(Nano Fios Si Fotovoltaico) - (Sun, K, 2011) - Compound Semiconductor Nanowire Solar Cells

IEEE JOURNAL OF SELECTED TOPICS IN QUANTUM ELECTRONICS, VOL. 17, NO.
4, JULY/AUGUST 2011
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Compound Semiconductor Nanowire Solar Cells

Ke Sun, Student Member, IEEE, Alireza Kargar, Student Member, IEEE, Namsoek Park,
Kristian N. Madsen, Student Member, IEEE, Perry W. Naughton, Timothy Bright,
Yi Jing, and Deli Wang
(Invited Paper)
AbstractThere have been many recent developments in compound semiconductor nanowire photovoltaic devices. Of these, advances in nanowire synthesis and performance enable nanowires to
be implemented for efficient and low-cost solar-energy-harvesting
devices. On the other hand, many challenges in device fabrication
must be resolved in order for nanowires to assure a role at the
forefront of solar cell technology.
Index TermsCompound semiconductor, nanowires, solar cell.
I. INTRODUCTION
NERGY production is among the top problems that humanity will face over the next century. Consequently, many
organizations from around the world are searching for alternatives to fossil fuels that are low cost, sustainable, and clean.
For example, as a national initiative, the USA has spent over
5 billion dollars on related research related to alternative and
cleaner energy. Among these clean energy sources, solar energy
is one of the most promising and fastest growing renewable energy sources worldwide. Over the past 10 years, the photovoltaic
(PV) industry has seen double-digit growth; in 2008, solar panel
installation increased by 110% from what it was in 2007. Converting solar energy into electricity or hydrogen fuel using PV
cells is one of the most attractive solutions to modern energy
issues because solar energy is produced energy with almost zero
carbon-emission, which limits carbon-emissions, limits the concentration of green-house gases in the atmosphere, potentially
slows the global climate change [1]. Despite this tremendous
growth, however, solar power still accounts for share less than
0.1% of global energy generation because of its high cost of
production [2].
A large variety of thin film and nanomaterial technologies
are being actively researched due to their potentially low-cost
production (less materials used) and possibility of higher performance than current crystal Si technology. These nanostructured
Manuscript received August 28, 2010; revised October 26, 2010; accepted
October 26, 2010. Date of publication January 20, 2011; date of current version
August 5, 2011. This work was supported in part by the Department of Energy
(DOE) under Grant DE-FG36-08G018016, and in part by the National Science
Foundation under Grant ARRA ECCS0901113. The work of D. Wang was
supported by the World Class University (WCU) Program at Sunchon National
University, Korea, Abgent, Inc., and AEM, Inc.
K. Sun, A. Kargar, N. Park, K. N. Madsen, P. W. Naughton, Y. Jing, and
D. Wang are with the University of California at San Diego, La Jolla, CA 92093
USA (e-mail: dwang@ece.ucsd.edu).
T. Bright is with the Oral Robert University, Tulsa, OK 74171 USA and was
with the University of California at San Diego, La Jolla, CA 92093 USA.
Color versions of one or more of the figures in this paper are available online
at http://ieeexplore.ieee.org.
Digital Object Identifier 10.1109/JSTQE.2010.2090342
materials offer very attractive advantages in photon absorption

and carrier confinement. In particular, when compared to conventional Si PV devices, semiconductor nanowires (NWs) offer
the advantages of enhanced light absorption, efficient carrier
separation and collection at contact electrodes, and low-cost
processing using fewer materials [3], [4]. Great efforts have
been made to fabricate 1-D NWs and ordered NW arrays for
PV device applications based on top-down or bottom-up techniques [5][7]. NW solar cells based on a single NW or NW arrays have been theoretically and empirically demonstrated using
group IV, IIIV, or IIVI compound semiconductors [8][15],
allowing semiconductor NWs to emerge as building blocks for
PV devices [16].
In this paper, we aim to review the recent developments of
compound semiconductor NW PV devices, including a comparison to Si NW devices. We illustrate advantages in material synthesis and device performance, along with challenges
of device fabrication, and conclude that NW structures provide
beneficial properties for efficient solar-energy-harvesting at low
cost. In Section II, we illustrate the structure of NW solar cells
and the advantages in light absorption, photogenerated charge
separation and collection. In Section III, we review compound
semiconductor NW solar cells, where Si/Ge NW solar cells are
summarized for comparison purposes. The use of NW arrays
for semiconductor-sensitized solar cells (SCSSCs) and organicinorganic hybrid solar cells are outlined in Section IV. Section
V concludes and provides perspectives.
II. NANOWIRE SOLAR CELLS
The process in which light is converted to electricity in a solar
cell involves four stages: light absorption, charged carrier generation, separation, and collection. Considering the efficiency
in each stage, we can formulate the overall light conversion
efficiency in the equation below:

i
(1)
=
i
where is the overall efficiency, and i = a, g, s, and c represent

efficiency for absorption, generation, separation and collection,
respectively. NW structures, particularly vertical NW arrays,
offer significant advantages in enhancing the efficiency of all
the stages in the light harvesting process, making them attractive
for solar cell devices.
A. Nanowire Solar Cell Structure
NW solar cells can be in the form of either a single NW or an
array of NWs, which are usually in an aligned vertical geometry
1077-260X/$26.00 2011 IEEE
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IEEE JOURNAL OF SELECTED TOPICS IN QUANTUM ELECTRONICS, VOL. 17, NO. 4, JULY/AUGUST 2011
Fig. 1. (a) Schematic of NW array solar cell structures, (b) NW with axial
multiple junctions from semiconductors with different band gaps, (c) NW with
radial multiple junctions, (d) NW with axial p/n junction, (e) NW with radial
p/n junction, and (f) NW with radial heterojunction.
[see Fig. 1(a)]. p/n junctions in NW solar cells can be formed

in radial or axial directions. For axial NW PVs, the electrode
contacts are placed on the p- and n- regions, respectively, while
the contacts of the core/shell NWs are placed at the bottom and
top of NWs. NW arrays for solar-cell applications are normally
freestanding NWs with abrupt junctions for charge separation.
These NWs have sizes comparable to characteristic scale of
fundamental solid-state phenomena [16], and offer potential
2-D semiquantum confinement of carriers. Vertical NW arrays enhance light absorption and improve both charge separation and collection efficiencies. Fig. 1(b) and (c) shows the
formation of axial and radial multijunction NW heterostructures, which enable-enhanced light absorption by solar spectrum and through the formation of stacked heterojunction solar
cell devices. Fig. 1(d)(f) show the axial p/n junction, radial
(core/shell) p/n junction, and type-II heterojunction structures,
along with their respective energy band diagrams. Other benefits
NWs offer are their large surface-to-volume ratio for effective
chemical and catalytic reactions and a large number of surface
states to minimize dark currents [17]. NW array PV devices allow the use of low-cost materials and substrates, because NWs
can be grown epitaxially on lattice mis-matched or amorphous
substrates. NWs are manufactured via sufficiently controllable
top-down and bottom-up fabrication techniques that can potentially lead to economical manufacturing [18].
B. Light Absorption in NW Arrays
Light absorption is critical for efficient energy conversion in
PV devices. Broadband suppression of specular and diffusive reflection using nanostructure arrays over a wide range of incident
angles has been demonstrated [19], [20]. As the theoretical work
by Huang et al. demonstrates [20], Si substrates decorated with
NW arrays show reduced reflection and are insensitive to the
light polarization and the angle of incidence incident (AOI) over
a broad range of wavelengths (2502000 nm). By comparison,
a polished planar Si structure shows significantly higher reflection and incident light polarization dependence, yielding 10%
differences in reflectance between s- and p-polarized light. In
contrast, the reflectance from an aperiodic Si NW array demon-
Fig. 2. (a) Gradient refractive-index profile simulation (reproduced with permission from [20], copyright Nature Publishing Group), and (b) transmission
spectrum of NW array (reproduced with permission from [19], copyright American Chemical Society).
strates minimum sensitivity to the AOI compared to periodically

coated and nonperiodic porous substrates. This improved light
absorption in NWs is primarily caused by a gradual reduction
of effective refractive index [21] and internal scattering centers [22].
In 1879, Lord Rayleigh proposed the principle of reflection
suppression based on a gradual reduction in effective refractive
index. He showed that inhomogeneous structures essentially
remove the sharp interface between the media and substrate
providing a gradual transition in the refractive index [21]. Like
Lord Rayleighs model, the functionality of an inhomogeneous
aperiodic Si NW layer can be modeled as a series of thin films
with small refractive index difference between each [23], [24].
In this model, size and shape of the NW plays an important role
in obtaining the best absorption. For example, Cuis group from
Stanford has demonstrated that nanocone arrays with gradually
varying radial size help to smooth the transition of effective
refractive index, and thus, reduces reflectance when compared
to Si NW arrays of fairly uniform radial size [25]. Also, other
recent work on ZnO-based nanostructures also supports this
phenomenon [26], and based on this physical concept, Javeys
group at UC-Berkley has introduced dual-diameter Ge NWs
to reduce light reflection and enhance light absorption. This is
achieved by using a structure composed of smaller NWs on
the top and large NWs at the bottom, capturing the gradient
effect [27].
Besides shape, NW length is also critical for light absorption
optimization [see Fig. 2(b)]. Generally, longer NWs are believed
to show better performance with short wavelength due to a
finer refractive-index gradient at the air-solid interface [20],
SUN et al.: COMPOUND SEMICONDUCTOR NANOWIRE SOLAR CELLS
which also shows dependence on the extinction coefficient of

the material [4]. However, the effect of NW length on light
absorption is sophisticated because diffuse scattering becomes
significant for longer NW devices, leading to diffuse reflectance.
This is more pronounced, particularly when the wavelength is
comparable to the physical dimensions of the NWs [22]. The
other drawback of longer and thinner NWs is a decrease in
their moment of inertia and spring constant. Longer and thinner
NWs are more flexible, allowing van der Waal forces to collapse
the NWs into disordered clusters, which consequently increases
diffuse reflectance also and charge recombination as well [28].
Light absorption enhancement in InAs/InP [29] and Si [30]
NW arrays has also been studied by simulations conducted using a 2-D wave-guiding approach. Power dissipation along the
NW array exhibits dependence on the dispersion characteristics,
which include the input light radiation and dielectric properties
of both the surrounding media and active material. Most importantly, these studies suggest that the absorption characteristics of
NW arrays are not primarily influenced by material composition,
but by the field distribution of various modes, mainly depending
on the structure geometry [29]. Moreover, the physical filling
ratio of a NW array on a surface has a significant effect on the
device performance. Intuitively, a smaller filling ratio reduces
reflection for a wider light spectrum. However, reduced filling
ratio decreases absorption for longer wavelengths and increases
absorption in shorter wavelengths, which effectively shifts the
absorption spectra [4].
Additional effects include optical leaky-mode resonance
(LMR) [31] and polarization with respect to the optical field
[32], [33]. Under exposure to normal incident light, azimuthally
rotating samples showed a four-fold pattern of birefringence
[32][34]. The relative orientation between the NW and the
polarized light vector contributes to this effect, resulting in an
azimuth-angle-dependent perpendicular and horizontal ratio of
light absorption (I /I// ). However, this absorption anisotropy
diminishes with decreased NW size and increased array density, due to pronounced disorder features in arrays with thin
NWs [35]. This is consistent with the contributions from the
aperiodic Si NW arrays discussed above. Additionally, scattering can be further suppressed by introducing higher refractive
index materials in between NWs [36]. In addition to the theoretical studies on ordered NW arrays [4], [22], [25], [37], optical
properties of disordered NW arrays are studied theoretically
and experimentally [38], [39], and is essentially determined by
multiple diffuse scattering of light [22].
Improvements in understanding NW synthesis, alloying, and
engineering at the nanoscale, such as the formation of heterostructures in both axial and radial directions, allow for better
control in fabricating nanostructures and provides ways to tailor
absorption spectra for specific applications [31].
C. Charge Generation and Separation in NWs
Generally speaking, incident photons with energy greater than
the semiconductor band gap will be absorbed by the semiconductor and will generate carriers (electrons and holes). This
generation process can be hindered by semiconductor imperfections, relaxations and other effects, which are discussed in
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detail in existing textbooks and will not be repeated here. NW

geometry offers many improvements for charge generation and
separation and can be organized according to the internal forces
of separation.
1) Charge Separation Assisted by Electrostatic Force: The
built-in field across the interface of p- and n-doped regions
creates an electrostatic force. The magnitude of this force is
proportional to the Fermi level offset and inversely proportional to the width of the depletion region. Theoretically, the
electrostatic force assists in the separation of photogenerated
electrons and holes, influencing the efficiency of the PV device.
A p-n junction in a NW can be in the radial or axial direction, as shown in Fig. 1(d) and (e). Unique geometric properties
of NW structures enhance charge generation and facilitate the
transportation of carriers. For example, in core/shell structures,
the geometry of the vertical NW array separates the pathways
of incident photon absorption (along the axial direction) and
charge separation by the built-in electric field (along the radial direction). In addition, NWs also offer enhanced junction
area (to volume), which greatly enhances the charge separation
efficiency.
Another junction configuration worth mentioning is a radial
p-n junction formed at the interface of a semiconductor and
electrolyte. This alternative construction is known as a photoelectrochemical cell (PEC) and has a theoretical potential for
high-efficiency energy conversion. This is due to the advantages of high quality, conformal, and rectifying liquid-solution
junctions, which can enhance minority carrier generation, separation and collection similar to core/shell junctions. This is
supported by findings that show photocurrent density enhancement in Si NW photoelectrodes when compared to planar Si
devices [40][42].
2) Charge Separation in Heterostructures (Nonelectrostatic
Force): Nonelectrostatic forces arise from composition variations in compound semiconductors, e.g., the composition (x)
of a binary compound semiconductor (Ax B1x C). Effective
masses of electrons and holes vary between materials, which
gives rise to a quasielectric field for electrons or holes [43].
Type-II, or staggered band core/shell, NW solar cell structures
[see Fig. 1(f)] are studied and distinguished from other solar
cells with junction structures driven by the electrostatic force.
The charge separation scheme in these devices suppresses the
intrinsic recombination at the junction [44] without the need for
additional doping processes.
Studies in thin film solar cells show that graded band-gap
materials demonstrate a broadened spectral response and therefore a high conversion efficiency [45][49]. Normally, a graded
band-gap solar cell has a wide band gap at the surface, creating a
window effect that significantly reduces surface recombination.
Meanwhile, the low gap gradient near the junction avoids the
occurrence of an inverted window effect, which would result in
incomplete absorption of photons with energies just greater than
the energy gap at the junction [50]. To the best of our knowledge,
no one has utilized graded band-gap structures with type-II junction NW solar cells. However, some works have demonstrated
the capability of synthesizing spatial composition-graded alloy
NWs [51][53], which may lead to improved solar power conversion efficiency.
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Recent interest has focused on strain engineering of Si NWs to

enhance charge separation through the controllability of the NW
morphology [54]. Technically, in a narrow tapered or strained
Si NW, both the quantum confinement strength and the surface
morphology vary significantly along the NW axis. This causes
different shifts in local near-gap energy levels along the NW
axis [55] and forms an ideal type-II junction. Therefore, tuning
the electronic structure offers another way of controlling intrinsic properties of nanostructure materials without introducing a
homo- or heterojunction.
TABLE I
DEVICE PERFORMANCES VERSUS PHYSICAL PARAMETERS
IN RADIAL JUNCTION
D. Charge Collection in NWs

Charge collection, or transportation, of photogenerated carriers to contacts is plagued by recombination, which can occur
at the surface, interface, and at bulk defects. In the case of NW
solar cells, surface recombination remains a major challenge
because of the inherently large surface-to-volume ratio. For example, in the case of core/shell NWs, charges generated and
separated into the shell or core far from the top or bottom contacts have a high chance to be trapped and recombined because
of the large distance they must travel. Traditional approaches,
such as transparent conducting oxide (TCO) deposition and interdigitated metal grid are insufficient to solve this problem.
Therefore, charge collection unfortunately limits NW solar cell
performance. Proper device design and fabrication based on
simulation is needed to improve NW PV performance. Initiative work has already begun demonstrating the advantages of
using uniform contact in solid-state devices [56]. On the other
hand, dye-sensitized solar cells (DSSCs) and PECs using NW
electrodes have demonstrated better charge collection efficiency
due to the uniform interfaces between semiconductor and electrolyte [35].
E. Nanowire Solar Cell Devices
There are distinct advantages regarding the use of radial junctions. First, the junction interface extends along the length of the
NW maximizing the junction area. Second, since the radial configuration yields orthogonalized pathways for light absorption
and carrier collection [3], a carrier collection distance comparable to or even smaller than the minority carrier diffusion length
(Ln ) is possible. This allows photogenerated carriers to reach the
p/n regions or electrodes (if in the surrounding geometry) with
high efficiency and substantially low bulk recombination, a key
limitation of conventional planar solar cells. Recent theoretical
studies have supported that core/shell NW structures improve
light absorption and carrier collection efficiencies when compared to planar PV devices [4], [19], [57]. Although, generally
speaking, generation and separation efficiencies are improved,
design and optimization issues remain in core/shell NW solar
cells. Detailed discussion can be found in Atwater and Lewiss
simulation study of nondegenerately doped Si and GaAs [3].
Their study addresses the effects of different design parameters
on the performance of solar cell devices, namely the minority carrier lifetime ( ), open-circuit voltage (VOC ), short-circuit
current density (JSC ), fill factor (FF), and eventually, conversion efficiency (). Like planar structures, optimization consid-
erations must be made with respect to some of the geometric

parameters of NW structures due to the inverse behavior of the
JSC and VOC (see Table I). This study offered guidance to later
experimental studies [8], [13], [58].
The axial junction can be formed by introducing different doping along the axial direction of NWs [59], [60], by
growing vertical NW arrays on substrates with opposite doping [5], [61][63], or by creating rectifying metal contacts to
unintentionally doped NWs [12]. In axial junction NWs, the
carrier transport direction is parallel to the NW growth direction and axial junctions do not have the same advantages in
charge separation that radial junctions do.
Heterostructures, such as tandem stacking of multiple p/n
junctions and multiple quantum well (MQW) structures, can
also be integrated in series in axial or radial junctions [see
Fig. 1(b) and (c)]. The fabrication of these tandem cell structures leads to a maximization of the absorption of solar spectrum
by using multiple materials with different band gaps and a minimization the hot electron effect. Also, quantum wells can act
as absorbers of additional photons, thus resulting in increased
JSC and .
To summarize, vertical NW solar cells offer enhanced energyconversion efficiency due to enhanced light absorption, improved charge separation and improved charge collection. The
vertical NW array geometry with varied size and/or composition
along the NW axis enhances light absorption due to the waveguiding effect, reduces surface reflectance and minimizes angular
dependence. Lastly, the formation of heterostructure solar cells
enables potential for further enhancements in overall efficiency.
III. COMPOUND SEMICONDUCTOR NANOWIRE SOLAR CELLS
A. Group IV Semiconductor Nanowire Solar Cells
For the purpose of drawing comparison to compound semiconductor NW solar cells, we must first recall recent reports on
silicon NW solar cells. To summarize the material, synthesis,
structure and performance, a table comparing each kind of compound semiconductor NW solar cell can be found in Table II.
Si is the dominant semiconducting material in todays technology and has been used extensively for PV applications [40], [64],
[65] because of its low cost, abundance on earth and tunability of
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TABLE II
SUMMARY OF NANOWIRE SOLAR CELL PERFORMANCES
doping and morphology [8], [60]. Si NWs have been applied to

solar-cell applications with different structures (e.g., single NW
or an array of NWs). Single coaxial p-i-n silicon NW solar cells,
consisting of a p-type core with intrinsic and n-type shells [see
Fig. 3(a)], have been fabricated by the vaporliquidsolid (VLS)
method and subsequent thin film deposition using chemical va-
por deposition (CVD) [8], resulting in a. conversion efficiency

of 3.4% which is owed to a high JSC caused by strongly improved absorption in the thin shell due to its nanocrystalline
feature and intrinsic layer. Alternatively, Kelzenberg et al. have
fabricated single-NW silicon solar cells using VLS method by
creating rectifying contacts [12] [see Fig. 3 (b)]. This cell has an
1038
Fig. 3. Si NW solar cells: (a) single NW with radial p-i-n junction (reproduced with permission from [8], copyright Nature Publishing Group), (b) single
NW with axial p-n junction (reproduced with permission from [12] copyright
American Chemical Society), (c) NW array with axial p-n junction (reproduced
with permission from [62] copyright American Chemical Society), and (d) NW
array with radial p-n junction (reproduced with permission from [13], copyright
American Chemical Society).
efficiency of 0.46%. When compared to single radial p-i-n NW

solar cells, the conversion efficiency is low, while the carrier
diffusion lengths are long (>2 m).
Meanwhile, several studies have been focused on silicon NWarray-based solar cells [9], [11], [19], [61], [65], [66]. Despite
high anti-reflecting characteristics of silicon NW arrays, the
PV conversion efficiency (9.31%) of the fabricated solar cells
consisting of n-type Si NW arrays on a p-type Si substrates
is not as high as efficiencies of conventional solar cells [61],
[67]. We believe that the low conversion efficiency is due to
the limited junction area (axial junction between n-NW and psubstrate) as well as surface states in etched Si NWs. These
effects, compounded by the ultrahigh surface area of the NW

arrays, eventually increase the surface recombination velocity
and limit the carrier collection efficiency. Other problems where
experienced by Tsakalakos et al. when they fabricated NW solar
cells by depositing a thin n-type amorphous Si layer on a p-type
silicon NW array to form a p-n junction through the VLS method
[11]. With this method they significantly reduce the reflectance
of a typical NW cell, but the power conversion efficiency was
low (0.1%) which is probably due to high series and low shunt
resistances. Sivakov et al. demonstrated higher efficiencies with
a solar cell based on Si NW arrays on glass substrates [see
Fig. 3(c)]. This multijunction device is formed by applying a
wet chemical etching process to form p+ nn+ polycrystalline
silicon layers on glass, and exhibits a conversion efficiency of
4.4% [62].
To improve the minority carrier collection in Si NW-arraybased solar cells, NWs with radial junctions are favorable. Si
NW arrays consisting of an n-type core and a p-type shell have
been fabricated and characterized [13] [see Fig. 3(d)]. The NW
cell which contains vertically aligned 18 m long NWs with high
packing density, is synthesized by a low-cost solution method
and gives a measured overall cell efficiency of 0.46%. Garnett
and Yang recently demonstrated the strong light-trapping properties of NW arrays, which improve the conversion efficiency
of Si-NW-array solar cells [19]. They reported that their 5-mNW-array radial p-n junction solar cells fabricated from 8 m
and 20 m thin Si absorbing layers generate conversion efficiencies of 4.83% and 5.30%, respectively, under AM 1.5G
illumination. The conversion efficiency of 4.83% for 8 m absorber Si-NW-array cells is about 20% higher than those on
8-m-thick Si ribbon solar cells (4% higher JSC ). However, the
power conversion efficiency of 5.30% for the 20 m absorber SiNW-array solar cells is about 35% lower than the corresponding
microfilm solar cells that yield an efficiency of 7.2% (14% lower
JSC ) [68]. Their device demonstrated a significant light-trapping
effect, above the theoretical limit for a randomizing system,
pointing out that there may be photonic crystal improvement effects. Nevertheless, the overall efficiency of these NW cells does
not surpass that of planar cells due to increased junction and surface recombination. Even in comparison, the efficiency is more
than ten times that of previous reported data [13]. Therefore,
such a kind of vertical NW array structure provides a feasible
path toward high-efficiency and low-cost solar cells by reducing both the quantity and quality of the needed semiconductor
materials.
One of the approaches to enhance the power conversion efficiency of Si NW-array-based solar cells is to decorate them with
nanoparticles (NPs) or quantum dots (QDs). Materials such as
insulators, metals, and semiconductors are widely used for this
purpose, each contributing a different improvement due to a different mechanism. Insulators such as SiO2 [69] and Al2 O3 [35]
provide efficient light scattering. These NPs disperse the incoming light towards the Si NWs in a way that light absorption is
maximized and AOI effect is suppressed. Alternatively, metal
NPs, such as Pt [70] and Au [71], can introduce plasmonic
effects besides efficient light scattering [72]. These NPs improve light trapping due to the interaction between the surface
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plasmon and metal NPs. For this reason, plasmon-enhanced solar cells are recognized as the next generation of solar cells [73].
Also, Si NWs decorated with Pt NPs show exceptional catalytic
activity at interfaces with liquids [70]. Semiconductor QDs normally have high refractive index, which is believed to offer better
light trapping performances. On the other hand, semiconductor
NPs (e.g., PbS) provide additional absorption over a broad spectrum due to their high absorption coefficient [74]. In addition,
resonant excitons with high mobility transfer to the adjacent Si
NW channel upon light absorption.
B. Group IIIV Semiconductor NW Solar Cells
IIIV compound semiconductors are believed to be excellent
candidates for solar-cell applications. To date, the highest
efficiency solar cells are constructed from multijunction IIIV
materials, which together with concentrated sunlight reach
efficiencies of 40.8% (326 suns) from Spectrolab (USA) [75]
and 41.1% (454 suns) from Institute of Solar Energy System
(Germany) [76]. IIIV semiconductor materials offer outstanding electrical properties, including: 1) tunable energy band
gaps and alloys; 2) a larger band gapthan Sieffectively
offering lower excess reversed saturation current with increased
VOC [77]; 3) excellent material qualitiespotentially defect
free; and 4) high absorption coefficient. In order to clearly illustrate the potential of compound semiconductor NW solar cells,
particularly due to the rational control over NW and heterostructure growth, we briefly summarize the advances in NW syntheses, and then focus on recently reported III/V and II/VI NW solar
cells.
1) Synthesis IIIV NWs: (Catalyst growth): Various metals,
such as Au, Pt, Ni, Ag, Al, as well as alloys such as Au/Pd,
have been used as agents for VLS NW (IV, III/V, and II/VI)
growth [78]. The most commonly used techniques for IIIV NW
growth include metalorganic CVD (MOCVD)/organicmetal
vapor phase epitaxy (OMVPE) [49], [79], [80], molecular beam
epitaxy (MBE) [81], [82], chemical beam epitaxy (CBE) [83],
[84], CVD [63], and laser ablation [85]. During VLS growth,
these agents act as sinks for atomic precipitation, resulting in
supersaturation that drives NW growth. With the exception of
group IV elements, little is known about these multicomponent
eutectic phases [86], but interactions between metal catalyst
and IIIV semiconductors have been studied, resulting in an expanded understanding of different growth behaviors [87][91].
Tremendous effort has been made by various research groups
to study the mechanisms of catalyzed InAs NW growth using
MOCVD [92][95]. It was discovered that adatom surface diffusion rates play a significant role in determining NW growth
rate and morphology. A recent review paper has summarized
position-dependent growth rates affected by adatom diffusion
at the catalytic tip, NW sidewall and substrate that are linear,
exponential, and parabolic, respectively [96]. Through catalyst
patterning [97], [98], NW growth can be confined to specific
locations allowing for the fabrication of arrays, as shown in
Fig. 4(a) [95]. Recently published data have demonstrated the
capability of growing NWs with square or rectangular cross
sections by simply controlling catalyst patterns [99].
Fig. 4. IIIV NW growth. (a) Catalyst growth of InAs using dispersed Au

particle (reproduced with permission from [95] copyright American Chemical
Society), (b) catalyst-free growth of InAs on Si substrate (reproduced with permission from [5] copyright American Chemical Society), (c) AlGaN/AlN/GaN
core/shell/shell NW (reproduced with permission from [124] copyright
American Chemical society), (d) InAs/InP NW with radial junction (reproduced with permission from [123] copyright American Chemical Society), and
(e) InAs/InP NW with axial junction (reproduced with permission from [84]
copyright American Institute of Physics).
Catalyst-free growth: Catalysts in VLS growth such as gold

provide preferential growth along a single axis even on latticemismatched substrates and are capable of accommodating strain
in two dimensions [1 0 0]. However, catalytic growth has presented some serious limitations. For example, it is believed that
gold atoms provide deep impurity levels in Si [1 0 1]; therefore, catalyst-free VLS growth on lattice mismatched substrate
is desired for electronic and optoelectronic applications. Mechanisms of catalyst-free NW growth include self-catalyzed VLS
through group-III elements [102], oxide-assisted growth [103],
[104], formation of facets [80], ligand-aided solutionsolid
growth or Si-assisted growth [5], and selective-area MOVPE
[105], [106]. It is believed that catalyst-free growth is not
a single-mechanism-governed process, but is multiple-factorcontrolled with nucleation and growth at the same condition.
Factors such as, growth temperature [80], IIIV ratio [107], precursor flux rate [82], partial pressure [102], and substrate orientation [108], [109] have been extensively studied in order to determine their effects on NW crystallinity, orientation, and morphology. Of particular interest is the large area hetero-epitaxy
of IIIV NWs on Si substrates by MOCVD [5], [103], [110],
[111] [see Fig. 4(b)], which enables the fabrication of lowcost high-efficiency IIIV solar cells. Many challenges remain
including, large-scale, low cost, reproducible/controllable synthesis of high quality, uniform, single crystal NWs, and heterostructure arrays on Si substrates and other cheap and/or flexible substrates.
2) Core/Shell NW Growth: As discussed in previous sections, the core/shell NW geometry offers enhanced separation
and collection efficiency of photogenerated carriers. Moreover,
the effective relaxation of lateral strain in coaxial heterostructured NWs can enable high-quality integration of materials
with large lattice mismatches [112]. Controllable doping and
composition modulation in NWs is critical, yet challenging
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for PV applications, especially in the case of GaAs and its

alloys, which have a large optical absorption coefficient and
an almost ideal band gap, but include a drawback, high surface
recombination velocities. Synthesis of p-i-n GaAs NWs with
Si-doped p-core and n-shell synthesized on SiO2 -coated (1 1 1)
GaAs substrate using MBE system has been demonstrated
by Morral et al. [113]. By switching dopants during growth,
LaPierres group has reported the growth of GaAs core/shell
NWs on GaAs (1 1 1)B substrates using Te instead of n-type
dopants [58]. In-situ doping on other material systems has also
been studied [114][117], along with other methods such as ion
implantation [118], [119]. However, nanoscale doping is still
challenging. The formation of compound heterostructures, such
as InP/InAs [105] or GaAs/GaP [120], InAs/GaAs [121] and
AlN/GaN [122][124] have been widely studied, leading to a
fundamental understanding that defect/stacking fault formation
in NW growth is due to a difference in supersaturation and
interfacial energy between III and V elements [125][129].
Fig. 4(c) and (d) shows the cross section of an AlGaN/AlN/GaN
core/shell/shell NW and high-resolution TEM image of an
InAs/InP core/shell NW [84], [123]. For NW solar cells,
core/multishell InP/InAs/InP grown using catalyst-free
selective-area MOVPE has been reported by Fukui and
coworkers [105], and synthesis of n-i-p InAs/GaAs/InGaP/GaP
core-multishell NWs on Si using MOCVD has been demonstrated by our group [121]. The successful control of radial
versus axial growth [130] demonstrates the potential for
building NW array solar cells with radial multijunction/MQW
foundations [105], [106]. However, due to the low surface
recombination velocity and high hole mobility, IIIV NW systems suffer from high sensitivity to surface defects, bulk defects,
and arsenic-antisite defects [131], all of which lead to degraded
quantum confinement, discontinuous electron wave functions,
reduced carrier lifetimes, and thus, poor electronic properties [132]. It is for this reason that controlling the crystalline
structures and defect density in IIIV NWs is of paramount
importance to improving their performance in solar-cell applications. A number of approaches have been demonstrated, such
as tuning their crystalline structure by varying the diameter and
growth temperature [126] and instituting control over twinning
defects, stacking faults [133] and kinks [134] by tuning the
growth parameters, changing growth direction from <111> to
<100> or <110> [117], and modifying the doping level [135].
3) Axial Junction NW Growth: Although less attractive to
PV applications, the NW axial junction solar cell structure, with
vertically stacked, varied band-gap semiconductors has drawn
interest in wideband solar-energy harvesting [see Fig. 4(e)],
in particular multijunction IIIV NWs, graded composition,
and MQW structures. The capability to form compositionally abrupt and structurally perfect junctions [136] by controlling the switching process via VLS catalytic growth is
fairly hard, due to the NW/catalyst interfacial energy difference [137]. Experimental work has been demonstrated in the
growth of InAs/InP/InAs [84] (using CBE), GaAs/InAs [137]
and InAs/GaAs (with suppressed change in growth orientation),
GaP/InP [138], GaSb/GaAs [139], and InAs/GaInAs/InAs axial
heterojunction NWs [140], etc., or by the catalyst-free growth
of GaAs/Inx Ga1x As/GaAs heterostructure from Ga/In alloy

droplets using MBE [141] and GaAs/GaAsSb/GaAs axial heterostructure NW on Si substrates also using MBE [142]. Nevertheless, further issues include, the synthesis of axial IIIV heterostructures with perfect crystalline segments, interface sharpness between segments, and minimization of defects/stacking
faults, all of which remain technically challenging.
C. IIIV Semiconductor Nanowire Solar Cells

There is significant interest in using IIIV compounds for
PV applications [5], [59], [60], [68], [124], [125]. III-nitrides
are very attractive due to large energy band tunability, from
ultraviolet (UV) to infrared (IR). GaN, in particular, has
several advantages including high carrier mobility, p- or n-type
selectivity [143], high stability, and a broad band gap for wide
spectrum coverage [144]. In addition, the dislocation defect
density due to lattice mismatch between NW and substrate
is potentially lower when compared to thin films. Vertically
aligned GaN nanorod arrays on Si substrates are of particular
interest for solar-cell applications, because GaN nanorod arrays
can reduce minority carrier recombination, rate increase optical
absorption at high frequencies, and decrease loss at visible
frequencies due to its antireflection property. The fabrication
of p-type GaN nanorod arrays on n-type Si substrates have
been reported [49], and good rectification characteristics, small
reverse currents and a maximum conversion efficiency of 2.73%
were achieved. Dong et al. [112] experimentally demonstrated
the synthesis of n-GaN/i-Inx Ga1x N/p-GaN core/shell/shell
NW solar cells using MOCVD. The variation of indium mole
fraction was used to control the active layer band gap and
light absorption. Electroluminescent (EL) measurement further
demonstrates band-gap tunability of the Inx Ga1x N active
layer (2.253.34 eV). The single NW device simulated with
AM 1.5G illumination yielded a maximum efficiency of 0.19%
with an Indium composition of 27%.
Another attractive candidate for PV applications of group III
V material is GaAs due to its large light absorption coefficient
and ideal band gap for solar-cell applications. LaPierres group
has fabricated GaAs NW radial p-n junction solar cells using
MBE [58], where Te and Be were used for n-type shell and
p-type core doping. The fabricated NWs show different morphologies due to the inclusion of dopants during NWs. growth.
Although the cell exhibits rectifying characteristics, the leakage
current is high, which can be explained based on the low breakdown voltage and possible tunneling effects. This cell shows
a low efficiency of 0.83%, which were partly due to the formation of nonuniform core/shell p-n junctions. The conversion
efficiency reduces reduced as the Te-doped growth duration increases, which may lead to lower shunt resistance. In another
study, Colombo et al. reported the fabrication of GaAs core/shell
NW p-i-n junction solar cells, consisting of a p-type core, intrinsic and n-type shell using MBE [15]. The achieved conversion
efficiency for this single NW solar cell structure is 4.5%, which,
to the best of our knowledge is the highest reported efficiency for
IIIV NW-based solar cells. The intrinsic layer between n- and
1041
p-type materials in the p-i-n junction cell [15] increases its cell
conversion efficiency over conventional p-n junction cells [58].
Goto et al. [145] reported high-quality core/shell InP NW
arrays for PV applications grown by a selective-area MOCVD,
with an overall conversion efficiency of 3.37%. This is attributed
to the higher optical absorption coefficient and the band-gap energy of InP, which is more optimally matched to the solar spectrum than Si [146]. Previous work from our group demonstrates
heteroeptaxial growth of vertical InAs NW arrays on Si using
catalyst-free MOCVD [5]. This type of solar cell with multipleband-gap absorber materials, InAs and Si, can efficiently harvest
solar energy due to enhanced broad-band light absorption.
The capability of forming heterostructures comprised of
IIIV semiconductors is another attractive feature, allowing
for the formation of multijunction solar cells, such as tandem
stacked multiple p/n junctions and axial or radial MQW structures. Similar to multi junction structures in planar solar cells,
tandem cell and MQW structured NW solar cells are believed
to offer much improved power conversion efficiency.
IV. GROUP IIVI NANOWIRE SOLAR CELLS
IIVI compound semiconductor NWs, such as CdS
[147][149], CdSe [148], [150], CdTe [150], ZnSe [151], ZnTe
[152], ZnO, and PbSe [153] can be produced by low-costsolution-based methods, thereby reducing the costly thermal
expenditures necessary to the production of group IV and III
V compound devices. This has increased the allure of developing IIVI compound semiconductor NW-based PVs. Moreover, these materials carry the intrinsic benefits of inorganic
nanomaterials, i.e., high carrier mobility, robust material stability, and high interfacial area. Research effort is needed to
explore the use of IIVI semiconductor NWs in conjunction
with semiconductor dyes and organic polymers in hybrid solar
cells to substantially increase their efficiency, and viability. Unfortunately, IIVI materials are limited by their native defects.
Controlled doping in IIVI semiconductors is still technically
challenging [154], [155], particularly for IIVI NWs grown by
low-temperature synthesis methods.
A. Core/Shell Nanowire Solar Cell
ZnO NWs are the most researched metal oxide semiconductor and have received a great deal of attention due to their ease
of growth, rich optical/electrical/piezoelectric properties and a
promising variety of applications. ZnOs band-gap (3.37 eV)
limits absorption to the UV portion of solar spectrum and the
materials itself does not promise high-efficiency solar cells [77].
However, ZnO NWs are intrinsically n-type and highly conductive. The NW geometry allows for large junction/contact area
for electron collection [44], [156][158].
Many techniques are employed using smaller band-gap materials to expand the absorbance, which in turn increase the light
harvesting and overall energy-conversion efficiency of the solar
cell. One of the most popular methods is to fabricate core/shell
structure by coating ZnO NWs with uniform thin film shell(s)
of IIVI group materials [158], [159], as shown in Fig. 5(a) and
(b). The core/shell type-II heterojunction between the ZnO NW
Fig. 5. IIVI NW solar cells. (a) Coreshell ZnO/CdS NW array (reproduced

with permission from [157] copyright Royal Society of Chemistry), (b) CdSe
QDs decorated ZnO NW solar cell (reproduced with permission from [158]
copyright American Chemical Society), (c) template free synthesis of CdS NW
array (reproduced with permission from [146] copyright American Chemical
Society), and (d) CdSe NWs in P3HT polymer (reproduced with permission
from [159] copyright American Association for the Advancement of Science).
and the semiconductor surrounding lead to effective charge separation, with the shell acting as an absorber/a generation site and
the ZnO NW core as an electron transporter [159], [160]. TypeII core/shell heterojunction solar cells provide advantages of
1) broadening the absorbed solar spectrum through weak interfacial transitions [44], 2) increasing the carrier lifetime due
to the slow electronhole recombination in the spatially charge
separated region [161] and minimizing radiative recombination
losses [162]. On the other hand, for effective transport of electrons in ZnO core and holes in shell, it is important to be able to
finely adjust the thickness of the cell to maximize the generation
of charge pairs while maintaining effective transport.
Theoretical work of effective charge separation is demonstrated by Zhang et al. [57], followed by experimental demonstrations using ZnO/ZnS and ZnO/ZnSe core/shell NWs [45],
[145]. Experimentally, Tak et al. are able to synthesize a
ZnO/CdS core/shell NW array, and moreover, tune the light
absorption spectrum by altering the thickness of the CdS shell
[158]. The thickness of the CdS is controlled by successive ion
1042
layer absorption and reaction. This technique is effective at providing a uniform and adjustable shell, enabling the optimization
of light absorption and carrier generation. The resulting performance boosts the JSC of the ZnO array from 0.37 mA/cm2
without a CdS shell to 7.23 mA/cm2 with a CdS shell and a
maximum power conversion efficiency of 3.53% is achieved.
ZnO/ZnSe core/shell NWs are also synthesized, although no
solar cell devices are characterized so far [44] [see Fig. 5(c)].
Fan et al. have demonstrated the growth of CdS NWs in anodic
aluminum oxide (AAO) templates using a VLS and embedded
in a CdTe thin film [163]. Further work by the same group has
demonstrated that CdS/CdTe NW heterostructures are capable
of realizing efficiencies >20% due to low recombination velocities at the interface [164].
B. SCSSCs and QDs/NW Solar Cells

The development in colloidal synthesis of 3-dimensional
confined QDs has boosted PV techniques [165], [166], due
its unique properties. These advantages include tunable band
gap [146][148], hot electron utilization [167], and multiple exciton generation [156], [168][172]. QDs such as CdS [143],
CdSe [173], CdTe [174], Sb2 S3 [175], PbS [168], [176], [177],
PbSe [167], InAs [171], InP [178], and Si [179], etc., extend
the absorption spectrum to VIS-IR range. Electrodes in NW
array configurations improve the transportation of electrons
rapidly, directly, and efficiently to the contact, compared to the
particle-to-particle hopping effect normally seen in NP configurations [159]. NWs also provide large surface-to-volume ratio
suggesting a large coverage of QD sensitizers, and thus, a high
quantum yield of phonon-to-electron efficiency.
One of the QD SCSSCs that has been tested to increase the PV
efficiency is CdSe. CdSe-decorated ZnO NWs show increased
absorbance. Without QDs, device produces very little photocurrent in the 400600 nm range. On the contrary, with CdSe QDs
there was a substantial photocurrent in this range [159]. CdSe
QDs form a type-II heterojunction with ZnO NWs allowing the
electron to be injected into ZnO NWs after being generated in
less than a nanosecond. Likewise, holes are able to leave the
QDs via an electrolyte. Unfortunately, the use of electrolyte
breaks down QDs, which will contaminate the electrolyte and
devices would degrade as well. Therefore, future technology
will probably have to find an alternative hole transport medium
rather than an electrolyte solution [156], [159]. The other example is using freestanding ZnO NWs with successive layers CdSe
(Eg = 1.7 eV) and CuSCN (Eg = 3.4 eV) composite nanostructures. This is synthesized through electrochemical and chemical
bath deposition techniques [160]. The substantially increased
surface area of the nanostructured interface allows for a reduced
thickness of the absorber layer. Meanwhile, devices exhibit an
effective absorption of 89% in the 400800 nm range [160].
C. Nanowire Hybrid Solar Cell

NWpolymer hybrid solar cells capitalize on the high electron affinity of inorganic semiconductors, and the low ionization
energy of organic polymers to generate fast Foster charge transfer [180]. Such hybrid solar cells utilize large absorption coefficients of polymers and large electron mobilities in inorganic
IIVI semiconductors. A high energy-conversion efficiency is
empowered by the fast charge separation between the donor
(polymer)/host (NWs).
High electron affinity of inorganic semiconductors and the
low ionization energy of organic polymers promise a fast charge
transfer rate [180]. Hybrid systems based on metal oxide, such
as ZnO [181][184] and TiO2 [185], [186] nanostructures are
widely investigated. TiO2 /ZnO coreshell [187] and CdS/ZnO
coreshell [188] heterostructures are also proposed to improve
device performances.
The other kind of compound semiconductor studied in hybrid
system is Cd-VI compounds, such as CdSe, CdS, and CdTe. Vertically aligned NW structures based on these materials can be
fabricated using various methods, such as electrodeposition in
AAO templates [189], [190], electroless deposition based on
solutionliquidsolid (SLS) mechanism [147], [191], and gasphase VLS growth [192]. Hybrid solar cell is then finished by
spin-coating photoactive polymers onto the surface of NWs. Devices containing the vertically aligned IIVI NWs show a drastic
improvement in energy-conversion efficiency over a polymer or
NW only device [190], [192].
By combining solution-phase-synthesized colloidal CdSe
nanorods with poly(3-hexylthiophene) (P3HT), this blend
solar cell shows improved absorption in the spectrum of
300720 nm and with tunable absorption spectra by controlling
the diameter [191]. The effect of aspect ratio on the performance is also characterized [180]. Devices containing nanorods
with higher aspect ratio demonstrated greater efficiencies, due
to improved charge mobility in longer nanorods. Moreover,
interface in hybrid system is critical for overall efficiency. It
was demonstrated that the efficiency of a polymer/CdS solar
cell can be increased through the use of pyridine as a solvent
when spin coating the active layer of the device [189]. Sample
processed using pyridine demonstrates a more even dispersion
of the nanotetrapods, which contributes to the increased efficiency [189]. Samples processed with chlorobenzene demonstrated power conversion efficiencies of 0.14% while those processed with pyridine showed efficiencies of 0.89%, which is
further increased to 1.17% through thermal annealing [189].
The solvent effect and the thermal treatment are believed to create phase separation and conducting polymer networks, which
leads to higher hole mobilities and consequently lower series
resistance [189].
For hybrid solar cells, vertical NW array offers: 1) improved
light absorption, 2) direct conducting pathway to electrode contact, and 3) potential guidance for aligned polymer morphology,
which leads to higher hole mobilities.
Although as for now efficiencies of the IIVI semiconductorbased devices are low compared to other classes of solar
cell, benefits of using group IIVI materials include low cost
of production, general abundance of materials, as well as
environmental-friendly. Through the research mentioned above,
it is clear that because of their economic feasibility, IIVI
compound semiconductors have good potential to replace or
1043
combine with some of the existing technologies to further improve solar cell performance.
V. CONCLUSION AND PERSPECTIVES
NW PVs have drawn great interests for research and development globally in both academia and industry. To conclude,
semiconductor NWs, particularly vertical NW arrays, offer advantages for PV applications, such as enhanced light absorption
and improved separation and collection efficiencies of photogenerated carriers. Furthermore, the capability of doping, alloying, and heterostructure formation at nanoscale enables band
gap and strain engineering along the nanowires axial and radial directions. Further improvements to light absorption and
charge separation/collection are realized by constructing tandem, MQW or superlattice NW solar cells. Moreover, NW
array PV devices decrease fabrication costs by reducing the
amount of required material, allowing the use of various substrates, through the capability of growth on lattice mis-matched
or amorphous substrates, and through the use of low-cost fabrication methods. Despite these advantages, the best reported
efficiency for NW solar cells is less than 10%, much lower
than the 41.1% energy-conversion efficiency achieved by thinfilm devices. We believe there is plenty of room for improvement of device design/modeling, rational growth, and the reproducible/controllable fabrication of NW devices. Also, there
exists great opportunities for NW-stacked multijunction arrays
for high-efficiency solar cells, light weight, flexible and printable PVs, low-cost and environmentally green processing, and
reduced material consumption.
Ultrahigh efficiency: Maximum efficiencies of 30% for single
junction solar cell [193], 72% for ideal 36-multijunction solar
cell [194], 68% for infinite stack of p-n junction solar cell with
graded band gap [195], [196], and 70% of intermediate band
solar cell [197], under 1 sun illumination is theoretically predicted based on the thermodynamic limits. All these efficiencies
were calculated based on thin film solar cells. With the promise
of engineering for near unity light absorption, efficient charge
separation and collection, compound semiconductor NW solar
cells have the potential to lead a new generation of the PVs with
superior conversion efficiency.
Light weight/portable, flexible, printable PVs: Light
weight/portable, flexible/foldable/stretchable solar cells are particularly interesting for various medical, military and civil applications, such as smart PV clothing, tents, beach umbrellas, curtains, etc. Both flexible organic and inorganic thin film solar cell
devices produced by various methods have been reported [198],
[199]. One possible approach is to embed micro- or nanoscale
solar cell devices into flexible polymers and transfer them from
the source substrate to the flexible carrier substrate. The most
widely used polymer is polydimethylsiloxane (PDMS). Si microwires from VLS growth are embedded into PDMS and peeled
off from source Si substrate. Lewis and Atwater have successfully demonstrated the application of this flexible device in PEC
solar cells [35], [200], shown in Fig. 6(a) and (b). The polymer supported, flexible, and inexpensive Si wire film shows
nondegradation in energy conversion performance comparing
Fig. 6. Current development in flexible NW solar cell devices: (a) SEM image of VLS silicon wire array, (b) SEM image of Si wires embedded in PDMS
polymer demonstrating flexible feature (insets show optical diffraction patterns)
(reproduced with permission from [35] copyright Wiley Inter-Science), (c) CdS
NW array embedded in AAO tempalate, and (d) devices with CdTe film embedded in PDMS demonstrating flexible feature (reproduced with permission from
[163] copyright Nature Publishing Group).
to the original unpeeled source substrate. Javeys group has

demonstrated similar devices, where n-CdS NWs are grown
via CVD using an AAO template, which is then coated with a
layer of p-CdTe film, and finally embedded in PDMS elastomer.
This flexible device is shown to sustain large bending without
structural and device performance degradation [163]. Along the
same line, researchers around the world are developing flexible
transparent electrode contact for the replacement of a layer of
traditionally used TCO film, which is brittle and unstretchable,
by using networks of metal NWs [201][205], carbon nanotubes
(CNTs) [206][209] and graphene [210], [211].
Cost effective and environmental friendly manufacturing process: NW solar cells utilize less material than thin film cells with
comparable absorption and conversion efficiency [18]. Generally, less material means cheaper solar cell devices. However,
a cost-effective manufacturing process has to be considered as
well. This cost is limited by the fact that NWs are easy to process
on high quality source substrates. Controlled growth of vertically aligned NWs on low-cost amorphous source substrates is
challenging. Therefore, research has focused on different routes
of reducing substrate cost. Novel techniques for handling NW
structures efficiently have been proposed. Releasable nanostructure through sacrificial etching [212], dry transfer [213], [214],
and soft transfer [163], [200] on to carrier processing substrates
have been widely used for NW-based devices, which could potentially offer a new scheme of fabrication using reusable source
substrates.
Self-cleaning: Retaining physical geometry and chemical
composition in nanostructured solar cells is critical for stable and uniform performances. Particles accumulated on solar panel coverings scatter light and reduce light absorption.
Routine maintenance to remove dirt, grime, bird droppings, or
1044
even snow is required to maximize energy production capacity. Self-cleaning features for the solar panels, particularly in
the unreachable area, is desired [25]. The photocatalytic [215],
[216] and superhydrophobic properties [217][219] offered by
vertical nanostructure arrays lead to unique and very interesting
self-cleaning capabilities.
Stability: Long-term stability and robustness is primarily discussed in polymer and hybrid solar cells [220] and DSSCs [221]
but not the NW array solar cells. Retaining physical geometry
and chemical composition, and thus related optical and electrical properties, in harsh environments are critical for stable
and uniform device performances. Long-term robustness and
stability of NW solar cells are needed and still require further
evaluation.
Device design/modeling, contact for effective charge
collection: Transportation of photogenerated electrons and holes
to ohmic contacts after charge separation is critical for the contribution to external current (output power), as discussed in earlier
section. Computer-assisted design, modeling of NW solar cell
devices and contacts, along with the fabrication, will enable
optimization of carrier collection and efficiency.
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
ACKNOWLEDGMENT
K.M. and P.N. would like to thank UCSD Cal-IT2 summer
undergraduate fellowship as part of the support of this work.
T.B. wants to appreciate UCSD Summer Training Academy for
Research in the Sciences (STARS) Fellowship Program for the
support.
[23]
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Ke Sun (S07) received the B.S. degree from Beijing

Institute of Technology, Beijing, China, in 2003, and
the M.S degree from the University of South Florida,
Tampa, in 2009. Since 2009, he has been working
toward the Doctoral degree in ECE, UC, San Diego.
His current research interests include renewable
solar-energy-related topics using IIIV nanowires
(NWs) synthesized from metalorganic chemical vapor deposition (MOCVD) and ZnO-based
heterostructures.
Mr. Sun is currently an active Student Member of
the Society of Photo-Optical Instrumentation Engineers (SPIE), Electrochemical Society (ECS), and The Minerals, Metals and Materials Society (TMS).
Alireza Kargar (S08M08) received the B.S. degree from Shiraz University, Shiraz, Iran, in 2008.
He is currently working toward the M.S. degree in
the Department of ECE, University of California at
San Diego (UCSD), La Jolla.
His research interests include nanomaterial-based
photovoltaics, nanoelectronics, nanofabrication, and
nanophotonics.
Mr. Kargar is a Student Member the Optical Society of America (OSA) and the Society of PhotoOptical Instrumentation Engineers (SPIE).
Namsoek Park received the B.S. degree in electrical engineering in 2004 from Inha University, Incheon, Korea. He is currently working toward the
M.S. degree in the Department of ECE, University of
California at San Diego (UCSD), La Jolla.
He was with the ARMY for two years as an
Administrative Specialist. His current research interests include the synthesis of transparent oxide semiconductors such as ZnO, NiO, and Cu2 O, and their
applications in optoelectronics.
1049
Kristian N. Madsen (S10) is currently with the University of California at San Diego (UCSD), La Jolla,
where he is completing his senior year as an undergraduate in the Department of ECE.
He is currently a Volunteer in Dr. Wangs lab at
UCSD. He was engaged in several fields of engineering including civil, mechanical and electrical, playing
a primary role in design development. His current research interests include nanoengineering, materials
science, and development of low-cost semiconductors for alternative energy.
Perry W. Naughton is currently working toward the

B.Sc. degree in the Department of ECE, University
of California at San Diego (UCSD), La Jolla.
He completed a position as a Summer Intern at
the World Minerals, and is currently completing a
position as a Summer Research Scholar through the
UCSDs Calit2 program. His current research interests include fabrication of low-cost solar cells using
the spray pyrolysis deposition method.
Mr. Naughton is currently a member in The Minerals, Metals and Materials Society TMS.
Timothy Bright received the B.S. degree in electrical

engineering from Oral Roberts University, Tulsa, OK,
in 2010.
He was a Summer Undergraduate Researcher in
Dr. Wangs group at the University of California at
San Diego (UCSD), La Jolla, during the summer of
2010. His current research interests include flexible
nanoscale sensors, and robotic prosthesis.
Yi Jing received the B.S. degree in physics from

Peking University, Beijing, China, in 2005, and the
M.S. degree in electrical engineering in 2007 from
the University of California at San Diego (UCSD),
La Jolla, where he is currently working toward the
Ph.D. degree.
His current research interest include Si and IIIV
semiconductor nanowires for applications of photovoltaics and photodetectors.
Mr. Jing is a Student Member of the Society of
Photo-Optical Instrumentation Engineers (SPIE).
Deli Wang received the Ph.D. degree in materials

sciences from University of California (UC) at Santa
Barbara in 2001.
He was a Postdoctoral Fellow at the Harvard
University. In 2004, he joined the Jacobs School of
Engineering, University of California at San Diego
(UCSD), La Jolla, where he is currently an Associate
Professor in electrical and computer engineering.
His current research interests include nanomaterials,
nanofabrication, electronics, optoelectronics, bionanotechnology, nanomedicine, and renewable energy.
He has authored or coauthored more than 45 scientific articles. He holds five
U.S. or pending patents.

(Nano Fios Si Fotovoltaico) - (Sun, K, 2011) - Compound Semiconductor Nanowire Solar Cells

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(Nano Fios Si Fotovoltaico) - (Sun, K, 2011) - Compound Semiconductor Nanowire Solar Cells

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IEEE JOURNAL OF SELECTED TOPICS IN QUANTUM ELECTRONICS, VOL. 17, NO.

Compound Semiconductor Nanowire Solar Cells

materials offer very attractive advantages in photon absorption

where is the overall efficiency, and i = a, g, s, and c represent

1077-260X/$26.00 2011 IEEE

[see Fig. 1(a)]. p/n junctions in NW solar cells can be formed

strates minimum sensitivity to the AOI compared to periodically

SUN et al.: COMPOUND SEMICONDUCTOR NANOWIRE SOLAR CELLS

which also shows dependence on the extinction coefficient of

detail in existing textbooks and will not be repeated here. NW

Recent interest has focused on strain engineering of Si NWs to

D. Charge Collection in NWs

erations must be made with respect to some of the geometric

SUN et al.: COMPOUND SEMICONDUCTOR NANOWIRE SOLAR CELLS

doping and morphology [8], [60]. Si NWs have been applied to

por deposition (CVD) [8], resulting in a. conversion efficiency

efficiency of 0.46%. When compared to single radial p-i-n NW

effects, compounded by the ultrahigh surface area of the NW

SUN et al.: COMPOUND SEMICONDUCTOR NANOWIRE SOLAR CELLS

Fig. 4. IIIV NW growth. (a) Catalyst growth of InAs using dispersed Au

Catalyst-free growth: Catalysts in VLS growth such as gold

for PV applications, especially in the case of GaAs and its

of GaAs/Inx Ga1x As/GaAs heterostructure from Ga/In alloy

C. IIIV Semiconductor Nanowire Solar Cells

SUN et al.: COMPOUND SEMICONDUCTOR NANOWIRE SOLAR CELLS

Fig. 5. IIVI NW solar cells. (a) Coreshell ZnO/CdS NW array (reproduced

B. SCSSCs and QDs/NW Solar Cells

C. Nanowire Hybrid Solar Cell

SUN et al.: COMPOUND SEMICONDUCTOR NANOWIRE SOLAR CELLS

to the original unpeeled source substrate. Javeys group has

surements in single-nanowire silicon solar cells, Nano Lett., vol. 8,

SUN et al.: COMPOUND SEMICONDUCTOR NANOWIRE SOLAR CELLS

in Si wire arrays for photovoltaic applications, Nat. Mater., vol. 9,

terface and photovoltaic cell on a single nanowire, J. Phys. Chem. Lett.,

SUN et al.: COMPOUND SEMICONDUCTOR NANOWIRE SOLAR CELLS

[127] R. E. Algra, M. A. Verheijen, M. T. Borgstrom, L.-F. Feiner, G. Immink,

reduction by photodoping in colloidal InAs quantum dots, J. Phys.

[193] S. William and J. Q. Hans, Detailed balance limit of efficiency of p-n

SUN et al.: COMPOUND SEMICONDUCTOR NANOWIRE SOLAR CELLS

[218] M. Wei-Lun, J. Bin, and J. Peng, Bioinspired self-cleaning antireflection

Ke Sun (S07) received the B.S. degree from Beijing

Perry W. Naughton is currently working toward the

Timothy Bright received the B.S. degree in electrical

Yi Jing received the B.S. degree in physics from

Deli Wang received the Ph.D. degree in materials

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