Effects of Na and MoS2 on Cu2ZnSnS4 thin‐film solar cell

Cu₂ZnSnS₄ (CZTS)‐based materials have a useful band gap and a high absorption coefficient; however, their power conversion efficiency is low compared with that of CdTe and Cu(In,Ga)Se₂‐based solar cells. Two of the factors that strongly affect CZTS solar cell characteristics are the MoS₂ layer and the presence of defects. In this study, Mo back‐contact layers were annealed to control MoS₂ layer formation and the Na content in the Mo layer before the absorber precursor layer was deposited. The increase in oxygen content in the Mo layer suppressed MoS₂ layer formation. In addition, the increase in Na diffusion during the initial stage of the absorber precursor deposition decreased the defect density in the absorber layer and in the absorber–buffer interface. These results were verified through measurements of the external quantum efficiency, the temperature dependence of the open‐circuit voltage (V_OC), and admittance spectra. The current densities (J_SC) and V_OC, as well as the power conversion efficiencies, improved as the annealing temperature of the Mo layer increased, which suggests that CZTS solar cell characteristics can be improved by suppressing MoS₂ layer formation and increasing Na content in the Mo layer before deposition of the absorber precursor layer. Copyright © 2014 John Wiley & Sons, Ltd.     

Inverted Organic Solar Cells with Sol–Gel Processed High Work‐Function Vanadium Oxide Hole‐Extraction Layers

For large‐scale and high‐throughput production of organic solar cells (OSCs), liquid processing of the functional layers is desired. We demonstrate inverted bulk‐heterojunction organic solar cells (OSCs) with a sol–gel derived V₂O₅ hole‐extraction‐layer on top of the active organic layer. The V₂O₅ layers are prepared in ambient air using Vanadium(V)‐oxitriisopropoxide as precursor. Without any post‐annealing or plasma treatment, a high work function of the V₂O₅ layers is confirmed by both Kelvin probe analysis and ultraviolet photoelectron spectroscopy (UPS). Using UPS and inverse photoelectron spectroscopy (IPES), we show that the electronic structure of the solution processed V₂O₅ layers is similar to that of thermally evaporated V₂O₅ layers which have been exposed to ambient air. Optimization of the sol gel process leads to inverted OSCs with solution based V₂O₅ layers that show power conversion efficiencies similar to that of control devices with V₂O₅ layers prepared in high‐vacuum.     

Wafer Scale Synthesis and High Resolution Structural Characterization of Atomically Thin MoS2 Layers

Synthesis of atomically thin MoS₂ layers and its derivatives with large‐area uniformity is an essential step to exploit the advanced properties of MoS₂ for their possible applications in electronic and optoelectronic devices. In this work, a facile method is reported for the continuous synthesis of atomically thin MoS₂ layers at wafer scale through thermolysis of a spin coated‐ammonium tetrathiomolybdate film. The thickness and surface morphology of the sheets are characterized by atomic force microscopy. The optical properties are studied by UV–Visible absorption, Raman and photoluminescence spectroscopies. The compositional analysis of the layers is done by X‐ray photo­emission spectroscopy. The atomic structure and morphology of the grains in the polycrystalline MoS₂ atomic layers are examined by high‐angle annular dark‐field scanning transmission electron microscopy. The electron mobilities of the sheets are evaluated using back‐gate field‐effect transistor configuration. The results indicate that this facile method is a promising approach to synthesize MoS₂ thin films at the wafer scale and can also be applied to synthesis of WS₂ and hybrid MoS₂‐WS₂ thin layers.     

All‐Solution‐Processed Indium‐Free Transparent Composite Electrodes based on Ag Nanowire and Metal Oxide for Thin‐Film Solar Cells

Fully solution‐processed Al‐doped ZnO/silver nanowire (AgNW)/Al‐doped ZnO/ZnO multi‐stacked composite electrodes are introduced as a transparent, conductive window layer for thin‐film solar cells. Unlike conventional sol–gel synthetic pathways, a newly developed combustion reaction‐based sol–gel chemical approach allows dense and uniform composite electrodes at temperatures as low as 200 °C. The resulting composite layer exhibits high transmittance (93.4% at 550 nm) and low sheet resistance (11.3 Ω sq^‐1), which are far superior to those of other solution‐processed transparent electrodes and are comparable to their sputtered counterparts. Conductive atomic force microscopy reveals that the multi‐stacked metal‐oxide layers embedded with the AgNWs enhance the photocarrier collection efficiency by broadening the lateral conduction range. This as‐developed composite electrode is successfully applied in Cu(In_1‐x,Ga_x)S₂ (CIGS) thin‐film solar cells and exhibits a power conversion efficiency of 11.03%. The fully solution‐processed indium‐free composite films demonstrate not only good performance as transparent electrodes but also the potential for applications in various optoelectronic and photovoltaic devices as a cost‐effective and sustainable alternative electrode.     

Covalent 0D–2D Heterostructuring of Co9S8–MoS2 for Enhanced Hydrogen Evolution in All pH Electrolytes

Ultrasmall Co₉S₈ nanoparticles are introduced on the basal plane of MoS₂ to fabricate a covalent 0D–2D heterostructure that enhances the hydrogen evolution reaction (HER) activity of electrochemical water splitting. In the heterostructure, separate phases of Co₉S₈ and MoS₂ are formed, but they are connected by Co–S–Mo type covalent bonds. The charge redistribution from Co to Mo occurring at the interface enhances the electron‐doped characteristics of MoS₂ to generate electron‐rich Mo atoms. Besides, reductive annealing during the synthesis forms S defects that activates adjacent Mo atoms for further enhanced HER activity as elucidated by the density functional theory (DFT) calculation. Eventually, the covalent Co₉S₈–MoS₂ heterostructure shows amplified HER activity as well as stability in all pH electrolytes. The synergistic effect is pronounced when the heterostructure is coupled with a porous Ni foam (NF) support to form Co₉S₈–MoS₂/NF that displays superior performance to those of the state‐of‐the‐art non‐noble metal electrocatalysts, and even outperforms a commercial Pt/C catalyst in a practically meaningful, high current density region in alkaline (>170 mA cm^?2) and neutral (>60 mA cm^?2) media. The high HER performance and stability of Co₉S₈–MoS₂ heterostructure make it a promising pH universal alternative to expensive Pt‐based electrocatalysts for practical water electrolyzers.     

Template‐Based Growth of Various Oxide Nanorods by Sol–Gel Electrophoresis

The ability to form oxide nanorods is of great interest in a number of areas. In this paper, we report the template‐based growth of nanorods of several oxide ceramics, formed by means of a combination of sol–gel processing and electrophoretic deposition. Both single metal oxides (TiO₂, SiO₂) and complex oxides (BaTiO₃, Sr₂Nb₂O₇, and Pb(Zr_0.52Ti_0.48)O₃) have been grown by this method. Uniformly sized nanorods of about 125–200 nm in diameter and 10 μm in length were grown over large areas with near unidirectional alignment. Desired stoichiometric chemical composition and crystal structure of the oxide nanorods was readily achieved by an appropriate procedure of sol preparation, with a heat treatment (700 °C for 15 min) for crystallization and densification.     

Titanium‐Doped Molybdenum Disulfide Nanostructures

Ti‐doped MoS₂ nanotubes are produced by pyrolyzing a H₂S/N₂ mixture over an oxidized Ti–Mo alloy powder at elevated temperatures. Partial substitution of Mo by Ti does not significantly alter the 2H–MoS₂ lattice.     

Atomic Vacancy Control and Elemental Substitution in a Monolayer Molybdenum Disulfide for High Performance Optoelectronic Device Arrays

Defect engineering of 2D transition metal dichalcogenides (TMDCs) is essential to modulate their optoelectrical functionalities, but there are only a few reports on defect‐engineered TMDC device arrays. Herein, the atomic vacancy control and elemental substitution in a chemical vapor deposition (CVD)‐grown molybdenum disulfide (MoS₂) monolayer via mild photon irradiation under controlled atmospheres are reported. Raman spectroscopy, photoluminescence, X‐ray, and ultraviolet photoelectron spectroscopy comprehensively demonstrate that the well‐controlled photoactivation delicately modulates the sulfur‐to‐molybdenum ratio as well as the work function of a MoS₂ monolayer. Furthermore, the atomic‐resolution scanning transmission electron microscopy directly confirms that small portions (2–4 at% corresponding to the defect density of 4.6 × 10¹² to 9.2 × 10¹³ cm^?2) of sulfur vacancies and oxygen substituents are generated in the MoS₂ while the overall atomic‐scale structural integrity is well preserved. Electronic and optoelectronic device arrays are also realized using the defect‐engineered CVD‐grown MoS₂, and it is further confirmed that the well‐defined sulfur vacancies and oxygen substituents effectively give rise to the selective n‐ and p‐doping in the MoS₂, respectively, without the trade‐off in device performance. In particular, low‐percentage oxygen‐doped MoS₂ devices show outstanding optoelectrical performance, achieving a detectivity of ≈10¹³ Jones and rise/decay times of 0.62 and 2.94 s, respectively.     

MoS2 Van der Waals p–n Junctions Enabling Highly Selective Room‐Temperature NO2 Sensor

Van der Waals p–n junctions of 2D materials present great potential for electronic devices due to the fascinating properties at the junction interface. In this work, an efficient gas sensor based on planar 2D van der Waals junctions is reported by stacking n‐type and p‐type atomically thin MoS₂ films, which are synthesized by chemical vapor deposition (CVD) and soft‐chemistry route, respectively. The electrical conductivity of the van der Waals p–n junctions is found to be strongly affected by the exposure to NO₂ at room temperature (RT). The MoS₂ p–n junction sensor exhibits an outstanding sensitivity and selectivity to NO₂ at RT, which are unavailable in sensors based on individual n‐type or p‐type MoS₂. The sensitivity of 20 ppm NO₂ is improved by 60 times compared to a p‐type MoS₂ sensor, and an extremely low limit of detection of 8 ppb is obtained under ultraviolet irradiation. Complete and very fast sensor recovery is achieved within 30 s. These results are superior to most of the previous reports related to NO₂ detection. This work establishes an entirely new sensing platform and proves the feasibility of using such materials for the high‐performance detection of gaseous molecules at RT.     

MoS2/Si Heterojunction with Vertically Standing Layered Structure for Ultrafast,High‐Detectivity,Self‐Driven Visible–Near Infrared Photodetectors

As an interesting layered material, molybdenum disulfide (MoS₂) has been extensively studied in recent years due to its exciting properties. However, the applications of MoS₂ in optoelectronic devices are impeded by the lack of high‐quality p–n junction, low light absorption for mono‐/multilayers, and the difficulty for large‐scale monolayer growth. Here, it is demonstrated that MoS₂ films with vertically standing layered structure can be deposited on silicon substrate with a scalable sputtering method, forming the heterojunction‐type photodetectors. Molecular layers of the MoS₂ films are perpendicular to the substrate, offering high‐speed paths for the separation and transportation of photo‐generated carriers. Owing to the strong light absorption of the relatively thick MoS₂ film and the unique vertically standing layered structure, MoS₂/Si heterojunction photodetectors with unprecedented performance are actualized. The self‐driven MoS₂/Si heterojunction photodetector is sensitive to a broadband wavelength from visible light to near‐infrared light, showing an extremely high detectivity up to ≈10¹³ Jones (Jones = cm Hz^1/2 W^?1), and an ultrafast response speed of ≈3 μs. The performance is significantly better than the photodetectors based on mono‐/multilayer MoS₂ nanosheets. Additionally, the MoS₂/Si photodetectors exhibit excellent stability in air for a month. This work unveils the great potential of MoS₂/Si heterojunction for optoelectronic applications.     

Van der Waals Bipolar Junction Transistor Using Vertically Stacked Two‐Dimensional Atomic Crystals

The majority of microelectronic devices rely on a p‐n junction. The process of making such a junction is complicated, and it is difficult to make layers that form a junction with an atomic thickness. In this study, bipolar junctions are made by using 2D atomic crystalline layers and even a single layer in which 2D layers adhere together to form a heterostructure via van der Waals forces. A vertical 2D bipolar junction transistor (V2D‐BJT) is studied for the first time. It uses an MoS₂/WSe₂/MoS₂ heterostructure and has an n‐p‐n configuration that exhibits a maximum common‐base current gain of ≈0.97 and a stable common‐emitter current gain (β) of 12 with a nanowatt power consumption. In the first attempt at gas sensing, it shows outstanding performance, exhibiting a very fast response and recovery time (9 and 35 s, respectively) with a power dissipation of only 2 nW. This study demonstrates the potential application of the V2D‐BJT in nanowatt power amplifiers as well as fast‐response and low‐power gas sensors.     

Optimization of a Quasi‐Solid‐State Dye‐Sensitized Photoelectrochemical Solar Cell Employing a Ureasil/Sulfolane Gel Electrolyte

A quasi‐solid‐state, dye‐sensitized photoelectrochemical solar cell employing a gel electrolyte obtained by sol–gel chemistry is described. The gel electrolyte is based on a ureasil precursor (i.e., a poly(propylene oxide) oligomer end‐capped by triethoxysilane groups through urea bridges) and sulfolane and it incorporates the I₃^–/I^– redox couple. It is shown that the combination of these two reagents prevents crystallization of KI, thus ensuring a long life for the cell and a satisfactory overall efficiency that surpasses 5 %. Cell efficiency increases with temperature. Optimization of gel‐electrolyte performance has been obtained by studying mobility with fluorescence‐quenching techniques complemented by direct‐current conductivity measurements.     

Bamboo‐Like Hollow Tubes with MoS2/N‐Doped‐C Interfaces Boost Potassium‐Ion Storage

Potassium‐ion batteries (KIBs) are new‐concept of low‐cost secondary batteries, but the sluggish kinetics and huge volume expansion during cycling, both rooted in the size of large K ions, lead to poor electrochemical behavior. Here, a bamboo‐like MoS₂/N‐doped‐C hollow tubes are presented with an expanded interlayer distance of 10 Å as a high‐capacity and stable anode material for KIBs. The bamboo‐like structure provides gaps along axial direction in addition to inner cylinder hollow space to mitigate the strains in both radial and vertical directions that ultimately leads to a high structural integrity for stable long‐term cycling. Apart from being a constituent of the interstratified structure the N‐doped‐C layers weave a cage to hold the potassiation products (polysulfide and the Mo nanoparticles) together, thereby effectively hindering the continuing growth of solid electrolyte interphase in the interior of particles. The density functional theory calculations prove that the MoS₂/N‐doped‐C atomic interface can provide an additional attraction toward potassium ion. As a result, it delivers a high capacity at a low current density (330 mAh g^?1 at 50 mA g^?1 after 50 cycles) and a high‐capacity retention at a high current density (151 mAh g^?1 at 500 mA g^?1 after 1000 cycles).     

Effects of Defects on the Temperature‐Dependent Thermal Conductivity of Suspended Monolayer Molybdenum Disulfide Grown by Chemical Vapor Deposition

It is understood that defects of the atomic arrangement of the lattice in 2D molybdenum disulfide (MoS₂) grown by chemical vapor deposition (CVD) can have a profound effect on the electronic and optical properties. Beyond these it is a major prerequisite to also understand the fundamental effect of such defects on phonon transport, to guarantee the successful integration of MoS₂ into the solid‐state devices. A comprehensive joint experiment‐theory investigation to explore the effect of lattice defects on the thermal transport of the suspended MoS₂ monolayer grown by CVD is presented. The measured room temperature thermal conductivity values are 30 ± 3.3 and 35.5 ± 3 W m^?1 K^?1 for two samples, which are more than two times smaller than that of their exfoliated counterpart. High‐resolution transmission electron microscopy shows that these CVD‐grown samples are polycrystalline in nature with low angle grain boundaries, which is primarily responsible for their reduced thermal conductivity. Higher degree of polycrystallinity and aging effects also result in smoother temperature dependency of thermal conductivity (κ) at temperatures below 100 K. First‐principles lattice dynamics simulations are carried out to understand the role of defects such as isotopes, vacancies, and grain boundaries on the phonon scattering rates of our CVD‐grown samples.     

Organic–Inorganic Nanohybridization by Block Copolymer Thin Films

A simple route for fabricating highly ordered organic–inorganic hybrid nanostructures, using polystyrene‐block‐poly(ethylene oxide) diblock copolymer (PS‐b‐PEO) thin films coupled with sol–gel chemistry, is presented. Hexagonally packed arrays of titania nanodomains were generated by one‐step spin‐coating from solutions containing a titania precursor and PS‐b‐PEO, where the precursor was selectively incorporated into the PEO domain. The PS‐b‐PEO template was subsequently removed by UV treatment, leaving behind a highly dense array of hexagonally packed titania dots. The size of the dots, as well as the lattice spacing of the array, could be fine‐tuned by simply controlling the relative amount of sol–gel precursor to PS‐b‐PEO.     

A Bottom‐Up Approach to Build 3D Architectures from Nanosheets for Superior Lithium Storage

Two‐dimensional (2D) atomic layers such as graphene, and metal chalcogenides have recently attracted tremendous attention due to their unique properties and potential applications. Unfortunately, in most cases, the free‐standing nanosheets easily re‐stack due to their van der Waals forces, and lose the advantages of their separated atomic layer state. Here, a bottom‐up approach is developed to build three‐dimensional (3D) architectures by 2D nanosheets such as MoS₂ and graphene oxide nanosheets as building blocks, the thin nature of which can be well retained. After simply chemical reduction, the resulting 3D MoS₂‐graphene architectures possess high surface area, porous structure, thin walls and high electrical conductivity. Such unique features are favorable for the rapid diffusions of both lithium ions and electrons during lithium storage. As a consequence, MoS₂‐graphene electrodes exhibit high reversible capacity of ≈1200 mAh g^?1, with very good cycling performance. Moreover, such a simple and low‐cost assembly protocol can provide a new pathway for the large‐scale production of various functional 3D architectures for energy storage and conversions.     

Nonvolatile Floating‐Gate Memories Based on Stacked Black Phosphorus–Boron Nitride–MoS2 Heterostructures

Research on van der Waals heterostructures based on stacked 2D atomic crystals is intense due to their prominent properties and potential applications for flexible transparent electronics and optoelectronics. Here, nonvolatile memory devices based on floating‐gate field‐effect transistors that are stacked with 2D materials are reported, where few‐layer black phosphorus acts as channel layer, hexagonal boron nitride as tunnel barrier layer, and MoS₂ as charge trapping layer. Because of the ambipolar behavior of black phosphorus, electrons and holes can be stored in the MoS₂ charge trapping layer. The heterostructures exhibit remarkable erase/program ratio and endurance performance, and can be developed for high‐performance type‐switching memories and reconfigurable inverter logic circuits, indicating that it is promising for application in memory devices completely based on 2D atomic crystals.     

Atomic Insight into Thermolysis‐Driven Growth of 2D MoS2

Understanding and controlling the transformations of transition metal dichalcogenides (TMDs) from amorphous precursors into two‐dimensional (2D) materials is important for guiding synthesis, directing fabrication, and tailoring functional properties. Here, the combined effects of thermal energy and electron beam irradiation are explored on the structural evolution of 2D MoS₂ flakes through the thermal decomposition of a (NH₄)₂MoS₄ precursor inside an ultrahigh vacuum (10^?9 Torr) scanning transmission electron microscope (STEM). The influence of reaction temperature, growth substrate, and the initial precursor morphology on the resulting 2D MoS₂ flake morphology, edge structures, and point defects are explored. Although thermal decomposition occurs extremely fast at elevated temperatures and is difficult to capture using current STEM techniques, electron beam irradiation can induce local transformations at lower temperatures, enabling direct observation and interpretation of critical growth steps including oriented attachment and transition from single‐ to multilayer structures at atomic resolution. An increase in the number of layers of the MoS₂ flakes from island growth is investigated using electron beam irradiation. These findings provide insight into the growth mechanisms and factors that control the synthesis of few‐layer MoS₂ flakes through thermolysis and toward the prospect of atomically precise control and growth of 2D TMDs.     

Layer‐By‐Layer Dendritic Growth of Hyperbranched Thin Films for Surface Sol–Gel Syntheses of Conformal,Functional, Nanocrystalline Oxide Coatings on Complex 3D (Bio)silica Templates

Here, a straightforward and general method for the rapid dendritic amplification of accessible surface functional groups on hydroxylated surfaces is described, with focus on its application to 3D biomineral surfaces. Reaction of hydroxyl‐bearing silica surfaces with an aminosilane, followed by alternating exposure to a dipentaerythritol‐derived polyacrylate solution and a polyamine solution, allows the rapid, layer‐by‐layer (LBL) build‐up of hyperbranched polyamine/polyacrylate thin films. Characterization of such LBL‐grown thin films by AFM, ellipsometry, XPS, and contact angle analyses reveals a stepwise and spatially homogeneous increase in film thickness with the number of applied layers. UV–Vis absorption analyses after fluorescein isothiocyanate labeling indicate that significant amine amplification is achieved after the deposition of only 2 layers with saturation achieved after 3–5 layers. Use of this thin‐film surface amplification technique for hydroxyl‐enrichment of biosilica templates facilitates the conformal surface sol–gel deposition of iron oxide that, upon controlled thermal treatment, is converted into a nanocrystalline (～9.5 nm) magnetite (Fe₃O₄) coating. The specific adsorption of arsenic onto such magnetite‐coated frustules from flowing, arsenic‐bearing aqueous solutions is significantly higher than for commercial magnetite nanoparticles (≤50 nm in diameter).     

Tuning the Electronic and Photonic Properties of Monolayer MoS2 via In Situ Rhenium Substitutional Doping

Doping is a fundamental requirement for tuning and improving the properties of conventional semiconductors. Recent doping studies including niobium (Nb) doping of molybdenum disulfide (MoS₂) and tungsten (W) doping of molybdenum diselenide (MoSe₂) have suggested that substitutional doping may provide an efficient route to tune the doping type and suppress deep trap levels of 2D materials. To date, the impact of the doping on the structural, electronic, and photonic properties of in situ‐doped monolayers remains unanswered due to challenges including strong film substrate charge transfer, and difficulty achieving doping concentrations greater than 0.3 at%. Here, in situ rhenium (Re) doping of synthetic monolayer MoS₂ with ≈1 at% Re is demonstrated. To limit substrate film charge transfer, r‐plane sapphire is used. Electronic measurements demonstrate that 1 at% Re doping achieves nearly degenerate n‐type doping, which agrees with density functional theory calculations. Moreover, low‐temperature photoluminescence indicates a significant quench of the defect‐bound emission when Re is introduced, which is attributed to the Mo O bond and sulfur vacancies passivation and reduction in gap states due to the presence of Re. The work presented here demonstrates that Re doping of MoS₂ is a promising route toward electronic and photonic engineering of 2D materials.