单层和双层二硫化钼化学气相沉积生长的动力学蒙特卡罗模拟研究

Controllable synthesis of MoS₂ with desired number of layers via chemical vapor deposition (CVD) remains challenging. Hence, it is highly desirable to develop a theoretical model that can be used to predict the single- and multilayer growth of MoS₂ quantitatively, and provide guidelines for experimental fabrication. Herein we have established a kinetic Monte Carlo (kMC) model to predict the CVD growth of mono- and bilayer MoS₂. First, we proposed that the growth rates of layer 1 and layer 2 were governed by the distribution of the adatom concentration, and the growth kinetics of compact triangular MoS₂ followed the kink nucleation-propagation mechanism. The adatom concentration was formulated in terms of adatom flux, effective lifetime of adatoms, growth temperature, binding energies, edge energies, and nucleation criterion. The kink nucleation and propagation were determined by energy barriers of the adatom attachments to the zigzag and armchair edges. We then employed an analytic thermodynamic criterion to extract these parameters. Using the calibrated model, we found that the growth rate of layer 2 strongly depended on the size of layer 1 and decreased monotonically with increasing size of layer 1, and might even become prohibited at the maximum size of layer 1. Furthermore, we analyzed the size and morphology evolutions of bilayer MoS₂ at different growth temperatures and adatom fluxes. Throughout the growth processes of bilayer MoS₂, the morphologies of layers 1 and 2 maintained triangular shapes with compact edges, consistent with the kink nucleation-propagation growth mechanism. Our simulations revealed that the growth of bilayer MoS₂ was promoted by increasing the growth temperature or decreasing the adatom flux, which corroborated the experimental observations. The increase in growth temperature led to reduced adatom concentration at the edge of layer 2 in accordance with the adatom concentration far from the edge of layer 2, resulting in a consistent difference in the adatom concentration to promote the growth of bilayer MoS₂. Similarly, the decrease in adatom flux lowered the difference between the adatom concentrations far from the edge and at the edge of layer 1, decelerating the growth of layer 1. The decelerated growth of layer 1 reduced the difference between the adatom concentrations far from the edge and at the edge of layer 2 to zero, permitting the growth of bilayer MoS₂. To guide the experimental synthesis, we constructed a phase diagram to delineate the permitted or prohibited growth of bilayer MoS₂ at different growth temperatures and adatom fluxes. Hence, this work not only unveils the conditions for the growth of mono- and bi-layer MoS₂, but also provides guidelines for controllable synthesis of MoS₂ with the desired number of layers.     

Electro‐oxidized Monolayer CVD Graphene Film Transducer for Ultrasensitive Impedimetric DNA Biosensor

We report the effect of electrochemical anodization on the properties of monolayer graphene as the main aim of this research and consequently using the resulting label‐free impedimetric biosensor for DNA sequences detection. Monolayer graphene was grown by chemical vapor deposition (CVD) with methane as precursor on copper foil, transferred onto a glassy carbon electrode and electrochemically anodized. Raman spectroscopy and X‐Ray photo electron spectroscopy revealed enhancement of defect density, roughness and formation of C−O−C, C−O−H and C=O functional groups after anodization. Amine‐terminated poly T probe was linked covalently to the carboxylic groups of anodized graphene by the zero‐length linker to fabricate the impedance‐based DNA biosensor. The anodized graphene electrode demonstrated a superior performance for electrochemical impedance detection of DNA. The DNA biosensor showed a large linear dynamic range from 2.0×10⁻¹⁸ to 1.0×10⁻¹² M with a limit of detection of 1.0×10⁻¹⁸ M using electrochemical impedance spectroscopy (EIS) method. Equivalent circuit modeling shows that DNA hybridization is detected through a change in charge transfer resistance.     

Effect of plasma carrier gas on the moisture barrier properties of plasma-enhanced chemical vapor deposited (PECVD) polyorganosiloxane thin film

Abstract

A polyorganosiloxane thin film was deposited on an optically transparent poly(ethylene 2,6-naphthalate) (PEN) film using plasma-enhanced chemical vapor deposition (PECVD) at room temperature to improve the moisture barrier property of the PEN film. In the PECVD process, hexamethyldisiloxane (HMDSO) was used as the monomer. Argon or oxygen and their mixture gases were used as the plasma carrier gas. Poly(HMDSO) thin film was successfully deposited through plasma-induced radical polymerization reaction on the surface of PEN film. It was observed that the mixture ratio of argon-oxygen carrier gas significantly affected the surface and the moisture barrier properties of the resulting poly(HMDSO) film. Chemical structures of the poly(HMDSO) were confirmed using FT-IR analysis. Surface properties of the poly(HMDSO) thin film were investigated by water contact angle measurement and atomic force microscopy (AFM). Water vapor transmission rate (WVTR) value was obtained by an electrical calcium test (Ca test) at 85?°C and 85% relative humidity condition. It was confirmed that the poly(HMDSO) thin film exhibited excellent water vapor barrier capability. WVTR value of the PEN film coated with poly(HMDSO) deposited with a mixture of argon and oxygen (Ar: O₂ = 2: 8) was 5.09?g/m²-day, which is much lower than 18.4?g/m²-day of a bare PEN film.     

Quantification of Polymer Fouling on Heat Transfer Surfaces During Synthesis

During the synthesis and processing of polymers, a significant amount of polymer may be deposited on the heat transfer surfaces. This deposit is unwanted and is usually named fouling. This study deals with the fouling behavior of a vinyl acetate/vinyl ester copolymer during emulsion polymerization and compares this to fouling of an already reacted vinyl acetate/ethylene copolymer dispersion. Besides the state of polymerization, also the influence of the wall temperature is investigated. The experiments are performed on cooled and heated surfaces. The deposition process is quantified by the mass‐based fouling resistance, the height of the fouling layer, and the surface coverage using a digital microscope. It is found that the state of polymerization and the temperature gradient between wall and bulk exert a strong influence on the fouling behavior, especially on the structure of the fouling layer.     

Effect of iron doping on the hydrophobicity of titanium dioxide film: experiment and simulation

In this study, we carried out experiments and molecular dynamics simulations to identify the effect of Fe doping on the hydrophobicity of a titanium dioxide film. TiO₂ and Fe-doped TiO₂ films were fabricated in situ by atomic layer deposition without annealing. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were used to characterise the crystal structure and elemental composition. Iron doping resulted in the TiO₂ becoming more hydrophobic at a macroscopic level, as estimated by atomic force microscopy observations and static contact angle measurements. Furthermore, the effect of iron doping on the structure and kinetics of water molecules on the exterior of TiO₂ were studied by molecular dynamics simulations. On the basis of the XPS results, the Fe-TiO₂ surface matrix has a Ti:Fe ratio of 36:5. In addition, the density distribution of oxygen and hydrogen atoms indicate that interfacial water molecules enter the Fe-TiO₂ film more easily and hydrogen atoms in the water molecules are oriented upward at the interface. The self-diffusion coefficients indicate that iron doping makes the TiO₂ more hydrophobic, which is consistent with the macroscopic test results.     

Photochemistry in the Low-Temperature Processing of Metal Oxide Thin Films by Solution Methods

Photochemistry has emerged in the last few years as a powerful tool for the low-temperature processing of metal oxide thin films prepared by solution methods. Today, its implementation into the fabrication procedure makes possible the integration of amorphous semiconductors or functional crystalline oxides into flexible electronic systems at temperatures below 350 °C. In this review, the effects of UV irradiation at the different stages of the chemical solution deposition of metal oxide thin films are presented. These stages include from the synthesis of the precursor solution to the formation of the amorphous metal-oxygen network in the film and its subsequent crystallization into the oxide phase. Photochemical reactions that can be induced in both the solution deposited layer and the irradiation atmosphere are first described, highlighting the role of the potential reactive chemical species formed in the system under irradiation, such as free radicals or oxidizing compounds. Then, the photochemical effects of continuous UV light on the film are shown, focusing on the decomposition of the metal precursors, the condensation and densification of the metal-oxygen network, and the nucleation and growth of the crystalline oxide. All these processes are demonstrated to advance the formation and crystallization of the metal oxide thin film to an earlier stage, which is ultimately translated into a lower temperature range of fabrication. The reduced energy consumption of the process upon decreasing the processing temperature, and the prospect of using light instead of heat in the synthesis of inorganic materials, make photochemistry as a promising technique for a sustainable future ever more needed in our life.     

Dual Metastability in Electroless Plating: Complex Inertness Enabling the Deposition of Composition-Tunable Platinum Copper Alloy Nanostructures

Autocatalytic deposition represents a facile, versatile, and scalable wet-chemical tool for nanofabrication. However, the intricate component interplay in plating baths containing multiple metal species impedes alloy deposition. We resolved this challenge in the bimetallic copper-platinum system by exploiting the kinetic stability of platinum complexes, which allows adjusting their ligand sphere and thus reactivity independently from the present copper ions in a preceding, thermally activated ligand exchange step. By using metastable Pt^IV precursors of varying degrees of complexation, copper-platinum alloys of adjustable atomic ratio were plated from solutions of identical composition and concentration, but differing local coordination environment. Due to its excellent conformity and nanoscale homogeneity, the reaction is compatible with ambitious 3D substrate morphologies, as demonstrated in the template-assisted fabrication of nanotubes with high aspect ratio. The ability to generate additional synthetic degrees of freedom by decoupling the metal complex speciation from the solution composition is of large interest for redox-chemical synthesis techniques, such as electrodeposition or nanoparticle colloid production.     

Fabrication of in situ alkali doped flexible CIGSSe solar cells by using aqueous spray deposition

Flexible Cu(In,Ga)(S,Se)₂ (CIGSSe) solar cells were fabricated on stainless steel foil by using aqueous spray deposition method. Since stainless steel foil is used, external alkali doping is necessary to passivate defects in CIGSSe absorber. We investigated effects of (Na, K) co-doping and selenization temperature on solar cell performance. With co-doping of Na and K, defect states were passivated significantly and highest power conversion efficiency (PCE) was obtained. However, at higher K concentration of more than 0.5%, different growth mode of CIGSSe was observed and deep defect states were developed, decreasing PCE. In addition, selenization temperature effects were studied by varying selenization temperatures. With higher selenization temperature, defect passivation for the CIGSSe absorber was more apparent, which facilitated increase of open circuit voltage. However, short circuit current was observed to be decreased at higher selenization temperature of 570 °C. This work demonstrates in-situ alkali co-doping into CIGSSe absorber with simple and low-cost spray deposition in an air environment.     

低温制备微晶硅薄膜生长机制的研究

采用热丝化学气相沉积技术制备了一系列处于不同生长阶段的薄膜样品，用原子力显微镜系 统地研究生长在单晶硅衬底和玻璃衬底上薄膜表面形貌的演化.按照分形理论分析得到：在 玻璃衬底上的硅薄膜以零扩散随机生长模式生长；而在单晶硅衬底上，薄膜早期以有限扩散 生长模式生长，当膜厚超过某一临界厚度时转变为零扩散随机生长模式.岛面密度与膜厚的 依赖关系表明，在临界厚度时硅衬底和玻璃衬底上的岛面密度均出现了极大值.Raman谱的测 量证实，玻璃衬底上薄膜临界厚度与非晶/微晶相变之间存在密切的关系.不同的衬底材料直 接影响反应 关键词： 生长机制 微晶硅薄膜 表面形貌 热丝化学气相沉积