Antireflection properties and solar cell application of silicon nanostructures

Huihui Yue, Rui Jia,a兲 Chen Chen, Wuchang Ding, Yanlong Meng, Deqi Wu, Dawei Wu,
Wei Chen, Xinyu Liu, Zhi Jin, Wenwu Wang, and Tianchun Ye
Institute of Microelectronics, Chinese Academy of Sciences, Beijing 100029, China
共Received 23 December 2010; accepted 21 April 2011; published 19 May 2011兲
Silicon nanowire 共Si NW兲 arrays were fabricated on polished and pyramids textured
mono-crystalline Si 共mc-Si兲 using an aqueous chemical etching method. The Si NWs and a hybrid
texture of NWs and pyramids both show strong anti-reflectance properties in the wavelength region
of 300–1000 nm, with the minimum average reflectance of 2.52% and 8%, respectively. The above
two nanostructures were fabricated on mc-Si solar cells with the area of 125⫻ 125 mm2. Then the
influences of Si NWs and hybrid textures on the performances of mc-Si solar cells created using
different fabrication processes were analyzed by internal quantum efficiency measurement and by
systematical comparisons of efficiency, filling factor, open circuit voltage and short-circuit current.
Passivation is found to be essential for the hybrid textured solar cells, and the average open circuit
voltage can be improved by 7% after a passivation layer was deposited. The short circuit current
could be increased when Si NWs were fabricated on a substrate with an initial PN junction. © 2011
American Vacuum Society. 关DOI: 10.1116/1.3591344兴

I. INTRODUCTION ished Si show a significantly low reflectance 共R兲 of 2.53% in

Surface antireflection techniques are important for perfor-
mance enhancement of many optical devices such as solar
cells and planar displays.1–3 Conventionally, transparent
quarter-wavelength layers of SiOx, TiOx, or SixNy with inter-
mediate or gradient refractive indices are used as antireflec-
tion coatings, although multilayered coatings have also been
used to broaden the spectral width of the antireflection. How-
ever, these coatings work effectively only in a limited spec-
tral range and for specific angles of incidence.4 An alternate
approach to minimize reflectivity utilizes a finely textured
surface comprising sub-wavelength structures. A sub-
wavelength structured surface with a deep and tapered profile
can suppress the Fresnel reflection substantially over a wide
spectral bandwidth. Recently, NW arrays structure attracts
much attention for solar cell applications due to their en-
hanced antireflection effects.5 NW has been fabricated by
several methods including chemical vapor deposition,6 laser
ablation7 and annealing in a reactive atmosphere.8–10 Al-
though these synthesis methods are quite acceptable and well
controlled, most need either high temperatures or long
times11 due to the limitation of the growth mechanism, and
therefore increased production cost. A silver-induced
aqueous-chemical-etching process conveniently synthesizes
Si NWs at a low cost compared to the above methods.11
However, no analyses have previously been on a method for
synthesizing NWs on pyramids textured Si wafer. In addi-
tion, Si NW arrays solar cells have been reported by many
institutes, but there are few studies on the loss mechanism
using internal quantum efficiency 共IQE兲.11–13
In this article, Si NW arrays were synthesized by a gal-
vanic displacement reaction from double-side polished and
pyramid textured Si. Si NW prepared on double-side pol-
a兲
Author to whom correspondence should be addressed; electronic mail:
jiarui@ime.ac.cn
the wavelength region of 300–1000 nm. The lowest R of the
hybrid texture prepared on pyramids textured Si is 8% which
is much lower than pyramids textured Si. Also, the R prop-
erties of the nanostructures as a function of etching duration
are studied in detail. Nanostructure textured solar cells were
made using a conventional process. The effects of the nano-
structures on the performance of the cells as demonstrated by
such parameters as IQE, conversion efficiency 共␩兲, open cir-
cuit voltage 共Voc兲, and short circuit current 共Isc兲 have been
systemically investigated. We also analyzed the differences
of the nanostructure textured solar cells fabricated on sub-
strates with an initial PN junction present or absent.
II. EXPERIMENT
Si NWs were fabricated on 280 ␮m p-type double-side
polished 共substrate A兲 and single side pyramids textured
共substrate B兲 Cz-Si 共100兲 substrates with resistivity of
0.9 ⍀-cm. Various lengths of Si NW arrays were obtained
by immersing the Si substrate in an aqueous hydrofluoric
acid 共HF兲 and silver nitrate 共AgNO3兲 mixture solution, and
soaking the wafers in a hydrothermal bath of 25 ° C for times
varying from 30 to 240 min. An increased etching time re-
sults in correspondingly longer wire lengths, l. During the
etching process, Ag particles were deposited on the Si sur-
face and catalyzed subsequent Si etching by acting as local
cathodes while the Si below the Ag acts as anodes. Concen-
trated nitric acid 共HNO3兲 etching for 1 h removed the re-
sidual Ag particles, followed by rinses in a 5% HF solution
for 30 s and in DI water three times to eliminate the oxide
layer and residual ions, respectively. Energy diffuse spec-
trometry analysis found that the Ag mass concentration ratio
falls below 0.5% in 10 ␮m2 areas at the bottom position of
Si nanostructure. R and transmittance of nanostructures of
various etching duration were measured using a 7-SC Spec
SC Spectral Measurements System.

031208-1 J. Vac. Sci. Technol. B 29„3…, May/Jun 2011 1071-1023/2011/29„3…/031208/5/$30.00 ©2011 American Vacuum Society 031208-1
031208-2 Yue et al.: Antireflection properties and solar cell application of silicon nanostructures
FIG. 1. 共a兲 Silver films on substrate A after being etched for 2 h. 共b兲 The
silver particles at the bottom of the nanowires. 共c兲 Cross-section view of the
Ag removed nanowires of substrate A etched for 2 h. 共d兲 The top view of
substrate A etched for 3 h. 共e兲 The top view of substrate B etched for 0.5 h
and 共f兲 for 3 h.
Solar cells were fabricated on NWs and hybrid texture of
NWs and pyramids textured substrates. The differences of
solar cells with and without SiNx passivation layer were ana-
lyzed. Conventional solar cell fabrication processes were
used to create a front phosphorous-diffused emitter, an Al
back-surface field and a metal grid. The basic parameters,
including conversion efficiency 共␩兲, Isc, Voc, FF, and IQE of
125⫻ 125 mm2 cells, are measured with calibrated 1-sun
simulators.
III. RESULTS AND DISCUSSION
A. Observation results
Figure 1 shows the surface morphology of NWs as ob-
served by scanning electron microscopy 共SEM兲. The bright
area in Fig. 1共a兲 is a loose Ag dendritic film on the NW
surface before being well cleaned by HNO3. Ag particles on
the surface and at the bottom of NW arrays are shown in Fig.
1共b兲. The NWs of sub-wavelength size and uniform length
are fabricated on large areas of Si as shown in a top view
perspective in Fig. 1共c兲. NW arrays of various lengths are
prepared by changing etch duration, and a sample of NWs
about 5 ␮m in length whose diameters range from 50 to 250
nm is shown in a cross-sectional SEM image in Fig. 1共d兲.
Etching of substrate B begins at the top of the pyramids
which would be mostly removed if the etching duration is
long enough, as observed in Figs. 1共e兲 and 1共f兲. Controlling
the etching time results in a hybrid structure composed of
pyramid arrays and NW arrays synthesized on substrate B as
J. Vac. Sci. Technol. B, Vol. 29, No. 3, May/Jun 2011
031208-2
FIG. 2. 共Color online兲 Relationship of Si nanowire arrays length versus
etching duration. The red dotted line is the linear fit relationship.
shown in Figs. 1共e兲 and 1共f兲. The NWs in the hybrid struc-
ture are grown on the sidewalls of the pyramid and are not
vertical to the wafer but instead to the sidewall of the pyra-
mids as confirmed by SEM observation in Figs. 1共e兲. In other
words, the wafer is in 关100兴 while the side wall of the pyra-
mids is in 关111兴. Therefore, the preferential crystallographic
orientation of NW arrays remains the same as on substrate A
though substrate B has the pyramid texture, which is consis-
tent with the analysis of Chen et al.14 The effect of etching
on the bases of the pyramids is less than the tops of the
pyramids, which are almost removed completely when the
etching duration is longer than 3 h. According to SEM stud-
ies of NWs on polished wafers etched for different durations,
a general relationship between the lengths of the NW versus
etching time can be found, as depicted in Fig. 2. The linear
fit relationship is also plotted in Fig. 2. Such nearly linear
etching behavior enables length control of NWs on a large
scale.
B. Reflection measurements
The as-synthesized samples appear black, which reveals
the possibility of excellent optical anti-reflectance properties.
7-SCSpec Solar Cell Spectral Measurements System is used
for R measurements of the NW arrays. The R spectra of NW
on double-side polished and pyramid textured surfaces with
varied etching times are shown in Figs. 3共a兲 and 3共b兲, respec-
tively. Increasing the etching duration decreases the R of
substrate A, with R less than 3% for wavelengths from 300 to
1000 nm when the etching duration is longer than 2 h, as
shown in Fig. 3共a兲. Since R共␭兲 = 1 − A共␭兲 − T共␭兲, where ␭ is
the optical wavelength, and R, T, and A are the wavelength-
dependent reflectance, transmission, and absorption of the
NW arrays, respectively, the reduced R of the NW arrays
also can significantly increase the absorption ability. The ab-
sorption of substrate A etched for 4 h is derived from trans-
mission and R measurements and is plotted in Fig. 4共a兲, in
which pyramids textured Si is also plotted as a reference. As
the figure shows, the absorption is greater than 95% and
031208-3 Yue et al.: Antireflection properties and solar cell application of silicon nanostructures
FIG. 3. 共Color online兲 共a兲 and 共b兲 Reflectance of substrates A and B etched
for different times, respectively.
shows a more than 10% increase compared with pyramids
textured Si for wavelengths in the region of 400–1000 nm.
This observed reduction of R in the etched substrate A can
be explained by scattering theory. Compared to the diameter
of the pyramids, which is on the order of ␮m, the diameter of
the NWs, e.g., from 50 nm to 300 nm, becomes comparable
to the wavelength of the incident light. The incident light
will be greatly scattered according to sub-wavelength scat-
tering theory and therefore increases the optical path length.
Also, the NW introduces a possible porosity gradient which
implies a change of refractive index with depth.11 The above
factors result in the enhanced light absorption of the samples.
The R of substrate B is more complex after the hybrid
nanostructure is fabricated, as shown in Fig. 3共b兲. The varia-
TABLE I. Group samples with different fabrication processes.
Group # Pyramids The first P-diffusion
C w/o
D w/o
E 冑
F 冑
G 冑
JVST B - Microelectronics and Nanometer Structures
031208-3
FIG. 4. 共Color online兲 共a兲 Transmission and absorption of substrate A etched
for 4 h and pyramids textured Si. 共b兲 The reflectance of nanowire arrays on
substrate A in 300–1600 nm wavelengths.
tions in diameter of the hybrid structure change the reflection
properties for all wavelengths. For short wavelengths, the
wavelength of the incident light is similar to the average
diameter of NWs. Consequently, the scattering effect would
be dominant, and thus significantly suppress the transmission
and decrease the reflection. However, for long wavelengths,
the NWs increase anti-reflection properties, whereas the
micrometer-scaled pyramids deteriorate the anti-reflection
properties. Therefore, there is a trade-off between the influ-
ence of the pyramids array and the NWs array on the reflec-
tion property for the long wavelength region. Accordingly,
the reflection is first reduced but then enhanced as the etch-
ing time increases. Simultaneously, we can conclude that the
reflection reduction using the hybrid nanostructure is not sig-
nificantly greater than that of the NW array as shown in Figs.
3共a兲 and 3共b兲. Thus, the main mechanism of reflection reduc-
tion should be due to the involvement of NWs, which ulti-
mately enhance the absorption of NW textured solar cells.
For both substrate A and substrate B, the R increases
sharply for wavelengths longer than 1000 nm as shown in
Fig. 4共b兲. According to the equation R̄ = 兰R共␭兲d␭ / 兰d␭, the
average R of substrate A is 2.52% for wavelengths 300–1000
nm, where ␭ is the optical wavelength and R共␭兲 is a
wavelength-dependent reflection coefficient. It is also note-
worthy that the R of the samples is comparable or much
lower than those reported in the literature. For example, Peng
et al.11 obtained reflectance of 1.4% for wavelengths from
300 to 600 nm using NWs prepared on mc-Si substrates.
NW The second P-diffusion SiNx
w/o 冑 冑 冑
冑 冑 冑 冑
w/o 冑 冑 w/o
w/o 冑 冑 冑
冑 冑 冑 冑
031208-4 Yue et al.: Antireflection properties and solar cell application of silicon nanostructures 031208-4

Also, Rappich et al.15 obtained R values for nanoporous Si

ranging from ⬃2 – 30% and ⬃2 – 20% in anodized nanowire-
like structures in the 300–850 nm wavelength range.

C. Nanostructure textured solar cells

Nanostructure textured mc-Si solar cells with different
fabrication processes were made and divided into five
groups, C, D, E, F, and G, as shown in Table I. In order to
eliminate the processing fluctuation, there are five solar cells
in each group. In Table I, the pyramids structure was fabri-
cated by etching in alkaline solution. The Si NWs were made
using the method as described in Sec. II. As to the first and
the second phosphorus diffusion 共P-diffusion兲, they were
performed before and after Si NW formation, respectively,
with POCl3 being the diffusion source at 840 ° C for 20 min.
The 80 nm SiNx passivation layer was deposited by plasma-
enhanced chemical vapor deposition 共PECVD兲. The metal
grids and the aluminum back-surface-fields were fabricated
by screen printing method for all the samples. Current-
voltage curves of 125⫻ 125 mm2 cells were measured under
calibrated 1-sun simulators. In order to compare the effect of
Si nanostructures to solar cells, control samples were made
from double-side polished mc-Si. Figure 5 shows the 1-sun
IV parameters for five groups samples normalized to the pla-
nar control cell.
From Fig. 5共a兲, we can see that almost all the perfor-
mances of solar cells with Si nanostructures are better than
the control samples without texture, which verify the impor-
tance of texturization. The parameters of FF, Voc, Isc, and ␩
of group E are improved as compared with group F. The only
difference between these two groups is passivation process.
Therefore, the passivation layers play an important role in
improving the efficiency of solar cells with Si nanostruc-
tures. By comparing group C and D, though the FF are
slightly decreased, the Isc and ␩ of group D are obviously
increased as compared with group C. Consequently, two-step
P-diffusion process helps to improve the Isc and thus the ␩.
Similarly, the Isc of Group G is improved significantly as
compared with group F. Regarding the differences in Voc, the
main reason is the different recombination velocity. Gener-
ally, large Voc reflects the relatively lower surface recombi-
nation velocity of the Si/electrode junction and good bulk
properties of NWs.10 The first P-diffusion process increased
the doping concentration of Si NWs, and thus increased au-
ger recombination rate.
In order to investigate the conversion ratio of absorbed
photon energy to the converted electron energy, the IQE was
FIG. 5. 共Color online兲 共a兲 Normalized value of Voc, Isc, FF and ␩ for differ-
measured and the average value was shown in Figs. 5共b兲 and ent Groups sample. 共b兲 The comparison of IQE of Groups C and D. 共c兲 The
5共c兲. For our 7-SCSpec Solar Cell Spectral Measurements comparison of IQE of Groups E, F, and G.
System, the measured area for IQE is about 2 ⫻ 2 cm2. The
IQE of group D is slightly greater than C from 900 to 1100
nm as shown in Fig. 5共b兲. From Fig. 5共c兲, the IQE of group Comparing the IQE of group E and F, we can conclude
G is also greater than F between 900–1100 nm. Therefore, that SiNx passivation layer can improve the optical-electrical
the first P-diffusion process may help to improve the optical- conversion ratio, especially in 550–850 nm wavelengths.
electrical conversion efficiency in 900–1100 nm wave- Due to the improvement of IQE, the normalized Isc of group
lengths. F was improved by 15% as compared with Group E. From

J. Vac. Sci. Technol. B, Vol. 29, No. 3, May/Jun 2011

031208-5 Yue et al.: Antireflection properties and solar cell application of silicon nanostructures
Fig. 5共a兲, it can be found that the group F has the best per-
formance with the highest FF and Voc than the other four
groups, whose conversion efficiency was improved by 40%
as compared with that of planar solar cell without any tex-
tures. Hence, we can conclude some general effects of nano-
structures on solar cells. First, passivation condition is im-
portant to the mc-Si solar cells with Si nanostructure texture.
The nanostructure has a high aspect ratio and a correspond-
ingly larger surface and interface than planar structure,
which induces much more recombination centers. Therefore,
the electron-hole pairs would not be collected effectively if
recombination centers are not effectively eliminated by sur-
face and interface passivation, as clearly shown in Fig. 5共a兲.
Second, it is necessary to optimize the metal grid fabrication
process so as to achieve a better ohmic contact. The FF of
nanostructure solar cells in Groups C, D, E, and G are lower
than 66% 共not shown兲. The lower FF is caused by higher
series resistance and reduced local shunting resistance due to
the decreasing contact area between electrode and nanostruc-
ture. At last, the average Isc will be improved nearly by 10%
compared with planar solar cells if adding the first
P-diffusion process before fabricating NW, which was owing
to the heavily doping at the tip of nanostructure. Thus the
contact resistance could be decreased between nanostructure
and electrode. With the improvement of Isc, the higher con-
version efficiency could be obtained.
IV. CONCLUSION
Si NWs vertical to the substrate, which exhibits strong
anti-reflectance ability, as well as hybrid structure of NWs
and pyramids, were fabricated by an aqueous chemical etch-
ing method. NWs of different lengths can be fabricated by
adjusting the etching duration or reaction temperature. Re-
flectance of the structures, NWs and a hybrid structure of
NWs and pyramids, was measured and analyzed. The ab-
sorption of NWs was improved over conventional pyramid
textured Si by more than 10%. NW solar cells were also
JVST B - Microelectronics and Nanometer Structures
031208-5
fabricated and IQE and 1-sun IV parameters were measured.
Our best nanostructure solar cell exhibits an improved effi-
ciency by 71%, an open circuit voltage by 32%, a short-
circuit current by 15% and a fill factor by 13%, as compared
with planar solar cells, respectively. However, the recombi-
nation rate and surface state density is increased due to the
high surface-to-volume ratio, which shrinks the Voc and cor-
respondingly decreases the cell efficiency. The Isc can be
improved and the IQE will be improved in 900–1100 nm
wavelengths by adding the fist P-diffusion process before
NW structure fabrication.
ACKNOWLEDGMENTS
This work was subsidized by the 973 Projects under Grant
No. 2009CB939703, by the Chinese NSF under Grant Nos.
60706023, 60676001, 90401002, 60977050, and 90607022,
and under the Chinese Academy of solar energy action plan.
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