Pulsed electrodeposition and characterization of molybdenum diselenide thin film

Molybdenum dichalcogenides are semiconductors with layered type structure, which can act as efficient electrodes in the realization of photoelectrochemical solar cells. The main advantage of this molybdenum diselenide (MoSe₂) semiconductor is the prevention of electrolyte corrosion because of the phototransitions involving non-bonding d-d orbital of the Mo atoms. Polycrystalline molybdenum diselenide thin films are prepared by pulsed electrodeposition on conducting glass and titanium substrates in galvanostatic mode from an ammoniacal solution of H₂MoO₄ and SeO₂. The growth kinetics of the film was studied and the deposition parameters such as electrolyte bath concentration, bath temperature, time of deposition, deposition current, pH of the electrolyte and duty cycle of the current are optimized. X-ray diffraction analysis of the as deposited and annealed films showed the presence of highly textured MoSe₂ films with polycrystalline nature. EDAX spectrum of the surface composition confirms the nearly stoichiometric MoSe₂ nature of the film. Surface morphology studies by scanning electron microscope (SEM) shows that the films are pinhole free and of device quality nature. The optical absorption spectra show an indirect band gap value of 1.16 eV. Conductivity measurements were carried out at different temperatures and electrical constants such as activation energy, trapped energy state and barrier height were calculated.     

Effects of hydrolysis on dodecyl alcohol modified β-CaSiO3 particles and PDLLA/modified β-CaSiO3 composite films

In this research, β-CaSiO₃ particles were surface modified with dodecyl alcohol, and Poly-(DL-lactic acid) (PDLLA)/modified β-CaSiO₃ composite films were fabricated with a homogenous dispersion of β-CaSiO₃ particles in the PDLLA matrix. The aim of the study was to investigate the properties of the composite films before and after hydrolytic treatment. SEM images showed retained homogenous dispersion of β-CaSiO₃ particles after hydrolysis and tensile test also showed maintained mechanical property. Simulated body fluid (SBF) incubation experiment suggested that hydrolytic treatment did not affect the formation of hydroxyapatite on the surface of the composite films. The hydrophilicity of the composites was greatly recovered (from 69.82° to 50.28°) after hydrolysis. In addition, cells cultured on composite films after hydrolysis presented the highest cell proliferation rate and differentiation level. All of these results suggested that the surface modification of silicate particles with dodecyl alcohol along with reversible hydrolytic treatment was an effective and feasible approach to fabricate polymer/silicate composite materials with improved properties.     

Oxidation behavior of (Ti1 − xAlx)N films perpared by r.f. reactive sputtering

(Ti, Al)N films have drawn much attention as alternatives for TiN coatings, which are oxidized easily in air above 500 °C. We have investigated the effect of Al content on the oxidation resistance of (Ti_{1 − x}Al_x)N films prepared by r.f. reactive sputtering.(Ti_{1 − x}Al_xN films (O ≤ x ≤ 0.55) were deposited onto fused quartz substrates by r.f. reactive sputtering. Composite targets with five kinds of Al-to-Ti area ratio were used. The sputtering gas was Ar (purity, 5 N) and N₂ (5 N). The flow rate of Ar and N₂ gas was kept constant at 0.8 and 1.2 sccm, respectively, resulting in a sputtering pressure of 0.4 Pa. The r.f. power was 300 W for all experiments. Substrates were not intentionally heated during deposition. The deposited films (thickness, 300 nm) were annealed in air at 600 900 °C and then subjected to X-ray diffractometer and Auger depth profiling.The as-deposited (Ti_{1 − x}Al_x)N films had the same crystal structure as TiN (NaCl type). Al atoms seemed to substitute for Ti in lattice sites. The preferential orientation of the films changed with the Al content of the film, x. Oxide layers of the films grew during annealing and became thicker as the annealing temperature increased. The thickness of the oxide layer grown on the film surface decreased with increasing Al content in the film. For high Al content films an Al-rich oxide layer was grown on the surface, which seemed to prevent further oxidation. All of the films, however, were oxidized by 900 °C annealing, even if the Al content was increased up to 0.55.     

Phase Modulation of (1T‐2H)‐MoSe2/TiC‐C Shell/Core Arrays via Nitrogen Doping for Highly Efficient Hydrogen Evolution Reaction

Tailoring molybdenum selenide electrocatalysts with tunable phase and morphology is of great importance for advancement of hydrogen evolution reaction (HER). In this work, phase‐ and morphology‐modulated N‐doped MoSe₂/TiC‐C shell/core arrays through a facile hydrothermal and postannealing treatment strategy are reported. Highly conductive TiC‐C nanorod arrays serve as the backbone for MoSe₂ nanosheets to form high‐quality MoSe₂/TiC‐C shell/core arrays. Impressively, continuous phase modulation of MoSe₂ is realized on the MoSe₂/TiC‐C arrays. Except for the pure 1T‐MoSe₂ and 2H‐MoSe₂, mixed (1T‐2H)‐MoSe₂ nanosheets are achieved in the N‐MoSe₂ by N doping and demonstrated by spherical aberration electron microscope. Plausible mechanism of phase transformation and different doping sites of N atom are proposed via theoretical calculation. The much smaller energy barrier, longer H? Se bond length, and diminished bandgap endow N‐MoSe₂/TiC‐C arrays with substantially superior HER performance compared to 1T and 2H phase counterparts. Impressively, the designed N‐MoSe₂/TiC‐C arrays exhibit a low overpotential of 137 mV at a large current density of 100 mA cm^?2, and a small Tafel slope of 32 mV dec^?1. Our results pave the way to unravel the enhancement mechanism of HER on 2D transition metal dichalcogenides by N doping.     

Surface morphologies and properties of pure and antimony-doped tin oxide films derived by sol–gel dip-coating processing

A simple laboratory technique for the routine preparation of antimony-doped tin oxide (ATO) on float glass substrates (25 mm × 76 mm × 1 mm) was described. As-prepared thin films were dried at temperature of 100 ± 5 °C and annealed at temperatures of 400–550 °C. Microstructural and morphological analyses of as-prepared films were performed at different conditions. The evolution of grain size and the morphologies of ATO films were analyzed by means of atom force microscopy (AFM) and digital microscope. The studies suggested that higher Sb-doped level and higher annealing temperature led to a decrease in the surface roughness of the deposited films. The XRD patterns revealed that as-prepared ATO films were in the crystallization of a tetragonal rutile structure of SnO₂ with highly (1 1 0) preferred orientation. Their optical properties were analyzed by U-3310 spectrophotometer. The transmission of the ATO thin films was obtained as high as 80–90% in visible region, but decreased substantially in IR region. The sheet resistance of the investigated thin films was determined by four-probe method, showing that it was about 85–100 Ω □⁻¹which decreased with the increase of antimony-doped concentration.     

Ferroelectric properties of Mn-Doped Bi3.15Nd0.85Ti3O12 thin films prepared under different annealing conditions

Mn-doped Bi_3.15Nd_0.85Ti₃O₁₂ (BNTM) thin films were fabricated on Pt/Ti/SiO₂/Si(100) substrates by a chemical solution deposition technique and annealed at different temperatures from 650 to 800 °C. The structures of the films were analyzed using X-ray diffraction, which showed that the BNTM films exhibit polycrystalline structures and random orientations. The surface morphologies of the samples were investigated using scanning electron microscopy. The average grain size of the films increases with increasing annealing temperature. Electrical properties such as remanent polarization (2P_r) are quite dependent on the annealing temperature of BNTM films. It is found that the film annealed at 750 °C exhibits excellent ferroelectricity with a remanent polarization of 2P_r = 89.3 μC/cm² and a coercive field of E_c = 99.2 kV/cm respectively.     

Fabrication of epitaxial conductive LaNiO3 films on different substrates by pulsed laser ablation

LaNiO₃ (LNO) thin films were deposited on (1 0 0) MgO, SrTiO₃ (STO) and LaAlO₃ (LAO) crystal substrates by pulsed laser deposition (PLD) under 20 Pa oxygen pressure at different substrate temperatures from 450 to 750 °C. X-ray diffraction (XRD), ex situ reflection high energy electron diffraction (RHEED) and atomic force microscopy (AFM) were employed to characterize the crystal structure of LNO films. LNO films deposited on STO and LAO at a temperature range from 450 to 700 °C exhibit high (0 0 l) orientation. XRD ψ scans and RHEED observations indicate that LNO films could be epitaxially grown on these two substrates with cubic-on-cubic arrangement at a wide temperature range. LNO films deposited at 700 °C on MgO (1 0 0) substrate have the (l l 0) orientation, which was identified to be bicrystalline epitaxial growth. La₂NiO₄ phase appears in LNO films deposited at 750 °C on three substrates. The epitaxial LNO films were tested to be good metallic conductive layers by four-probe method.     

Two-dimensional interface structures of epitaxial (Ba,Sr)TiO3 film on miscut (001) MgO

We report on the effect of substrate miscut on the 2-dimensional interfacial structure and dielectric properties of the epitaxial Ba_0.6Sr_0.4TiO₃/MgO. Epitaxial Ba_0.6Sr_0.4TiO₃ films on vicinal (001) MgO grown by pulsed-laser ablation were studied using transmission electron microscopy (TEM). Plan-view TEM showed that the films grown on the substrate with miscut angles of 1.2°, 3.5°, and 5.3° have lattice mismatches of − 5.6%, − 6.0% and − 5.7% at the interface, larger than the values (− 5.4%, − 5.7% and − 5.5%, respectively) obtained using cross-section TEM. The films grown on 1.2° and 5.3° miscut substrates consist of commensurate domains with sizes about 30 to 40 nm at the interface, significantly larger than those of 10 to 20 nm obtained for the films grown on the 3.5° miscut substrate. The films with larger commensurate domains at the interface exhibit about 30% higher dielectric constant and dielectric tunability than those with smaller commensurate domains. Initial measurements show that their interfacial differences have a tremendous effect on the dielectric properties of the films.     

Second harmonic generation in surface crystallized 30GeS2 · 35Ga2S3 · 35AgCl chalcohalide glasses

The infrared transmitting surface crystallized chalcohalide glasses containing nontoxic and excellent nonlinear optical AgGaGeS₄ crystallites were fabricated by heat-treatment of the as-prepared 30GeS₂ · 35Ga₂S₃ · 35AgCl chalcohalide glass at 350 °C (T_g −10 °C) for 24 h. An intensive second harmonic generation (SHG) was observed clearly using the Maker fringe technique, and the origin of SHG was mainly ascribed to the AgGaGeS4 nonlinear optical crystallites contained in the surface crystallized layer. The thickness of the surface crystallized layer showing SHG activation is approximate 50 μm. The χ⁽²⁾ susceptibility of the prepared surface crystallized 30GeS₂ · 35Ga₂S₃ · 35AgCl chalcohalide glass is calculated to be about 12.4 pm/V at a fundamental wavelength of 1064 nm, which indicates a promising nonlinear optical material in the infrared spectral region.     

Efficient and Layer‐Dependent Exciton Pumping across Atomically Thin Organic–Inorganic Type‐I Heterostructures

The fundamental light–matter interactions in monolayer transition metal dichalcogenides might be significantly engineered by hybridization with their organic counterparts, enabling intriguing optoelectronic applications. Here, atomically thin organic–inorganic (O–I) heterostructures, comprising monolayer MoSe₂ and mono‐/few‐layer single‐crystal pentacene samples, are fabricated. These heterostructures show type‐I band alignments, allowing efficient and layer‐dependent exciton pumping across the O–I interfaces. The interfacial exciton pumping has much higher efficiency (>86 times) than the photoexcitation process in MoSe₂, although the pentacene layer has much lower optical absorption than MoSe₂. This highly enhanced pumping efficiency is attributed to the high quantum yield in pentacene and the ultrafast energy transfer between the O–I interface. Furthermore, those organic counterparts significantly modulate the bindings of charged excitons in monolayer MoSe₂ via their precise dielectric environment engineering. The results open new avenues for exploring fundamental phenomena and novel optoelectronic applications using atomically thin O–I heterostructures.     

Infrared light absorption of silver film coated on the surface of femtosecond laser microstructured silicon in SF6

Absorptive properties of 100 nm thick silver (Ag) films coated on the surface of microstructured silicon prepared by femtosecond laser pulses irradiation in SF₆ were measured in a wavelength range of 1.33–16.7 µm. Greatly enhanced light absorption of Ag films was observed in the entire measured wavelength range. For sample with 6–8 µm spikes, the absorptance is approximately 0.9 and essentially unchanged in the wavelength region of 1.33–10 µm, and decreases slightly when λ > 10 µm, but keeps higher than 0.75 over the whole measured wavelength range. The infrared absorption is strongly related to the height and density of the spikes. While for the samples without Ag coating, the absorption is much lower than that of the Ag films. Multiple reflection of light between spikes and surface plasmon excitation of nano-particles on the spikes surface may lead to the strongly enhanced infrared absorption in such a wide wavelength range.     

Quantifying Quasi‐Fermi Level Splitting and Mapping its Heterogeneity in Atomically Thin Transition Metal Dichalcogenides

One of the most fundamental parameters of any photovoltaic material is its quasi‐Fermi level splitting (?µ) under illumination. This quantity represents the maximum open‐circuit voltage (V_oc) that a solar cell fabricated from that material can achieve. Herein, a contactless, nondestructive method to quantify this parameter for atomically thin 2D transition metal dichalcogenides (TMDs) is reported. The technique is applied to quantify the upper limits of V_oc that can possibly be achieved from monolayer WS₂, MoS₂, WSe₂, and MoSe₂‐based solar cells, and they are compared with state‐of‐the‐art perovskites. These results show that V_oc values of ≈1.4, ≈1.12, ≈1.06, and ≈0.93 V can be potentially achieved from solar cells fabricated from WS₂, MoS₂, WSe₂, and MoSe₂ monolayers at 1 Sun illumination, respectively. It is also observed that ?µ is inhomogeneous across different regions of these monolayers. Moreover, it is attempted to engineer the observed ?µ heterogeneity by electrically gating the TMD monolayers in a metal‐oxide‐semiconductor structure that effectively changes the doping level of the monolayers electrostatically and improves their ?µ heterogeneity. The values of ?µ determined from this work reveal the potential of atomically thin TMDs for high‐voltage, ultralight, flexible, and eye‐transparent future solar cells.     

Relationship between photoluminescence and structural properties of the sputtered Zn1−xCdxO films on Si substrates

Zn_1−xCd_xO (x=0.2, 0.4) alloyed crystal thin films have been deposited on Si(1 1 1) substrates at different temperatures by using dc reactive magnetron sputtering technique. The Zn_1−xCd_xO films are of highly (0 0 2)-preferred orientation possessing the hexagonal wurtzite structure of pure ZnO. At 450 °C, the films have better crystal quality and photoluminescent characteristics. For the films with x=0.2 and 0.4, the corresponding near-band-edge (NBE) energies are 3.10 and 3.03 eV, respectively, both have red-shifts compared with that of ZnO (3.30 eV). For the substrate temperatures lower or higher than 450 °C, the other NBE emission peak appears, the X-ray diffraction intensity of (0 0 2) peak decreases and the related FWHM increases. With the Cd addition up to x=0.4 both the XRD and PL intensity of the Zn_1−xCd_xO films decrease sharply in comparison with x=0.2.     

Photoluminescence and electrochemistry behavior of well-dispersible poly-N-[5-(8-quinolinol)ylmethyl]aniline/nano-TiO2 composite

Well-dispersible poly-N-[5-(8-quinolinol)ylmethyl]aniline/nano-TiO₂ composite was synthesized by the surface modification of nano-TiO₂ particles using poly-N-[5-(8-quinolinol)ylmethyl] (PANQ), and it was characterized by Fourier-transform infrared spectroscopy, photoluminescence spectroscopy, thermogravimetric analysis and scanning electron microscope, as well as conductivity and cyclic voltammogram were given. The conductivity of this composite was 2.1 × 10⁻² S cm⁻¹ at 25 °C, and showed good redox reversibility. It was easy to cast a transparent conducting film with photoluminescent property.     

Effect of oxygen pressure of SiOx buffer layer on the electrical properties of GZO film deposited on PET substrate

The present work was made to investigate the effect of oxygen pressure of SiO_x layer on the electrical properties of Ga-doped ZnO (GZO) films deposited on poly-ethylene telephthalate (PET) substrate by utilizing the pulsed-laser deposition at ambient temperature. For this purpose, the SiO_x buffer layers were deposited at various oxygen pressures ranging from 13.3 to 46.7 Pa. With increasing oxygen pressure during the deposition of SiO_x layer as a buffer, the electrical resistivity of GZO/SiO_x/PET films gradually decreased from 7.6 × 10^− 3 to 6.8 × 10^− 4 Ω·cm, due to the enhanced mobility of GZO films. It was mainly due to the grain size of GZO films related to the roughened surface of the SiO_x buffer layers. In addition, the average optical transmittance of GZO/SiO_x/PET films in a visible regime was estimated to be ~ 90% comparable to that of GZO deposited onto a glass substrate.     

Enhancement of fatigue endurance and retention characteristic in Bi3.25Eu0.75Ti3O12 thin films

The effects of moderate annealing temperature (600–800 °C) on the microstructure, fatigue endurance, retention characteristic, and remnant polarization (2P_r) of Bi_3.25Eu_0.75Ti₃O₁₂ (BET) thin films prepared by metal-organic decomposition (MOD) were studied in detail. 2P_r (66 µC/cm² under 300 kV/cm), fatigue endurance (3% loss of 2P_r after 1.2 × 10¹⁰ switching cycles), and retention characteristic (no significant polarization loss after 1.8 × 10⁵s) for BET thin film annealed at 700 °C are better than those for thin films annealed at other temperature. The mechanisms concerning the dependence of microstructure and ferroelectric properties on the annealing temperature were discussed.     

Out‐of‐Plane Strain Induced in a Moiré Superstructure of Monolayer MoS2 and MoSe2 on Au(111)

Making contact of transition metal dichalcogenides (TMDCs) with a metal surface is essential for fabricating and designing electronic devices and catalytic systems. It also generates strain in the TMDCs that plays significant role in both electronic and phonon structures. Therefore, detailed understanding of mechanism of the strain generation is important to fully comprehend the modulation effect for the electronic and phonon properties. Here, MoS₂ and MoSe₂ monolayers are grown on Au surface by chemical vapor deposition and it is demonstrated that the contact with a crystalline Au(111) surface gives rise to only out‐of‐plane strain in both MoS₂ and MoSe₂ layers, whereas no strain generation is observed on polycrystalline Au or SiO₂/Si surfaces. Scanning tunneling microscopy analysis provides information regarding consequent specific adsorption sites between lower S (Se) atoms in the S? Mo? S (Se? Mo? Se) structure and Au atoms via unique moiré superstructure formation for MoS₂ and MoSe₂ layers on Au(111). This observation indicates that the specific adsorption sites give rise to out‐of‐plane strain in the TMDC layers. Furthermore, it also leads to effective modulation of the electronic structure of the MoS₂ or MoSe₂ layer.     

Construction of MoO3/MoSe2 nanocomposite-based gas sensor for low detection limit trimethylamine sensing at room temperature

In this paper, MoO₃/MoSe₂ nanocomposite was constructed by an improved hydrothermal and spin coating method for fabricating trimethylamine (TMA) gas sensor. The surface morphology and microstructure of the prepared materials were analyzed by XRD, XPS, SEM and TEM characterization methods. The microstructural characterization results demonstrated that the MoO₃/MoSe₂ nanocomposite had been successfully synthesized, in which the MoSe₂ had a flower-shaped structure, and MoO₃ had a rod-shaped structure. At the same time, the MoSe₂ surface exhibited periodic honeycomb structure. The gas sensitivity experimental results showed that the proposed MoO₃/MoSe₂ sensor had excellent TMA sensing performance at room temperature, including high response capability, low detection limit (20 ppb), short response/recovery time (12 s/19 s), long-term stability, good repeatability and outstanding selectivity. The heterostructure of MoO₃/MoSe₂ had made outstanding contributions to the enhanced TMA gas sensing performance at room temperature.

     

Preparation of TeO2 based thin films by nonhydrolytic sol–gel process

To solve the problem of the extremely high hydrolytic reactivity of tellurium alkoxides in hydrolytic sol–gel method, the nonhydrolytic sol–gel process has been applied as a novel route for producing TeO₂ based thin films. The transition of nonhydrolytic sol–gel was monitored by means of ¹H NMR, FT-IR and Raman techniques. These results show that the formation of Te–O–Te bonds in gel networks mainly resulted from the nonhydrolytic cross-condensation reaction between different Te–OR groups. The decomposition process and structure evolution of the nonhydrolytic gel products were investigated and managed. Results from DTA and XRD analyses show that metallic tellurium, β-TeO₂ and α-TeO₂ phase appeared in the film during heat-treatment process at around 300, 350 and 400 °C, respectively. The formation of metallic tellurium can be alleviated through preheating the gel films under O₂ atmosphere or by additions of the second component. Crystallization of α-TeO₂ could be retarded by additions of TiO₂ or Al₂O₃, and the transparent, homogeneous amorphous TeO₂ based thin films were obtained by the methods above. The nonhydrolytic sol–gel process developed in this study offers a simple and practical method for fabricating TeO₂ based thin film devices.     

Extending the Colloidal Transition Metal Dichalcogenide Library to ReS2 Nanosheets for Application in Gas Sensing and Electrocatalysis

Among the large family of transition metal dichalcogenides, recently ReS₂ has stood out due to its nearly layer‐independent optoelectronic and physicochemical properties related to its 1T distorted octahedral structure. This structure leads to strong in‐plane anisotropy, and the presence of active sites at its surface makes ReS₂ interesting for gas sensing and catalysts applications. However, current fabrication methods use chemical or physical vapor deposition (CVD or PVD) processes that are costly, time‐consuming and complex, therefore limiting its large‐scale production and exploitation. To address this issue, a colloidal synthesis approach is developed, which allows the production of ReS₂ at temperatures below 360 °C and with reaction times shorter than 2h. By combining the solution‐based synthesis with surface functionalization strategies, the feasibility of colloidal ReS₂ nanosheet films for sensing different gases is demonstrated with highly competitive performance in comparison with devices built with CVD‐grown ReS₂ and MoS₂. In addition, the integration of the ReS₂ nanosheet films in assemblies together with carbon nanotubes allows to fabricate electrodes for electrocatalysis for H₂ production in both acid and alkaline conditions. Results from proof‐of‐principle devices show an electrocatalytic overpotential competitive with devices based on ReS₂ produced by CVD, and even with MoS₂, WS₂, and MoSe₂ electrocatalysts.