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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
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 031208-2
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
FIG. 1. 共a兲 Silver films on substrate A after being etched for 2 h. 共b兲 The words, the wafer is in 关100兴 while the side wall of the pyra-
silver particles at the bottom of the nanowires. 共c兲 Cross-section view of the mids is in 关111兴. Therefore, the preferential crystallographic
Ag removed nanowires of substrate A etched for 2 h. 共d兲 The top view of orientation of NW arrays remains the same as on substrate A
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.
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
Solar cells were fabricated on NWs and hybrid texture of pyramids, which are almost removed completely when the
NWs and pyramids textured substrates. The differences of etching duration is longer than 3 h. According to SEM stud-
solar cells with and without SiNx passivation layer were ana- ies of NWs on polished wafers etched for different durations,
lyzed. Conventional solar cell fabrication processes were a general relationship between the lengths of the NW versus
used to create a front phosphorous-diffused emitter, an Al etching time can be found, as depicted in Fig. 2. The linear
back-surface field and a metal grid. The basic parameters, fit relationship is also plotted in Fig. 2. Such nearly linear
including conversion efficiency 共兲, Isc, Voc, FF, and IQE of etching behavior enables length control of NWs on a large
125⫻ 125 mm2 cells, are measured with calibrated 1-sun scale.
simulators.
B. Reflection measurements
III. RESULTS AND DISCUSSION
The as-synthesized samples appear black, which reveals
A. Observation results
the possibility of excellent optical anti-reflectance properties.
Figure 1 shows the surface morphology of NWs as ob- 7-SCSpec Solar Cell Spectral Measurements System is used
served by scanning electron microscopy 共SEM兲. The bright for R measurements of the NW arrays. The R spectra of NW
area in Fig. 1共a兲 is a loose Ag dendritic film on the NW on double-side polished and pyramid textured surfaces with
surface before being well cleaned by HNO3. Ag particles on varied etching times are shown in Figs. 3共a兲 and 3共b兲, respec-
the surface and at the bottom of NW arrays are shown in Fig. tively. Increasing the etching duration decreases the R of
1共b兲. The NWs of sub-wavelength size and uniform length substrate A, with R less than 3% for wavelengths from 300 to
are fabricated on large areas of Si as shown in a top view 1000 nm when the etching duration is longer than 2 h, as
perspective in Fig. 1共c兲. NW arrays of various lengths are shown in Fig. 3共a兲. Since R共兲 = 1 − A共兲 − T共兲, where is
prepared by changing etch duration, and a sample of NWs the optical wavelength, and R, T, and A are the wavelength-
about 5 m in length whose diameters range from 50 to 250 dependent reflectance, transmission, and absorption of the
nm is shown in a cross-sectional SEM image in Fig. 1共d兲. NW arrays, respectively, the reduced R of the NW arrays
Etching of substrate B begins at the top of the pyramids also can significantly increase the absorption ability. The ab-
which would be mostly removed if the etching duration is sorption of substrate A etched for 4 h is derived from trans-
long enough, as observed in Figs. 1共e兲 and 1共f兲. Controlling mission and R measurements and is plotted in Fig. 4共a兲, in
the etching time results in a hybrid structure composed of which pyramids textured Si is also plotted as a reference. As
pyramid arrays and NW arrays synthesized on substrate B as the figure shows, the absorption is greater than 95% and
C w/o w/o 冑 冑 冑
D w/o 冑 冑 冑 冑
E 冑 w/o 冑 冑 w/o
F 冑 w/o 冑 冑 冑
G 冑 冑 冑 冑 冑
Fig. 5共a兲, it can be found that the group F has the best per- fabricated and IQE and 1-sun IV parameters were measured.
formance with the highest FF and Voc than the other four Our best nanostructure solar cell exhibits an improved effi-
groups, whose conversion efficiency was improved by 40% ciency by 71%, an open circuit voltage by 32%, a short-
as compared with that of planar solar cell without any tex- circuit current by 15% and a fill factor by 13%, as compared
tures. Hence, we can conclude some general effects of nano- with planar solar cells, respectively. However, the recombi-
structures on solar cells. First, passivation condition is im- nation rate and surface state density is increased due to the
portant to the mc-Si solar cells with Si nanostructure texture. high surface-to-volume ratio, which shrinks the Voc and cor-
The nanostructure has a high aspect ratio and a correspond- respondingly decreases the cell efficiency. The Isc can be
ingly larger surface and interface than planar structure, improved and the IQE will be improved in 900–1100 nm
which induces much more recombination centers. Therefore, wavelengths by adding the fist P-diffusion process before
the electron-hole pairs would not be collected effectively if NW structure fabrication.
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 ACKNOWLEDGMENTS
process so as to achieve a better ohmic contact. The FF of This work was subsidized by the 973 Projects under Grant
nanostructure solar cells in Groups C, D, E, and G are lower No. 2009CB939703, by the Chinese NSF under Grant Nos.
than 66% 共not shown兲. The lower FF is caused by higher 60706023, 60676001, 90401002, 60977050, and 90607022,
series resistance and reduced local shunting resistance due to and under the Chinese Academy of solar energy action plan.
the decreasing contact area between electrode and nanostruc-
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