyramid texture in antireflection and light-trapping properties
was highlighted. Silicon solar cells texturization is important
for the reflection losses reduction, increased light absorption as
well as for an overall conversion efficiency improvement. More-
over, surface texture with nano-dimensions [4,5] is proven to be
effective for broadband reflection suppression. The nanotextures
∗ Corresponding author at: Green Energy & Environment Research Labs, Industrial
Technology Research Institute (ITRI), 195 Sect. 4, Chung Hsing Rd., Bldg. 51, R.1144,
Chutung, Hsinchu, Taiwan. Tel.: +886 3 5915987; fax: +886 3 5822157.
E-mail address: dzd1955@gmail.com (D.Z. Dimitrov).
example, pyramids etched mono crystalline silicon) to improve
even further the solar cell devices functionality [6]. Indeed on
the micro/nanostructured two scale surfaces a weighted light
reflectance of 3.8% in the 300–1000 nm wavelength was measured
[3]. Electroless stain etching in HF/HNO3 [7] and HF/Fe(NO3 )3 [8]
solutions, as well as electrochemical etching [9,10] was further
employed for formation of nanoporous layer on pyramids pre-
textured wafers. The prepared solar cells using these methods as
well as metal-assisted electroless etching however possess rather
low conversion efficiency [11].
In this paper a relatively simple method for producing a hier-
archical (micro/nano) structure on the crystalline silicon surface is
presented. The preparation method is using only electroless wet
chemistry processes at room temperature. Solar cells with this
multi-scale surface structure incorporated were prepared, by using
the standard screen-printing process, and their performance mea-
sured.
2. Experimental
The p-type CZ c-Si (1 0 0) wafers with thickness of 180–240 ␮m
and resistivity 3–6  cm were fabricated to solar cells using the
processing sequence shown in Fig. 1. A texturization with micron-
sized random pyramids was performed in KOH-IPA solution at a
temperature 80 ◦ C for 45 min. The textured wafers were cleaned in
HCl:H2 O2 :H2 O (HPM) mixture at 80 ◦ C for 10 min and then wafer
surfaces H-terminated in diluted HF. The nanotexture onto the ran-
dom pyramids was formed by two-step process consisting of an
electroless treatment in an acidic aqueous solution of Na2 S2 O8 and

0169-4332/$ – see front matter © 2012 Published by Elsevier B.V.

http://dx.doi.org/10.1016/j.apsusc.2012.10.081
2 D.Z. Dimitrov, C.-H. Du / Applied Surface Science 266 (2013) 1–4

diffusion and phosphor-silicate glass (PSG) removal in diluted HF

Damage-etched c-Si was measured to be approximately 80 /sq. After PECVD deposi-
tion of a SiNx passivation and anti-reflection layer on the front side
Random pyramids texturization of the wafers, silver pattern contact and aluminum back surface
field were formed by using screen-printing and co-firing in a belt
IR furnace. The total reflectance of the texturized wafers and the
Nanotexturization solar cells was measured with a Hitachi U-3010 spectrophotome-
ter equipped with an integrating sphere, in the wavelength range
POCl3 diffusion 300–900 nm. The wafers surface morphology was studied by using
scanning electron microscopy (SEM) technique. For SEM (JEOL JSM-
6500F) measurements square pieces of size 20 mm × 20 mm were
PSG etching prepared using laser cutting. The finished solar cells performance
was analyzed by reflectance, quantum efficiency and I–V measure-
PECVD SiNx AR coating ments. The solar cells current-voltage (I–V) parameters assessment
was performed at 25 ◦ C under AM 1.5 G solar spectrum using a solar
simulator Wacom WXS-220S-L2 with power density of 1000 W/m2 .
Contacts screen printing
3. Results and discussion
Contacts co-firing
3.1. Surface structures
Laser edge isolation
Micron-sized surface pyramids were formed by anisotropic
etching of silicon wafers with (1 0 0) orientation in an aqueous
Fig. 1. Processing sequence for the preparation of crystalline silicon solar cells with KOH-IPA solution. The treatment in Na2 S2 O8 activated by AgNO3
micro/nano surface texturing.
electroless solution and following 2 min etching in HF/H2 O2 /H2 O
resulted in production of a nanostructure directly onto the pyra-
AgNO3 (pH < 3) for 6 min followed by an etching in an aqueous solu- mids covered silicon surface. The hierarchical (nanotexture on
tion of HF and H2 O2 for 2 min. Both treatments were performed at microtexture) structure prepared in the above described tech-
room temperature on 125 cm × 125 cm pseudo square wafers. The niques is shown in Fig. 2 as plan-view as well as cross-sectional
electroless solution preparation details are described in [12]. The SEM images. The pyramids surface is covered uniformly with
average sheet resistance after the phosphorous oxychloride (POCl3 ) fine nanoporous layer. The pores lateral dimensions are less than

Fig. 2. (a and b) Plan-view SEM images with different magnification of Si pyramid surfaces covered with nano-texture, (c) nano-texture on pyramid surface (high magni-
fication), (d) cross-sectional SEM image, of the multi-scale surface texture. The inset in (b) shows higher magnification (100,000×) image of the nano-texture (scale bar –
100 nm).
 D.Z. Dimitrov, C.-H. Du / Applied Surface Science 266 (2013) 1–4 3

60
100
c-Si, pyramids (macrotexture)
50 c-Si (after nanotexturization)

80
40
Reflection (%)

E Q E (%)
30
60 c-Si/pyramids
c-Si/pyramids/nanotex
20

40
10

0 20
300 400 500 600 700 800 900
200 400 600 800 1000 1200
wavelength (nm)
wavelength (nm)
Fig. 3. Light reflection of silicon surfaces with pyramids texture and pyramids/nano
two-scale texture. Fig. 5. External quantum efficiency spectra of solar cells with random pyramids
texture and pyramids/nanotexture.

100 nm, with a dept less than 200 nm. Surface micro/nano com-
bined two-scale structures attracted increasing interest due to
the various potential applications. On silicon these structures
possess multi-functionality with super hydrophobic and antireflec-
tive properties suitable for improving the reliability and conversion
efficiency of the solar cells.
3.2. Surface reflectance and quantum efficiencies
The surface reflectance of silicon wafers with random upright
pyramids texture and nano/micro textured as well as the
reflectance evolution of solar cells textured with hierarchical
texture (nanotexture on macro/pyramids texture) after the consec-
utive preparation steps according to the standard screen-printing
preparation process for solar cells are shown in Figs. 3 and 4 respec-
tively. Over the measured interval (300–900 nm) of wavelengths
the reflectance of two-scale pyramids/nanotexure surface is below
3% – significantly lower than the reflectance of the random pyra-
mids textured surface. The reflectance of the two-scale textured
solar cells is lower especially at shorter wavelengths. The sup-
pressed reflectance implies that the absorption of the sunlight will
stability. Mechanical testing [13] also revealed good resistance of
such kind of surfaces.
Fig. 5 presents the measured external quantum efficiency
(EQE) of solar cells with random pyramids texture and pyra-
mids/nanotexture. The estimated internal quantum efficiency
(IQE), and reflectance of solar cells with random pyramids texture
and pyramids/nanotexture are compared in Fig. 6. The IQE spec-
tra show improved blue response (wavelength range 300–450 nm)
of the pyramids/nanotexture textured solar cell, suggesting that
passivation properties are not disturbed by the presence of the
nanostructured surface layer.
3.3. I–V measurements on solar cells
The I–V parameters measured on solar cells with hierarchi-
cal texturing as well as cells with conventional random upright
pyramids texture for comparison are presented in Table 1. The
100
I Q E, Reflectance (%)

be improved. The optimized reflectance of the cells with hierarchi-

80
cal texture combined with the self-cleaning capability single out
this approach as very attractive for solar cells with enhanced func-
tionality. The solar cell reflectance is changed a little during the 60 sc-Si/pyramids
high-temperature processing suggesting the nano/micro texture sc-Si/pyramids/nanotexture

40
60
c-Si
c-Si/pyramids textured 20
50 nanotextured c-Si/pyramids
after emitter formation
Reflection (%)

40 after SiNx ARC deposition 0

300 400 500 600 700 800 900

30 wavelength (nm)

Fig. 6. Internal quantum efficiency and reflectance of solar cells with random pyra-
20 mids texture and pyramids/nanotexture.

10 Table 1
I–V parameters of pyramids textured and two-scale textured c-Si cells.

0 Cell type Voc (mV) Jsc (mA/cm2 ) FF (%)  (%)

300 400 500 600 700 800 900
Reference average 615 33.9 77.9 16.3
wavelength (nm)
Reference best 615 33.9 79.9 16.7
Micro/nano texture average 622 35.6 77.0 17.1
Fig. 4. Light reflection evolution after different stages of solar cell device prepara-
Micro/nano texture best 623 35.5 79.3 17.5
tion.
4 D.Z. Dimitrov, C.-H. Du / Applied Surface Science 266 (2013) 1–4
Fig. 7. Plan-view SEM images of nanotexture on pyramids textured c-Si (a) and (b and c) inverted pyramids formation after KOH etch-back for different time. Etch-back time
of (c) was 2 times longer than (b). Scale bars – 1 ␮m.
conventional cells were prepared with a 55 /sq emitter, which is
typical for solar cells with diffused junction. The open circuit volt-
age (Voc ) and the short circuit current (Jsc ) are both improved in
the solar cells with hierarchical surface texture. The nanoporous
structure with relatively shallow pore depth and the emitter with
reduced doping (80 /sq compared to 55 /sq) lead to improved
blue-response and the gain in Jsc and Voc in the two-scale textured
cells. On the best cell an efficiency of 17.5% was measured proofing
the feasibility of the two-scale structure approach for incorporation
in high-efficiency crystalline silicon solar cells. The improvement of
these parameters reflects also on the efficiency being with 0.8% in
average higher for the nano/micro textured solar cells. These results
are similar to the recently published [14] on small form factor cells
prepared by using multi-scale texturing on FZ silicon.
3.4. Formation of inverted pyramids nanostructure on random
upright pyramids texture
Fig. 7 shows a plan view SEM images for samples with nan-
otexture on pyramids texture etched in HF/H2 O2 /H2 O solution for
prolonged time of 4 min as well as the surface morphology evo-
lution after nanoporous layer etch-back for 2 different times of
6 min and 12 min in diluted alkaline solution. The samples with-
out etch-back possess round shaped pores onto the pyramids with
pore diameter less than 200 nm. The pore dimensions depend on
the etching time in the HF/H2 O2 /H2 O solution. After an etch-back
in diluted KOH however the nanoporous surface layer dissolved
and square base random inverted pyramids are formed. The size of
these pyramids was below 500 nm. With longer etch-back time the
size of the inverted pyramids increase up to 1 ␮m. Therefore, finally
a complex structure consisting on random square based inverted
nano pyramids onto the surface of random upright micro pyramids
is formed.
4. Conclusions
Nanostructured silicon surfaces onto random upright pyramids
microtexture were prepared by electroless treatment in activated
Na2 S2 O8 solution followed by etching in HF/H2 O2 /H2 O. The silicon
surfaces manufactured in this way showed low light reflection, an
improved short wavelength spectral response and enhanced solar
cells efficiency. The results confirm the feasibility of two-scale sur-
face texture for further incorporation in high-efficiency crystalline
silicon solar cells.
Acknowledgements
The authors would like to acknowledge the financial support
from the Bureau of Energy of Ministry of Economics, Taiwan.
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