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Materials Chemistry
Cite this: J. Mater. Chem., 2012, 22, 19
www.rsc.org/materials HIGHLIGHT
Metal sulfide nanostructures: synthesis,
properties and applications in energy conversion
and storage
Chen-Ho Lai, Ming-Yen Lu and Lih-Juann Chen*
Published on 10 November 2011. Downloaded on 4/18/2024 6:16:48 PM.

DOI: 10.1039/c1jm13879k

Metal sulfide nanomaterials have attracted great attention because of their excellent
properties and promising applications in electronic, optical and optoelectronic devices. Well-
aligned nanostructure arrays on substrates are highly attractive for their enhanced properties
and novel applications. The general solution route and thermal evaporation under controlled
conditions have been utilized for oriented growth of various metal sulfide nanostructure arrays
and demonstrated their applications in energy conversion and storage. The article provides an
overview of recent research and significant advances reported in the literature, covering from
synthesis to properties and to applications especially in energy conversion and storage, such
as lithium-ion batteries, solar cells, fuel cells and piezoelectric nanogenerators.

Introduction dimensions of such materials, and the fuel cells, piezoelectric nanogenerators
entire behaviors of nanostructured mate- and lithium-ion batteries.5,6 One-dimen-
Nanostructured materials have attracted rials show combinations of surface and sional (1D) nanostructures are ideal for
great interest due to their electrical, bulk properties.1–4 Low-dimensional investigating the dependence of electrical
optical, magnetic and mechanical prop- nanostructured materials have been transport, optical and mechanical prop-
erties contributed by confining the successfully synthesized and have drawn erties on size and dimensionality. Well-
much attention because of their funda- aligned one-dimensional nanostructures
mental roles in understanding the on substrates are highly attractive for
Department of Materials Science and
Engineering, National Tsing Hua University, quantum size effect and great potential device applications in particular. They are
Hsinchu, Taiwan, Republic of China. E-mail: applications in light-emitting diodes, gas expected to play key roles as both inter-
ljchen@mx.nthu.edu.tw; Fax: +886-3-5718328; sensors, nanothermometers, solar cells, connects and functional components in
Tel: +886-3-5731166

Chen-Ho Lai received his BS in Ming-Yen Lu studied Materials

Mechanical Engineering from Science and Engineering at
National Central University in National Tsing Hua University
2005 and his PhD in Materials in Taiwan where he also received
Science and Engineering from his PhD degree in 2009 working
National Tsing Hua University on synthesis and applications of
in 2011 under the supervision of ZnS-based nanostructures under
Prof. Lih-Juann Chen. His the supervision of Prof. L. J.
research interests include the Chen. He is currently a post-
controlled synthesis and charac- doctoral fellow with Prof. L. J.
terization of various metal chal- Chen and Prof. S. Gwo (physics,
cogenide nanostructures with National Tsing Hua University,
novel applications in electronics, Taiwan). His research interests
Chen-Ho Lai optoelectronics, and energy Ming-Yen Lu include flexible electronic nano-
conversion and storage devices. devices, in situ TEM observa-
tions for dynamic study on solid state and liquid reactions, and III-
Nitride nanostructures for solid state lighting.

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developing new generation nanodevices opportunities to improve performance of semiconductor photocatalyst to remove
with high performance.7,8 Many unique these renewable energy conversion and toxic or organic water pollutants owing to
and excellent properties have already storage technologies due to their unique the highly negative reduction potentials of
been proposed or demonstrated in recent characteristics. Nanostructured materials excited electrons and the rapid generation
years, such as lower turn-on voltage for are potential materials for renewable of electron–hole pairs.11 Copper sulfide
field emitters, superior mechanical energy conversion and storage. Advan- (Cu2S) is an important p-type semi-
toughness, higher efficiency for solar cells, tages include (i) improving cycle life with conductor and has great potential appli-
enhancement of thermoelectric figure of better flexibility, (ii) providing additional cations as cathode materials for lithium-
merit and better electrochemical perfor- reactive sites and catalytic activity, (iii) ion batteries, solar radiation absorbers
mance for lithium-ion batteries.9,10 Two- improved conductivity of the developed and nonlinear optical materials.7 It is
dimensional (2D) nanostructures, such as composite nanostructured materials re- appealing as an extremely thin absorber
nanoplates, nanosheets and nanowalls, sulting in the decrease of inner resistance layer in solar cells due to its nearly ideal
are suggested to be ideal components for and Ohmic loss, and (iv) short path bandgap of 1.2 eV and low cost. Cu2S can
nanoscale devices used in biological lengths for transport of electrons.14,15 also be used as nanoscale switches
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sensors, nanoswitches and data storage Nanostructured metal sulfides have because it is a mixed Cu ionic/electronic
due to their high surface-to-volume ratio, been extensively studied due to their conductor.21,22 Transition metal sulfides
nanometre-scale thickness and fasci- importance in interpreting quantum size such as cobalt sulfide (Co9S8) and nickel
nating optical and photocatalytic effects and applications in a variety of sulfide (Ni3S2) are very important hydro-
activities.11 devices, such as solar cells, light-emitting desulfurization (HDS) catalysts because
One of the great challenges in the 21st diodes, sensors, thermoelectric devices, they are stable under severe sulfo-reduc-
century is undoubtedly energy conversion lithium-ion batteries, fuel cells and tive conditions in hydroprocessing of
and storage. The present energy- nonvolatile memory devices.16–18 Metal petroleum-based feedstocks. Nickel
conscious society calls for light-weight, sulfides are a major group of minerals that sulfides are very interesting materials
low-cost, high-efficiency and environ- provide the crystal chemist a rich field for because of their potential as a trans-
mentally friendly renewable energies due investigation due to their diverse struc- formation toughening agent for materials
to the increasing demand for oil and tural types. They are abundant and cheap used in the semiconductor industry,
environmental issues.12 Much important since they usually exist in nature as coating for photogalvanic cells, hydrogen
progress has been made in the develop- minerals such as heazlewoodite (Ni3S2), storage, cathode materials for lithium-ion
ment of advanced energy conversion and chalcocite (Cu2S), pyrite (FeS2) and so on. batteries, anode materials for solid oxide
storage technologies such as solar cells, We have synthesized various metal sulfide fuel cells, selective hydrogenation of
biofuels, piezoelectric nanogenerators, nanostructure arrays, such as ZnS, Cu2S, chloronitrobenzene and electrocatalysts
fuel cells and lithium-ion batteries. A Ni3S2 and Co9S8. Zinc sulfide (ZnS) is an for cathodic H2 evolution in water elec-
variety of new alternative energy conver- important II–VI semiconducting material trolysis.23,24 Single crystalline Ni3S2 is
sion and storage technologies have been with a wide bandgap energy of 3.7 eV and a good metallic conductor with a room
developed and made renewable energies a large exciton energy (
40 meV). ZnS temperature resistivity of about 1.8 
more competitive with fossil fuels, but nanostructures have versatile potential 105 U cm leading to ease in trans-
they have not been in widespread use due applications as optoelectronic devices due portation for lithium ions and electrons.
to limitation of the materials properties. to their excellent properties of lumines- The magnetic susceptibility of Ni3S2 was
Further improvements are needed to cence and photochemistry, e.g., flat-panel found to be temperature independent,
satisfy the great challenges for today’s displays, injection lasers and light-emit- which is consistent with Pauli para-
information and mobile society.13 Novel ting diodes.19,20 On the other hand, ZnS magnetism.25 The electronic and magnetic
nanostructured materials provide great can also serve as an important properties of Ni3S2 have attracted more
interest which can be ascribed to strong
electron–electron correlation, insulating
ground state and magnetic instabilities.
Lih J. Chen is the President of National Tsing Hua
Recently, Ni3S2 has also been recognized
University (NTHU), Taiwan. He received PhD degree
to have high lithium activity and storage
in physics from University of California, Berkeley in
capacity for fabricating the cathode
1974 and is currently National Chair Professor at the
material of rechargeable lithium-ion
Department of Materials Science and Engineering,
batteries.26,27 Co9S8 has attracted much
NTHU. His main interests in research are synthesis and
attention because of its promising uses as
applications of low-dimensional nanomaterials, atomic
anode materials for solid oxide fuel cells
scale structures and dynamic processes of advanced
(SOFCs), rechargeable lithium-ion
materials as well as metallization in integrated circuit
batteries and supercapacitors. Co9S8 was
devices.
found to have the highest catalytic
activity for dioxygen reduction in acidic
solution among a variety of transition
metal sulfides. Magnetic susceptibility
Lih-Juann Chen
measurement result revealed that Co9S8 is

20 | J. Mater. Chem., 2012, 22, 19–30 This journal is ª The Royal Society of Chemistry 2012
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also of Pauli paramagnetism and can be have been a new and promising focus in synthesized by the thermal evaporation
used for fabricating the magnetic the production of various kinds of metal method using different amounts of
devices.28 Metallic property of Co9S8 may sulfide nanomaterials.32 Besides the CoCl2$6H2O powders as dopant source
also promise potential application as in- reductive properties of biomolecules, they via the vapor–liquid–solid (VLS) growth
terconnector and electrode material for also have strong shape or size directing mechanism.34 Axial heterostructured
lithium-ion batteries.29 functionality in the reaction process.33a ZnO–ZnS NW arrays have been synthe-
Herein we present an overview and Although great progress has been ach- sized based on a one-step thermal evapo-
discuss future promising areas of metal ieved on the synthesis approach, most ration with ZnS powders. Further, ZnS
sulfide nanostructures, covering from growth methods usually require high NW arrays can be obtained by etching the
synthesis to properties and to applications temperature, a series of complicated ZnO top portion away with KOH solu-
in energy conversion and storage. We will procedures, expensive equipment, tion.35 Intercrossed sheet-like ZnS nano-
focus on the electronic, optoelectronic, surfactants, catalysts or templates which structures with Ga dopant (ZnS:Ga
magnetic, piezoelectric and electro- will increase the cost, contamination and nanowalls) have been grown on Si
chemical devices based on potential energy-consumption. Therefore, search- substrates by thermal evaporation of
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applications of oriented metal sulfide ing for a simple, efficient, low cost, and mixed powders of ZnS and Ga2O3 via
nanostructures including lithium-ion environmentally benign approach for the a self-catalyzed growth mechanism.11
batteries, fuel cells, solar cells and piezo- high-yield production of one-dimensional
electric nanogenerators. Furthermore, the metal chalcogenide nanomaterials is
future outlook is addressed. necessary. Properties
Optical properties
Synthesis General solution route
Some of the metallic sulfides in the natural
Metal sulfide nanostructures have been We have developed a facile solution mineral state have very interesting optical
synthesized by a variety of chemical or method for the oriented growth of large- properties. The spectral reflectivities,
physical methods. Among these are solu- scale metal sulfide nanostructure indices of refraction, and extinction
tion-phase reactions,16 hydrothermal arrays.7,27 The preparation strategy indices of Sb2S3, MoS2, PbS, and FeS2
growth,22 high-pressure autoclave combines metal chelation chemistry and have been widely studied.36a Wide-band
processes,23,31 physical vapor deposition dioxygen catalytic reactions. Interactions semiconducting metal sulfide nano-
(PVD)19,20 and chemical vapor deposition between molecules and metal surfaces can structures are good electrically driven
(CVD).30 Deposition-based synthesis result in energy exchange with the elec- lasing material and active optical wave-
methods are the most popular among trons of the metal.33b The coordination of guide material, which may find extensive
these methods. Thermal evaporation ethylenediamine–chalcogen solutions and applications in near-field optical lithog-
methods (PVD and CVD), arc discharge, hydrazine in alkali solution has been raphy and telecommunications. One-
and laser-assisted growth are members of proved to have great advantages for the dimensional nanostructured ZnS and
this group. The most common deposition- fabrication of metal sulfides with fewer CdS have received great attention for
based synthesis methods are PVD and instrumental limitations. This method is various optoelectronic applications, such
CVD.19 These methods consist of the reliable and operates under mild as waveguides, field-effect transistors,
physical transport of the vapor species to template-free conditions for single-crys- lasers, solar cells, photodetectors, thin
the site. In order to grow metal sulfide talline metal sulfide nanostructures film electroluminescent displays and light
nanostructures at lower temperature and production without using high-pressure emitting diodes.36b,c It is very important to
without using catalysts, high-pressure autoclave processes. Fig. 1 shows a series fabricate nanomaterials with continuous
autoclave processes are commonly used of oriented metal sulfide nanostructures tunable physical properties. II–VI group
to overcome the high interfacial energy grown by our method on corresponding materials in the form of superlattices,
between substrate, liquid and particle for metal substrates indicating the generality heterostructures and quantum dots have
oriented growth of metal sulfide nano- of this route. been utilized for band gap engineering. To
structures.23,31 There has been an date, major problems continue to hamper
increased emphasis on the topic of the development of II–VI group materials
Thermal evaporation
‘‘green’’ chemistry and chemical for optoelectronic applications. First, the
processes. Environmentally benign As shown in Fig. 2, various zinc sulfide presence of defects which are derived
reducing agents and nontoxic solvent nanostructures, such as ZnS nanowire from the polytypism of II–VI semi-
media are some of the key issues that arrays, ZnO–ZnS heterojunction nano- conducting materials. Second, the lack of
merit significant consideration in a green wire arrays, ZnS:Ga nanowalls and reproducible doping to achieve desired
synthetic strategy. As life’s basic building CoxZn1xS nanowires, have been electrical conductivity. Finally, the lack of
blocks, biomolecules have special struc- synthesized by thermal evaporation in high quality bulk single-crystalline II–VI
tures and fascinating self-assembling a vacuum tube furnace under controlled semiconducting materials used as
functions, which make them an appro- conditions.11,34,35 substrates.37,38 The ‘‘bottom-up’’
priate medium for the design and One-dimensional single-crystalline approach of utilizing nanomaterials may
synthesis of nanostructures. Recently, DMS CoxZn1xS nanowires with help to overcome these major problems.
biomolecule-assisted synthesis routes different doping levels have been Recent investigations show that band gap

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otherwise difficult in bulk materials. At

the nanoscale level, surface effects and
small-size interface can exert considerable
influence on the formation of high-quality
heterojunctions free of dislocations in
nanosized domains. However, the
synthesis of ZnO–ZnS heterojunction
NW arrays remains a challenge. We have
successfully synthesized for the first time
axial heterostructure ZnO–ZnS NW
arrays based on a one-step thermal
evaporation.35 Room-temperature cath-
odoluminescence (CL) spectra of the
ZnO–ZnS NW arrays and ZnS NW
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arrays are shown in Fig. 3. The CL peaks

for the ZnO–ZnS NW arrays and ZnS
NW arrays are centered at 509 and
549 nm, respectively. The luminescence of
Fig. 1 SEM images of a series of oriented metal sulfide nanostructures grown by a general solution
ZnS at 509 nm was proposed to be due to
route on corresponding metal substrates to demonstrate the generality of this route: (a) Ni3S2, (b)
the presence of Cu or Au impurities in the
Co9S8, (c) Cu2S and (d) ZnS nanostructures.27
literature.42b Thus the blue-green emission
may result from the Au employed in our
tuning in II–VI semiconducting nano- systematically studied. These works show synthesis. The luminescence from ZnO–
materials via controlling the constituent the feasibility of wavelength-controlled ZnS NW arrays is located in the green
stoichiometry is more effective and effi- lasing in 1D ternary metal sulfide semi- region with its maximum intensity
cient. Advances in ternary metal sulfide conductor nanostructures, covering the centered at 549 nm. Multipeak Gaussian
semiconductor nanostructures, such as whole visible spectral range and may find fitting gives two Gaussian bands due to
ZnxCd1xS nanoribbons, CdSxSe1x significant applications in the tunable the asymmetric shape of the peak, and the
nanobelts and ZnSexS1x nano- photoelectric nanodevices in the visible Gaussian curve fits well with the experi-
architectures, have shown that their region. mental curve as shown in Fig. 3b. The
energy gaps and optical emissions can be Recently, the studies of ZnO–ZnS het- blue-green peak supposedly results from
tuned continuously by changing their erostructures with various morphologies ZnS as we discussed above. The other
constituent stoichiometry, dimensionality have been reported.40–42a These results peak located at 557 nm is contributed
and size.37–39 The relationships between demonstrate the feasibility of synthesizing from ZnO, and the emission arises from
the constituent stoichiometry and lattice high-quality crystalline heterostructure at the recombination between electrons
constants, and that between the chemical the nanoscale level from two materials trapped at the oxygen vacancy and holes
composition and band gap energy are with a large lattice mismatch, which are trapped at the surface defects.42c The
SEM image and the corresponding CL
image of ZnO/ZnS NW arrays are shown
in the inset of Fig. 3b. The bright area of
the CL image reveals the luminescent
positions, and the main light-emitting
locations are consistent with the positions
of NW arrays. The findings point to
versatile applications in the tunable
optoelectronic nanodevices in the visible
region. These special kinds of component-
modulated nanomaterials not only offer
the benefit of designing and producing
nanoscale devices without further assem-
bling, but also provide novel desirable
properties.

Magnetic properties
Among the various metal sulfide nano-
Fig. 2 SEM images of various zinc sulfide nanostructures grown by the thermal evaporation materials we have synthesized, the tran-
method: (a) ZnS NW arrays, (b) ZnO–ZnS heterojunction NW arrays, (c) intercrossed sheet-like Ga- sition-metal sulfides are an interesting
doped ZnS nanostructures and (d) CoxZn1xS nanowires.11,34,35 group for magnetic studies due to the fact

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by introducing impurities as dopants. electronic interactions rendered them to

Semiconductors doped with transition be of marginal importance.25,28 They have
metals may possess magnetic properties attracted much attention because of their
due to the partially filled d or f valence promising uses as cathode materials for
electron states of transition metals. In rechargeable lithium-ion batteries, inter-
accordance with their spin, partially filled connectors, supercapacitors and anode
d or f valence electron states contain materials for solid oxide fuel cells
unpaired electrons that may exhibit (SOFCs).26,27,29,47 Cu2S is a p-type semi-
a magnetic phenomenon. Substitutional conducting material with a bulk bandgap
doping of semiconductors with para- of 1.2 eV and can be potentially used as
magnetic transitional-metal ions can nanoswitches due to its mixed Cu ionic/
produce materials called dilute magnetic electronic conductivity.21 ZnS is a II–VI
semiconductors (DMSs).44 The inter- semiconducting material with a wide
esting magneto-optical and magnetic bandgap energy of 3.7 eV.48
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properties of DMSs are spin-exchange Doping is an effective approach to tune

interactions between the semiconductor the electrical properties of semi-
charge carriers and the dopant ions.45 conductors and it has been widely used in
Great efforts have been devoted to the the semiconductor industry. We success-
research of DMSs due to their promising fully synthesized Co-doped ZnS nano-
applications in nanoscale spintronic wires by using a chemical vapor transport
devices, such as spin light-emitting method. The metal chloride plays a crit-
Fig. 3 (a) Room-temperature CL spectra of
diodes, nonvolatile memory and spin- ical role in the substitution of Zn with
ZnO–ZnS NW arrays. (b) Multipeak Gaussian
valve transistors.46 One-dimensional dopants. We demonstrate that the elec-
fitting of the received CL spectra. Blue-green
and green emissions are contributed from ZnS
single-crystalline DMS CoxZn1xS trical properties of Co-doped ZnS nano-
and ZnO, respectively. The inset shows the nanowires with different doping levels wires can be tuned by introducing
SEM image and the corresponding CL image have been synthesized by the thermal different doping levels.34 Fig. 5 reveals the
of ZnO–ZnS NW arrays.35 evaporation method.34 An example is concentration dependence of conduc-
shown in Fig. 4. Fig. 4a shows the tivity in CoxZn1xS nanowires. The
hysteresis loop of the magnetization as conductivity of nanowires is tuned by
that electrons are in the partially filled a function of the applied magnetic field of introducing different amounts of
d subshells. The magnetic susceptibility CoxZn1xS nanowires with different Co dopants.49 In most cases of semi-
measurement results of various phases of contents at 5 K, showing that the conductors, the increase in doping
cobalt sulfides revealed that CoS, Co3S4, CoxZn1xS nanowires are magnetic. The concentration leads to the increase in
and Co4S3 exhibit temperature-indepen- loops of CoxZn1xS nanowires with low conductivity because of excess free
dent paramagnetism. CoS2 is ferromag- Co content show weak magnetization. carriers. The 3d-transition metals have
netic with a Curie temperature of 116 K The magnetism of the CoxZn1xS nano- higher solubility (10–25%) in II–VI
and Co9S8 is antiferromagnetic with wires is maintained at room temperature, compound semiconductors than that in
a Neel temperature above the decompo- and the saturated magnetization dramat- III–V compound semiconductors.50 These
sition temperature.28 The magnetic ically increases with the Co content in results show that the Co-doped ZnS
susceptibility of Ni3S2 was found to be ZnS. Fig. 4b shows the hysteresis loops of nanowires can be further utilized in
temperature-independent, which is CoxZn1xS nanowires with 5.16% Co at practical device applications, such as
consistent with Pauli paramagnetism. 4, 40, and 300 K. The saturation magne- magnetic and optical nanodevices.
There exist various types of iron sulfides tizations at 4, 40, and 400 K are 1.7 
with different Fe : S ratios in nature.43a In 104, 1.49  104, and 7.45  105 emu,
Field-emission properties
general, iron sulfides present interesting respectively. The magnetization of
magnetic properties which are related to CoxZn1xS nanowires may arise from the Field-emission (FE) is one of the main
the stoichiometric ratio between Fe and S magnetic exchange interaction between characteristics of nanomaterials and
as well as their crystalline structures. Co ions. The result indicates that DMS nanostructures, and is of great commer-
Among natural iron sulfide minerals, CoxZn1xS nanowires are expected to cial interest in displays. As compared with
marcasite and pyrite are diamagnetic; open up a number of opportunities for conventional technologies, nano-
greigite and pyrrhotite are ferrimagnetic; fundamental studies and ensure their structures have many advantages such as
troilite is antiferromagnetic, and mack- promising applications for nanoscale faster device turn-on time, sustainability
inawite is paramagnetic. Magnetic spintronic devices. and compactness.51 Recent progress in the
measurements showed that Fe7S8 and research on FE and stimulated emission
Fe9S8 nanostructures are ferromagnetic properties of 1D wide band-gap semi-
Electrical properties
materials, showing magnetic hysteresis conducting metal sulfide nanostructures
loops at room temperature.43b Many metal sulfides, such as Co9S8 and has resulted in an important increase in
The intrinsic properties of semi- Ni3S2, are good metallic conductors the current density and decrease in the
conductors can be permanently modified whereas magnetic instabilities and turn-on voltage. It has become forefront

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photoelectrical properties that make them

promising nanomaterials for photovol-
taics and photodetectors.61b,62 We have
reported intercrossed sheet-like ZnS
nanostructures with Ga dopant (ZnS:Ga
nanowalls) grown on Si substrates by
thermal evaporation of the mixed
powders of ZnS and Ga2O3 via a self-
catalyzed growth mechanism.11 As shown
in Fig. 7 and 8, the photoresponse of ZnS:
Ga nanowalls shows superior photocon-
Fig. 4 (a) M–H curves of CoxZn1xS nanowires with different Co contents at 5 K. (b) M–H curves
ductive properties due to their high
of CoxZn1xS nanowires with 5.16% Co content at different temperatures.34 surface area and unique morphology. The
increased conductivity of metal–semi-
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conductor–metal (Ag–ZnS:Ga nano-

energy of 3.2 eV. The development of new walls-Ag) Schottky photodetectors under
visible light-active photocatalysts is one light illumination is attributed to the
of the most important subjects in photo- lowering of the Schottky barrier height,
catalysis research. A number of metal photogenerated electron–hole pairs, and
sulfide semiconductor photocatalysts the desorption of oxygen molecules on the
have been achieved for the development ZnS:Ga surface. Because of the high
of visible-light sensitive photocatalysts, photosensitivity and fast response, ZnS
such as CdS, CuS, ZnS, Bi2S3 and and the doped semiconducting metal
Sb2S3.56–58 Nanostructured semi- sulfide nanostructures are promising
conductors have faster electron migration materials systems for optical switches,
and charge generation rate due to their sensors and photodetectors in the visible
Fig. 5 Room temperature I–V measurements higher surface area-to-volume ratio than light region.63
of CoxZn1xS nanowires with different Co the bulk.59,60 Doping of metal ions into
contents (black: Co ¼ 1.42%, r ¼ 15.38 U cm; wide band gap metal sulfide semi-
red: Co ¼ 2.59%, r ¼ 7.14 U cm; blue: Co ¼ conductor nanomaterials has been used to Thermoelectric properties
5.16%, r ¼ 1.04 U cm). The inset shows the prepare photocatalysts.11 Fig. 6 shows Nanoscale thermoelectric elements have
SEM image of the nanowire device.34 excellent photocatalytic activity of ZnS: demonstrated the ability to substantially
Ga nanowalls. ZnS nanowalls doped with increase the thermoelectric figure of merit
research due to growing demands of Ga ions show superior results of photo- beyond what is achievable with the bulk
nanotechnologies and great commercial catalystic properties and the results indi- counterparts. Much research still needs to
interest in flat panel displays. Effects of cate that metal ion doped metal sulfide be done in order to obtain nanostructures
structural parameter, morphology and nanomaterials can potentially serve as which possess the right characteristics.
heterostructures on FE properties of excellent photocatalysts for the degrada- Metal sulfide nanomaterials, such as
semiconducting metal sulfide nano- tion of organic pollutants in water and bismuth sulfide (Bi2S3), antimony sulfide
structure arrays have been widely environmental protection technologies. (Sb2S3) and lead sulfide (PbS) nano-
studied.52,53 Various metal sulfide semi- structures, have recently attracted
conductor nanostructures with tailored increasing interests due to their potential
Photoelectric properties
geometries are ideal systems for investi- applications in the thermoelectric field.
gating the dimensionality and size To date, nanomaterial-based gas, chem- Bi2S3 and Sb2S3 are semiconducting
dependence of their properties for poten- ical, biological and optical sensors have materials with a direct band gap of 1.3 eV
tial applications in displays.54,55 been fabricated and studied with respect and 1.78 eV, respectively. They belong to
to their optical and electrical properties. the family of compounds M2X3 (where M
SnS is an important IV–VI group semi- ¼ Bi, Pb, Sb and X ¼ S, Se, Te), which are
Photocatalytic activity
conductor material with a band gap of considered to be the potential materials
Semiconductor nanomaterials for photo- 1.33 eV. It belongs to the group of layered for thermoelectric applications.64,65 The
catalytic degradation of organic contam- semiconductor materials. In particular, theoretical predictions and subsequent
inants are promising materials in SnS has attracted much attention due to experimental results have proved the
environmental protection nanotech- its potential applications in near-infrared possibility of a significant enhancement in
nology. Titanium dioxide is an excellent detectors, photovoltaic materials with the thermoelectric figure of merit ZT in
photocatalyst because of its low cost, high high conversion efficiency, and photo- superlattices based on lead chalcogenide
stability and environmental friendliness. conductors.61a As important II–VI semi- compounds.66 The thermoelectric power
TiO2 has photoactivity only under ultra- conductor materials, ZnS and CdS factor of these metal sulfide nano-
violet light irradiation, which is the major nanostructures have attracted much structures is larger than that of their bulk
drawback owing to its large band gap attention due to their excellent counterparts and comparable to that of

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composed of tin atoms sandwiched

between two layers of hexagonally close-
packed sulfur atoms.70 The two-dimen-
sional layered characteristics of these
lamellar compounds are advantageous to
alkali metal intercalation phenomena.
One-dimensional nanowire arrays are
promising electrode materials for lithium-
ion batteries. The one-dimensional
nanostructured electrode has several
advantages. First, there is high contact
area between the nanostructured elec-
Fig. 6 (a) Absorption spectrum of methylene blue (MB) solution in the presence of ZnS:Ga
trode and electrolyte so that higher
nanowalls under exposure to UV light for various durations. The decrease in the intensity of
absorbance peaks at 664 nm is attributed to the decomposition of MB. (b) Variation with time of
charge/discharge rates can be performed.
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photodegradation of MB under different conditions: (a) ZnS:Ga nanowalls, dark, (b) without Second, the small nanowire diameter
catalysts, under UV light, (c) ZnS:Ga film, under UV light, (d) P25 TiO2 film, under UV light, and (e) allows for improved cycle life with better
ZnS:Ga nanowalls, under UV light. The inset in (b) shows the data plotted into logarithmic scale. flexibility for accommodating the strain
The data fit well with the equation of first order reaction kinetics.11 of lithium ions insertion/extraction
without the fracture that can occur in
micron-sized or bulk materials. Finally,
Applications in energy short path distances allow for efficient
conversion and storage charge transport of electrons from the
current collector and lithium ions from
Lithium-ion batteries
the electrolyte.72 Direct growth of nano-
Much novel research and important wire arrays onto working electrodes of
progress have been made in the develop- lithium-ion batteries has many advan-
ment of advanced energy conversion and tages. It can make better and larger
storage technologies due to the increasing contact between the nanostructured
demand for depletion of oil and environ- material and working electrode leading to
mental issues. Undoubtedly, lithium-ion easier transportation for electrons,
batteries have long been considered an simplify the cell assembly resulting in
attractive rechargeable power source for improvements of the time, yield rate and
consumer electronic products because of cost saving.73
their advantages such as low-cost, light- We have used nickel sulfide and copper
weight, highly efficient and environ- sulfide nanowire arrays which were
mental friendliness.68 Among the various directly grown on metal current collector
candidates for cathode materials, metal substrates by a general solution route as
sulfides are suitable cathode materials for working cathodes of lithium-ion
lithium-ion batteries because of their high batteries.7,27 Fig. 9 shows the cycle
theoretical capacity, high lithium activity performances and the variation of the
and low cost.69,70 They are abundant and normalized capacity with respect to the C-
Fig. 7 (a) Typical current–voltage curves of
cheap due to the existence of minerals in rate of the (a) Ni3S2 and (b) Cu2S nano-
ZnS:Ga nanowall metal–semiconductor–metal
nature. The reactions of transition metal wire arrays/Li cells cycled at ambient
(MSM) photodetectors measured at room
temperature. The inset shows the band diagram
chalcogenide electrodes involve two or temperature. LiCoO2 is the commonly
of metal–ZnS–metal with different Schottky more electrons per 3d metal as compared used cathode material in commercial
barrier heights at two contacts under zero bias. with only one of the commonly used lithium-ion batteries. The theoretical
J is the Schottky barrier height at the metal/ commercial electrodes. In addition, the capacity of LiCoO2 is 145mA h g1 and
ZnS interface. (b) The temperature dependent potential of the transition metal sulfides can be regarded as the criterion for the
I–V characteristics of ZnS:Ga nanowall MSM versus lithium conversion process reac- cathode material. Therefore, the capacity
photodetectors measured at temperatures tions depends on the ionocovalence of the of the Ni3S2 and Cu2S nanowire arrays
between 300 and 448 K. The inset is the plot of bonding between the transition metal and derived here can be close to 2.5 and 1.6
ln (I/T2) versus 1/T at V ¼ +1 and 1 V and the the chalcogenide, and therefore can be times of the LiCoO2, respectively. It is
effective Schottky barrier heights are extracted
tuned continuously from 0 to 3.5 V by believed that the superior rate capability
to be 0.16 and 0.39 eV, respectively.11
changing the nature of the anion chalco- is attributed to better accommodation of
genide.71a Layered transition-metal di- the strain of lithium insertion/extraction
top state-of-the-art materials. These metal chalcogenides, such as WS2, MoS2 and and the higher electrode/electrolyte
sulfide thermoelectric nanomaterials have SnS2, are of particular interest due to their contact area.72,73 These experimental
great potential applications in solid-state special structural properties.71b,c SnS2 has results demonstrate that better rate
power generation from heat sources.67 a layered CdI2-type structure which is capability property is feasible by using

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 View Article Online

Cu2S, are potential storage materials as

the cathodes for practical use in the next
generation lithium-ion batteries.

Fuel cells
Fuel cells have many advantages, such as
high energy storage and rapid recharge
time. Solid oxide fuel cells (SOFCs) are
flexible fuel cells with respect to fuel
selection. They have great potential for
power generation from alternative fuels
including hydrocarbons, biogas and
syngas.74 Anode poisoning caused by H2S
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in commercially available hydrocarbon

resource-derived fuels is one of the major
challenges for extended fuel applications
in SOFCs. It is highly desirable to develop
new anode materials with high catalytic
activity and good sulfur tolerance for
SOFCs.75,76 Transition metal sulfides, such
Fig. 8 (a) Current–voltage (I–V) curves of the ZnS:Ga nanowall photoconductor measured in the as NiS and CoS, have been investigated as
dark and upon light illumination with a sweep voltage from 0 to 5 V. The inset is a schematic potential candidates for sulfur-tolerance
illustration of the ZnS:Ga nanowall photoconductor configuration. (b) The photoresponse of ZnS: anode materials for SOFCs.47 In addition,
Ga nanowall (black square line) and film (red circle line) for five cycles. Each interval is 30 s. I0 is the there is a strong motivation to find alter-
dark current at T ¼ 0 s. (c) The detailed photoresponse of a single cycle, indicating the fast response native cathode materials for proton-
and recovery time of ZnS:Ga nanowalls. (d) The combined photoresponse curves showing the exchange-membrane fuel cells (PEMFCs),
consistency for different cycles.11 which are less expensive and more active
than platinum. Co9S8 has been theoreti-
nanostructured electrodes and indicating higher reversible lithium storage capacity, cally studied for its catalytic activity in O2
that one-dimensional nanowire arrays are longer cycle life, better cyclic stability and electroreduction.77a Hydrogen is proposed
effective at higher C-rates. As compared superior rate capability have demon- as a major energy carrier for the future.
to the Ni3S2 and Cu2S thin film/Li cell or strated that the one-dimensional metal Water is the most desirable source of
reports of powder electrodes,26,69 the sulfide nanowire arrays, such as Ni3S2 and hydrogen and it contains no carbon. Ni
based catalyses are often employed in
commercial alkaline electrolyzers for the
hydrogen evolution reaction. Pt and its
composites are the most active catalysts
for hydrogen evolution. However, the
large scale application of Pt catalysts is
limited by their low abundance and high
cost.77b Recently, amorphous molyb-
denum sulfide films for efficient hydrogen
evolution catalysis in water have been re-
ported. The catalysts are prepared in
a simple, rapid, and scalable manner at
atmospheric pressure and room tempera-
ture. The catalysis is compatible with
a wide range of pHs from 0 to 13. Using
these catalysts, significant geometric
current densities are achieved at low
overpotentials. The amorphous molyb-
denum sulfide films are among the most
active non-precious catalysts for hydrogen
evolution reactions.77c With the unique
characteristics of nanostructured mate-
rials, metal sulfide nanostructures have
Fig. 9 Cycle performances and profiles of the normalized capacity with respect to the C-rate of the attracted interests in high-performance
(a) Ni3S2 and (b) Cu2S nanowire arrays/Li cells cycled at ambient temperature.7,27 fuel cells and nanosized power sources.78

26 | J. Mater. Chem., 2012, 22, 19–30 This journal is ª The Royal Society of Chemistry 2012
 View Article Online

Hydrogen is considered one of the ideal heterojunction due to Cu+ ions diffusion
alternative fuels due to its highly abun- and doping of the CdS layer led to long-
dant, lightweight and non-polluting term performance degradation.84 With
nature, but storage remains a problem the progress of nanotechnologies and
and less than 1% is present as molecular nanocrystal-based approaches, Cu2S
hydrogen gas, H2.14,15 The development of nanocrystals in combination with CdS
hydrogen storage technology with a safe, nanorods have been demonstrated in their
effective, and inexpensive system for application as solution-processed solar
hydrogen fuel cells with a desired density cells on both flexible plastic substrates
is difficult. Most of the hydrogen is and usual glass substrates with long-term
chemically bound as H2O in water and stability.16,85 In addition, Cu2S can be
some is bound to liquid or gaseous used as an ideal light absorbing material
hydrocarbons.79 Many alloys are capable in extremely thin absorber (ETA) solar
of reversibly storing hydrogen through cells due to its non-toxicity, low cost,
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absorbing gaseous hydrogen at certain abundance and good absorption

temperature and pressure to form metal characteristics.84
hydrides.80 In addition to the gas-phase The ternary I–III–VI2 chalcogenide
reaction, hydrogen can also be stored in chalcopyrites (CuMX2) (M ¼ In, Ga and Fig. 10 Application of ZnO–ZnS hetero-
nanostructured materials through elec- X ¼ S, Se) have been developed with their juction NW arrays for energy generation. (a)
trochemical processes in aqueous solu- power efficiencies now approaching Topography (red curve with filled squares) and
tions under moderate conditions. 20%.17,86–88 These chalcopyrite compound voltage output (blue curve with open squares)
Nanostructured metal sulfide materials, materials possess advantages for photo- line profiles across a heterostructure ZnO–ZnS
such as MoS2 nanotubes and Bi2S3 voltaic applications: (i) they are direct NW array received by a conductive AFM tip.
nanorods, have attracted much attention bandgap semiconducting materials with (b) Three-dimensional output of the voltage
for electrochemical hydrogen storage corresponding high optical absorption output image received from the AFM scan
because of their unique characteristics coefficients, (ii) their bandgap energy is at across a heterostructure ZnO–ZnS NW array
with an area of 30  30 mm2.35
such as large surface area, high surface the red edge of the solar spectrum, and
reactivity and strong gas adsorption.81,82 (iii) they are stable under long-term exci-
In comparison with conventional low tation. Metal sulfide nanostructures can nanogenerators.98,99 As another member
temperature–high pressure hydrogen also be applied in dye-sensitized solar cells in the wurtzite family, ZnS is an impor-
storage technology, electrochemical (DSSCs) because of high optical absorp- tant semiconducting, piezoelectric and
hydrogen storage is a more convenient tion coefficient and low cost.89,90 FeS, optoelectric material. We have reported
and efficient method for hydrogen storage FeS2 and NiS nanostructures have been the synthesis of axial heterostructured
at ambient temperature and pressure, by reported as novel photocathodes in ZnO–ZnS nanowire arrays for the first
which hydrogen is absorbed in electrode tandem solar cells with dye-sensitized time by a thermal evaporation process in
materials during electrochemical decom- TiO2 nanostructures as the corresponding the presence of residual oxygen and
position of water. This method has been photoanode.91,92 Because of the unique demonstrated the first application of het-
widely used in nickel/metal hydride electronic features which are due to the erostructured ZnO–ZnS and ZnS nano-
accumulators.14 The novel metal sulfide large band edge excitation of the metal wire arrays for converting mechanical
nanostructures may find potential appli- centered d–d transition, layered metal energy into electricity.35
cations in hydrogen storage and high- sulfide semiconducting nanomaterials Piezoelectric responses of the hetero-
energy batteries because of their fast such as MoS2 and WS2 have been inves- structured ZnO–ZnS and ZnS nanowire
sorption kinetics, high tolerance to re- tigated for use in solar cells, photo- arrays were examined using AFM in
cycling and high volumetric/gravimetric electrochemical, photovoltaic and contact mode. The experimental setup is
capacity. photoelectrolysis cells.93a,b the same as first used demonstrating the
piezoelectric nanogenerator.3 Applica-
tions of ZnO–ZnS heterojuction and ZnS
Solar cells Nanogenerators
nanowire arrays for energy generation are
Solar energy is the most environmentally Recently, nanogenerators based on shown in Fig. 10 and 11, respectively. The
friendly and technologically promising of wurtzite-structured nanomaterials, such AFM tip scanned across the samples to
the alternative energy sources. Cu2S is as ZnO, GaN and InN nanowire arrays, bend the nanowires and output electrical
a p-type semiconducting material with an have been demonstrated for converting signals were continuously monitored. The
indirect bandgap of 1.21 eV. The earliest mechanical energy into electric energy by process for generating electrical signals
thin-film solar cells were based on CdS/ utilizing the coupling effects of their can be derived from detailed analyses of
Cu2S heterojunctions and the efficiencies semiconducting and piezoelectric proper- the topological profile and output voltage
could be reached up to
10% in the early ties.3,94–97 Among wurtzite-structured peak received by the tip when scanned
1980s.83 CdS/Cu2S solar cells showed metal sulfide nanomaterials, CdS nano- across nanowires. As proposed previously
significant potential in thin-film studies, wire arrays were also successfully for ZnO and CdS nanowires,3,98 the
however, the instability of the demonstrated for piezoelectric physical principle for creating electric

This journal is ª The Royal Society of Chemistry 2012 J. Mater. Chem., 2012, 22, 19–30 | 27
 View Article Online

nanostructures. They present ample

opportunities for scientists and technolo-
gists to engage in the research and devel-
opment of nanostructured materials.
Nanodevices with nanostructured metal
sulfide materials have been demonstrated,
especially in energy conversion and
storage to confront grand challenges of
energy shortage and global warming.
With the rapid development of nano-
technology and increasing attention from
the industry, it is expected that commer-
cial applications will be realized soon.
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Acknowledgements
The authors would like to thank Dr K. W.
Huang for his contributions to the work
reviewed in this article. The work was
supported by the Republic of China
National Science Council through grant
no. NSC 98-2221-E-007-104-MY3.

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