Published on Web 04/28/2010

High-Performance Silicon Nanohole Solar Cells

Kui-Qing Peng,*,† Xin Wang,† Li Li,† Xiao-Ling Wu,† and Shuit-Tong Lee*,‡
Department of Physics and College of Nuclear Science and Technology, Beijing Normal UniVersity, Beijing 100875,
China, and Center of Super-Diamond and AdVanced Films (COSDAF) and Department of Physics and Materials
Science, City UniVersity of Hong Kong, Hong Kong SAR, China
Received December 7, 2009; E-mail: [email protected]; [email protected]

Photovoltaic (PV) solar energy conversion represents a promising

approach to green, renewable energy. Despite its advantages and
continuing advances, PV technology remains non-cost-competitive
against traditional fossil fuels and thus has not yet been mass-
deployed. Recent research has focused on developing new PV
systems that incorporate optically active nanostructures such as
nanoparticles,1 quantum dots,2 nanotubes,3 nanorods,4,5 and
nanowires,6-19 which offer substantial potential for new device
structures. Functional PV devices based on conformal radial p-n
junction nanowires (alos called coaxial core/shell nanowires) are
of particular interest as an optimal way to decouple light absorption
from minority carrier collection.8-16 Tian and co-workers have
reported a single coaxial silicon nanowire (SiNW) solar cell with
a short-circuit current density (Jsc) of 23.9 mA/cm2 and a power
conversion efficiency of 3.4% under 1 sun AM1.5G illumination.10
Most of the current PV research on nanowires has focused on arrays Figure 1. SEM images of silicon nanoholes produced in an 8-12 Ω cm
of nanowires with solid-state radial p-n junctions.12-16 For p-Si(100) wafer. (a) Top-view SEM image of ordered, shallow, flat-bottomed
example, scalable SiNW-based solar cells with radial p-n hetero- pits in Si formed during the initial etching stage. Silver is seen at the bottom
of these pits. (b, c) Top-view SEM images of ordered silicon nanoholes
junctions have been fabricated with vapor-liquid-solid grown12 with large depths after prolonged immersion in HF and H2O2 solution. (d)
and electrolessly etched SiNW arrays.13 Unfortunately, all of those Cross-sectional view of silicon nanoholes; the hole channels are cylindrical
attempts thus far have yielded unsatisfactory results. The poor and vertical with respect to the Si surface.
performance is predominantly attributed to large shunting across prolonged immersion in the oxidizing HF solution. Figure 1b,c
the cells and excessive surface or junction recombination losses. shows top-view SEM images of large-area silicon nanoholes. They
More recently, Garnet and Yang reported SiNW solar cells with show that the holes are regularly distributed on the Si surface and
an efficiency above 5% and short-circuit photocurrents higher than that the thicknesses of the hole walls are 280 and 880 nm for the
those of planar control samples.20 In this work, we report the first-neighbor and second-neighbor holes, respectively. Figure 1d
fabrication of a novel Si nanohole solar cell incorporating radial is a SEM image of a cross section of the holes, showing that the
p-n junctions via thermal phosphorus dopant diffusion. Such a channels are cylindrical and vertical with respect to the wafer
nanohole geometry exhibits superior mechanical robustness in surface.
comparison with free-standing nanowire counterparts, which are Figure 2 illustrates the fabrication process of the radial p-n
fragile and easily cracked. Moreover, the nanohole array structures junctions in our Si nanohole solar cell. The Si nanohole sample
display superior optical absorption ability resulting from effective was first washed with excess deionized water, and silver was
optical coupling between the nanohole array and the incident light removed with concentrated nitric acid. RCA cleaning was carried
as well as a large density of waveguide modes.21 out to further eliminate the residual metal and organic species, after
The wafer-scale ordered Si nanohole array was fabricated by which Si oxide was removed with a buffered HF solution. Next, a
the combination of deep ultraviolet lithography (UVL) and metal- continuous thin n+ layer ∼150-200 nm in thickness was formed
assisted Si etching in aqueous oxidizing hydrofluoric acid (HF).22 on the exposed external and internal surfaces of the Si nanoholes
Figure S1 in the Supporting Information illustrates the fabrication via phosphorus dopant diffusion at 910 °C for 20 min using a liquid
process. Figure 1 shows typical scanning electron microscopy POCl3 source. After removal of the phosphorosilicate glass layer
(SEM) images of Si nanoholes produced from a p-type Si(100) in a diluted HF solution, an aluminum layer was evaporated onto
wafer with a resistivity of 8-12 Ω cm in an aqueous solution of the rear surface and treated at 980 °C to remove the rear parasitic
HF and H2O2. The concentrations of HF and H2O2 were 10 and p-n junction and concurrently form a back-surface field on the
0.6%, respectively. The pore diameters and wall thicknesses were back side of the wafer. Afterward, a 200 nm aluminum layer and
defined by a chromium mask and deep UVL, while the nanohole Ti/Pd/Ag grid contacts were deposited onto the rear and front sides
depths were adjusted by the etching time. Figure 1a is a top-view of the Si nanoholes, respectively. Good Ohmic contacts were
SEM image of the ordered, shallow, flat-bottomed pits in Si formed achieved by annealing at 380 °C. A prototype Si nanohole solar
during the initial etching stage, where a silver film can be clearly cell was created after removal of the circumferential parasitic p-n
seen. These shallow pits would grow into deep holes upon junction, as shown in Figure S2. Such a nanohole solar cell offers
†
Beijing Normal University.
several distinct advantages associated with its unique geometry.
‡
City University of Hong Kong. First, it consists of well-separated functional radial p-n junctions,
6872 9 J. AM. CHEM. SOC. 2010, 132, 6872–6873 10.1021/ja910082y  2010 American Chemical Society
 COMMUNICATIONS
tions. The Si nanohole device shows a substantively larger Jsc and
efficiency than its counterparts based on planar Si, pyramid-textured
Si, and SiNWs, demonstrating that nanohole arrays are better than
other geometrical textures in PV performance improvement and
thus represent a meritorious and viable approach for efficient solar
PVs. This observation is supported by recently theoretical results.21
According to the mask used for the front electrode, 20% of the
front surface area of the nanohole device was covered by the front
contact; thus, the effective Jsc for the nanohole solar cell is 40 mA/
cm2 after exclusion of the front contact area. Figure S3 shows the
external quantum efficiency (EQE) for the nanohole solar cell,
which exhibits a spectrally broad EQE response. We expect device
optimization (e.g., improved coupling of light into the device),
surface passivation, and better contacts to further enhance the
performance of the Si nanohole solar cell.
In summary, we have demonstrated the fabrication of a silicon
Figure 2. Sectional elevation of the process of fabricating the Si nanohole nanohole solar cell consisting of three-dimensional radial p-n
solar cell with radial p-n junctions via thermal phosphorus dopant diffusion. junctions. Under 1 sun AM1.5G illumination, the nanohole solar
The n+ layer is shown in purple bronze, the p-Si substrate in gray, and the
cell exhibited a Voc of 566.6 mV, a Jsc of 32.2 mA/cm2, and a power
rear electrode in red; the front Ti/Pd/Ag grid electrode is not shown here.
conversion efficiency of 9.51%, which are superior to those of its
counterparts based on SiNWs, planar Si, and pyramid-textured Si.
The nanohole array geometry holds great potential for cost-efficient
PV solar energy conversion.
Acknowledgment. This work was supported by the National
973 Project of China (Grant 2006CB933000), the NSFC (Grant
50702010), National Excellent Doctoral Dissertations of China
(Grant 200743), Beijing Natural Science Foundation (Grant 2082013),
NCET-08-0060, Beijing Nova Program 2008B24, a Research Grants
Council of Hong Kong SAR-CRF Grant (Grant CityU5/CRF/08),
and the Joint Research Project of RGC and NSFC (Grant
Figure 3. (a) I-V curves for Si nanohole solar cells in the dark and under
AM1.5 illumination. (b) I-V curves for solar cells with different geometries N_CityU108/08). Dr. Y. Xu is thanked for her contributions.
fabricated under identical conditions.
Supporting Information Available: Experimental details of fabrica-
because the thin walls between the first-neighbor pores are fully tion of silicon nanohole arrays and solar cells. This material is available
depleted, while the thick walls between the second-neighbor pores free of charge via the Internet at http://pubs.acs.org.
remain quasi-neutral for efficient channeling of holes to the p-type References
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