Chemical Deposition Research Articles

CVD graphene with high electrical conductivity: empowering applications

Abstract Graphene is an extraordinary material boasting a unique structure, enthralling properties, and promising application vistas. Particularly, the remarkable electrical conductivity of graphene confers it with an inimitable superiority in multiple fields. Endeavors have been continuously made to progressively elevate the conductivity of graphene materials that are synthesized using chemical vapor deposition (CVD), the primary means to prepare high-quality graphene in batches. From this perspective, we offer a comprehensive analysis and discussions on the growth, transfer, and post-treatment strategies evolved towards highly conductive graphene over the past five years. Large-area graphene films, ranging from monolayer to multilayer ones, are initially addressed, succeeded by graphene-based composites which enable traditional metals and non-metal materials to showcase novel or enhanced electrical performances. Eventually, an outlook for future directions to achieve higher electrical conductivity and to develop novel applications for CVD graphene materials is provided.

Inside Ceramics and Between MgO Grains: Solid-State Synthesis of Intergranular Semiconducting or Magnetic Spinels.

Configurations of composite metal oxide nanoparticles are typically far off their thermodynamic equilibrium state. As such they represent a versatile but so far overlooked source material for the intergranular solid-state chemistry inside ceramics. Here, it is demonstrated how the admixture of Fe3+ and In3+ ions to MgO nanoparticles, as achieved by flame spray pyrolysis, can be used to engage ion exsolution, phase separation, and subsequent spinel formation inside the network of diamagnetic and insulating MgO grains. Extremely high uniformity in the distribution of intergranular ferrimagnetic MgFe2O4 films and grains with resulting magnetic coercivity values that depend on the nanoparticles' initial Fe3+ concentration is achieved. Moreover, percolating networks of semiconducting MgIn2O4 are derived from MgO nanoparticles with admixtures of 20 at% In3+ that gives rise to an enhancement of dc conductivity values by more than five orders of magnitude in comparison to the insulating MgO host. The here presented approach is general and applicable to the synthesis of a variety of functional spinel nanostructures embedded inside ceramic matrices. Nanoparticle loading with aliovalent impurity ions, the level of nanoparticle powder density after compaction, and sintering temperature are key parameters for this novel type of solid-state chemistry in between the host grains.

Ultrafast Charge and Exciton Diffusion in Monolayer Films of 9-Armchair Graphene Nanoribbons.

Determining the electronic transport properties of graphene nanoribbons is crucial for assessing their suitability for applications. So far, this has been highly challenging both through experimental and theoretical approaches. This is particularly the case for graphene nanoribbons that are prepared by chemical vapor deposition, which is a scalable and industry-compatible bottom-up growth method that results in closely packed arrays of ribbons with relatively short lengths of a few tens of nanometers. In this study, the experimental technique of spatiotemporal microscopy is applied to study monolayer films of 9-armchair graphene nanoribbons prepared using this growth method, and combined with linear-scaling quantum transport calculations of arrays of thousands of nanoribbons. Both approaches directly resolve electronic spreading in space and time through diffusion and give an initial diffusivity approaching 200 cm2 s-1 during the first picosecond after photoexcitation. This corresponds to a mobility up to 550 cm2 V-1 s-1. The quasi-free carriers then form excitons, which spread with a diffusivity of tens of cm2 s-1. The results indicate that this relatively large charge carrier mobility is the result of electronic transport not being hindered by defects nor inter-ribbon hopping. This confirms their suitability for applications that require efficient electronictransport.

Super High-k Unit-Cell-Thick α-CaCr2O4 Crystals.

High-dielectric-constant (high-k) insulators are indispensable components to integrate semiconductors into metal-oxide-semiconductor field-effect transistors with sub-10 nm channel length, where the equivalent oxide thickness (EOT) of high-k insulator needs to be decreased to subnanometer scale. The traditional insulators, including Al2O3, SiO2, and HfO2, fit well with the existing silicon industry but suffer from serious degeneration of insulating properties, such as large leakage currents caused by high-density borders and interface traps, when their thicknesses are reduced to a few nanometers. Here, we synthesize a high-quality nonlayered ultrathin α-CaCr2O4 crystal down to unit-cell thickness (∼1.2 nm) by an elements slow-supply chemical vapor deposition (CVD) method. The unit-cell-thick α-CaCr2O4 crystals show a super high dielectric constant of 87.34, which is over 20 times higher than that of well-known layered insulator h-BN and corresponds to an EOT below 1 nm. Furthermore, it has a high breaking strength (39 GPa) and excellent stability. This strategy can also be used to fabricate other ultrathin ternary oxides, such as high-k ultrathin FeNb2O6 crystals, demonstrating the universality of the CVD method.

Modulating the Electrical Transport in Superconducting NbC Crystals by Fractal Morphology.

The self-similar fractal morphology mediated by nonequilibrium processes is widely observed in low-dimensional materials grown by various techniques. Understanding how these fractal geometries affect the physical and chemical properties of materials and devices is crucial for both fundamental studies and various applications. In particular, the interplay between superconducting phase fluctuations and disorder can give rise to intriguing phenomena depending on the dimensionality. However, current experimental studies on low-dimensional superconductors are limited to two- and one-dimensional systems, leaving fractional dimensional systems largely unexplored. Here, we use chemical vapor deposition to successfully synthesize ultrathin NbC crystals with a well-defined fractal geometry at the nanoscale. By performing electrical transport measurements, we find that both the superconducting and normal-state properties are strongly affected in the fractal samples, where the intrinsic and geometric disorder is induced. In contrast to the 2D crystal, the fractal NbC crystals show a significant low-temperature resistive upturn before the onset of superconducting transition, which can be attributed to the disorder-enhanced electron-electron interaction effect. From transport data analysis, we demonstrate that the superconducting transition in NbC is correlated to the strength of disorder and the fractional dimensions, revealing that nanoscale fractal structures can significantly modify the electronic properties of low-dimensional superconductors. Our work paves the way for the explorations of mesoscopic transport and intriguing superconducting phenomena in fractional dimensions.

Growth Kinetics of Graphene on Cu(111) Foils from Methane, Ethyne, Ethylene, and Ethane.

Chemical vapor deposition of carbon precursors on Cu-based substrates at temperatures exceeding 1000 °C is currently a typical route for the scalable synthesis of large-area high-quality single-layer graphene (SLG) films. Using molecules with higher activities than CH4 may afford lower growth temperatures that might yield fold- and wrinkle-free graphene. The kinetics of growth of graphene using hydrocarbons other than CH4 are of interest to the scientific and industrial communities. We measured the growth rates of graphene islands on Cu(111) foils by using C2H2, C2H4, C2H6 and CH4, respectively (each mixed with H2). From such kinetics data we obtain the activation enthalpy (ΔH≠) of graphene growth as shown in parentheses (C2H2 (0.93±0.09 eV); C2H4 (2.05±0.19 eV); C2H6 (2.50±0.11 eV); CH4 (4.59±0.26 eV)); C2Hy (y=2, 4, 6) show similar growth behavior but CH4 is different. Computational fluid dynamics and density functional theory simulations suggest that C2Hy differs from CH4 due to different values of adsorption energy and the lifetime of relevant carbon precursors on the Cu(111) surface. Combining experimental and simulation results, we find that the rate determining step (RDS) is the dissociation of the first C-H bond of CH4 molecules in the gas phase, while the RDS using C2Hy is the first dehydrogenation of adsorbed C2Hy that happens with assistance of H atoms adsorbed on the Cu(111) surface. By using C2H2 as the carbon precursor, high-quality single-crystal adlayer-free SLG films are achieved on Cu(111) foils at 900 °C.

Effect of experimental conditions on the fabrication of SnO2 thin films via spray pyrolysis technique

Effect of experimental conditions on the fabrication of SnO2 thin films via spray pyrolysis technique

Supercapacitor performance of pure and Ni-doped CuO electrodes prepared by USP

Abstract In this study, the ultrasonic spray pyrolysis (USP) technique was employed to fabricate pure and 3% Ni-doped copper oxide (CuO) thin films (TFs) on In2O3/SnO2 (ITO) coated glass substrates. X-ray diffraction (XRD) analysis revealed that both pure and 3% Ni-doped CuO TFs exhibit a polycrystalline structure with the tenorite phase oriented preferentially along the (111) plane. The morphological properties of these TFs were characterized using scanning electron microscopy (SEM) and atomic force microscopy (AFM) imaging. Energy dispersive x-ray spectroscopy (EDX) confirmed that the deposited TFs achieved the desired stoichiometry. The electrochemical properties of both pure and 3% Ni-doped CuO TFs were evaluated using cyclic voltammetry (CV), galvanostatic charge/discharge (GCD), and electrochemical impedance spectroscopy (EIS). At a current density of 1 A g−1, the specific capacitance of pure CuO TFs was found to be 78 F g−1, decreasing to 2 F g−1 at 10 A g−1. In contrast, Ni-doped CuO TFs exhibited a specific capacitance of 722 F g−1 at 1 A g−1 and 20 F g−1 at 10 A g−1. These results indicate that Ni-doping significantly enhances the specific capacitance values. The superior performance of Ni-doped CuO electrodes is attributed to their uniformly high porosity and improved electrical conductivity, demonstrating Ni-doped CuO as an optimal electrode material for pseudocapacitors.

Online Three-Dimensional Fuzzy Reinforcement Learning Modeling for Nonlinear Distributed Parameter Systems

Distributed parameter systems (DPSs) frequently appear in industrial manufacturing processes, with complex characteristics such as time–space coupling, nonlinearity, infinite dimension, uncertainty and so on, which is full of challenges to the modeling of the system. At present, most DPS modeling methods are offline. When the internal parameters or external environment of DPS change, the offline model is incapable of accurately representing the dynamic attributes of the real system. Establishing an online model for DPS that accurately reflects the real-time dynamics of the system is very important. In this paper, the idea of reinforcement learning is creatively integrated into the three-dimensional (3D) fuzzy model and a reinforcement learning-based 3D fuzzy modeling method is proposed. The agent improves the strategy by continuously interacting with the environment, so that the 3D fuzzy model can adaptively establish the online model from scratch. Specifically, this paper combines the deterministic strategy gradient reinforcement learning algorithm based on an actor critic framework with a 3D fuzzy system. The actor function and critic function are represented by two 3D fuzzy systems and the critic function and actor function are updated alternately. The critic function uses a TD (0) target and is updated via the semi-gradient method; the actor function is updated by using the chain derivation rule on the behavior value function and the actor function is the established DPS online model. Since DPS modeling is a continuous problem, this paper proposes a TD (0) target based on average reward, which can effectively realize online modeling. The suggested methodology is implemented on a three-zone rapid thermal chemical vapor deposition reactor system and the simulation results demonstrate the efficacy of the methodology.

A Spray-Deposited Modified Silica Film on Selective Coatings for Low-Cost Solar Collectors

Solar collectors represent an attractive green technology for water heating, where sunlight is efficiently absorbed by a selective coating and the generated heat is transferred to water. In this work, the improvement and scale-up of an electrodeposited black nickel selective coating with a modified silica (MS) film deposited by spray pyrolysis are reported. The MS material was prepared by the sol–gel method using tetraethyl orthosilicate with the addition of n-propyl triethoxysilane to obtain a porous film with an adequate refractive index and enhanced flexibility. The reflectance of electrodeposited selective coatings was characterized with and without the MS film and compared to a commercially available coating of black paint. The MS film increased the solar absorptance from 89% to 93% while maintaining a much lower thermal emittance than the painted coating. The reflectance of the MS film remained unchanged after prolonged thermal treatment at 200 °C (200 h). The fabrication process was scaled up to 193 cm × 12 cm copper fins, which were incorporated in commercial-size flat-plate solar collectors. Three complete collectors of an area of 1.7 m2 were fabricated and their performance was evaluated under outdoor conditions. The results show that the electrodeposited selective coating with the MS film outperformed both the commercial black paint system and the system without the modified silica film.

Nanostructured Coatings of 3d-Metals Produced by Green Chemistry Methods: Analysis of Inhomogeneities by Static and Dynamic Magnetic Methods

The study investigates carbon-containing coatings of 3d-metals (Ni, Co, Fe) produced by chemical deposition method using arabinogalactan. The coatings were analyzed using X-ray diffraction, FMR, and M(H) magnetometry. Measurement of M(H) in plane and perpendicular to the plane of the magnetic coatings allowed determining the distribution of demagnetizing factor in the studied coatings. The obtained distributions of the demagnetizing factor were used to analyze the angular dependences of the ferromagnetic resonance field. The values of magnetization and perpendicular anisotropy field were estimated. The paper illustrates the effect of texture on the magnetic parameters.

Unusual Anomalous Hall Effect in Two-Dimensional Ferromagnetic Cr7Te8

Two-dimensional (2D) materials with inherent magnetism have attracted considerable attention in the fields of spintronics and condensed matter physics. The anomalous Hall effect (AHE) offers a theoretical foundation for understanding the origins of 2D ferromagnetism (2D-FM) and offers a valuable opportunity for applications in topological electronics. Here, we present uniform and large-size 2D Cr7Te8 nanosheets with varying thicknesses grown using the chemical vapor deposition (CVD) method. The 2D Cr7Te8 nanosheets with robust perpendicular magnetic anisotropy, even a few layers deep, exhibit a Curie temperature (TC) ranging from 180 to 270 K according to the varying thickness of Cr7Te8. Moreover, we observed a temperature-induced reversal in the sign of the anomalous Hall resistance, correlating with changes in the intrinsic Berry curvature. Additionally, the topological Hall effect (THE) observed at low temperatures suggests the presence of non-trivial spin chirality. Our findings about topologically non-trivial magnetic spin states in 2D ferromagnets provide a promising opportunity for new designs in magnetic memory spintronics.

Improvement of curing efficiency and heat resistance of CFRP by the growth of SiCNWs on CF

Carbon fiber-reinforced polymer composites are widely used in modern industry. However, poor heat transfer between layers of carbon fiber cloth during the curing process leading to poor curing of the substrate, long curing cycles, and excessive heat accumulation has become an urgent problem to be solved. A common approach is dispersing highly thermally conductive fillers in the polymer matrix to improve the curing efficiency of the composites. Different from adding fillers, we report a novel method of in situ growth of SiC nanowires (SiCNWs) on the surface of carbon fiber (CF) by the chemical vapor deposition (CVD) method and study the effects of CVD deposition time on curing efficiency and thermal stability of the composites. The results indicate that the nano bridge effect of SiCNWs significantly improves the curing efficiency of the composites. Compared with pure CF/epoxy composites, the curing efficiency can be increased by 38.72%. The cross-linking point between SiCNWs and the resin matrix enhances the thermal stability of the composites and increases the heat resistance index ( T HRI) by 8.4°C.

Preparation of high strength and rigidity carbon layer on SiO material surface by dynamic CVD method using gas carbon source C2H2

The main issue in the application of silicon-based negative electrode materials is the inevitable volume expansion, leading to negative electrode material fracture, which severely impacts the performance of batteries. This study employed Chemical Vapor Deposition (CVD) (C2H2@SiO), solid-phase coating method (Pitch@SiO), and liquid-phase coating method (RGFQ@SiO) to coat the surface of SiO materials with a dense amorphous carbon structure. Material property analysis revealed that C2H2@SiO has a relatively small specific surface area (1.8 m2 g−1) and surface carbon increment (2.4 %). It exhibited high reversible specific capacity (1563.4 mAh g−1), high initial Coulombic efficiency (81.45 %), and low volume expansion rate (9.3 %). Mechanical performance testing indicated that the surface carbon layer Young's modulus of C2H2@SiO was the highest (35 GPa), suggesting that using the CVD method to obtain a dense carbon layer can enhance the structural strength of the material. Based on the electrochemical-mechanical coupling theory simulation analysis of the stress during the charge-discharge process of electrode materials, the evolution of concentration and stress field during lithium insertion process was obtained, showing that the coating can further improve the electrochemical and mechanical performance of the negative electrode materials effectively. Additionally, the negative electrode sheets fabricated using sample C2H2@SiO were assembled into 18650 cylindrical batteries, exhibiting excellent cycling performance in 1000 cycles at 25 °C with a capacity retention rate of 85.7 %, along with good rate capability and high/low-temperature performance. The conclusions of this study provide certain guidance for the design and optimization of negative electrode materials for battery electrodes.

Enhancement of removing OH bonds from low-temperature deposited silicon oxide films by adding water vapor into NH3 gas annealing at 130 oC

Abstract It was found that annealing with water-vapor-added NH3 gas (water-added NH3) is more effective than with dry NH3 at removing residual OH bonds in silicon oxide (SiOx) films deposited by atmospheric chemical vapor deposition with an organic silicon source. Fourier transform infrared spectra showed that reduction amount of OH bonds using the water-added NH3 was ~4 or ~1.3 times larger than using the conventional dry N2 or dry NH3 mixed with N2 gas without water, respectively. This result is something strange because water can be a potential candidate of OH sources. The effect of water vapor on OH-bond removal can be explained by considering following three factors. One is that low-temperature SiOx films are constrained somewhat, the second is that strained Si-O-Si bonds are in higher or more unstable energy state than strain-free ones, and the third is that highly strained bonds are easily hydroxylated to form Si-OH bonds.

Flexible p-Type WSe2 Transistors with Alumina Top-Gate Dielectric.

Tungsten diselenide (WSe2) field-effect transistors (FETs) are promising for emerging electronics because of their tunable polarity, enabling complementary transistor technology, and their suitability for flexible electronics through material transfer. In this work, we demonstrate flexible p-type WSe2 FETs with absolute drain currents |ID| up to 7 μA/μm. We achieve this by fabricating flexible top-gated FETs with a combined WSe2 and metal contact transfer approach using WSe2 grown by metal-organic chemical vapor deposition on sapphire. Despite moderate WSe2 crystal grain size, our devices show similar or higher |ID| and ID on/off ratio (∼105) compared to most devices with exfoliated single-crystal WSe2 from the literature. We analyze charge trapping in our devices using pulsed and bias stress measurements. Notably, the high |ID| values are preserved during pulsing, where charge trapping is minimized. Overall, we demonstrate a fabrication approach advantageous for high drain currents in flexible 2D transistors.

Direct One-Stage Plasma Chemical Synthesis of Nanostructured Thin Films of the System β-Ga<sub>2</sub>O<sub>3</sub>-GaN of Different Composition

For the first time, nanostructured thin films of the β-Ga2O3−GaN system were obtained by plasma chemical deposition from the gas phase (PECVD) on c-sapphire substrates. High-purity metallic gallium, as well as high-purity gaseous nitrogen and oxygen were used as sources of macro components. The low-temperature nonequilibrium plasma of an inductively coupled HF (40.68 MHz) discharge at a reduced pressure (0.01 Torr) was the initiator of chemical transformations between the starting substances. A mixture of oxygen and nitrogen was used as a plasma-forming gas. The plasma chemical process was studied using the optical emission spectroscopy (OES) method. The obtained thin films of the β-Ga2O3−GaN system with a GaN phase content of 2 to 7% were characterized by various analytical methods.

Saturation Mobility of 100 cm2 V-1 s-1 in ZnO Thin-Film Transistors through Quantum Confinement by a Nanoscale In2O3 Interlayer Using Spray Pyrolysis.

In this study, we present a comprehensive study on the fabrication and characterization of heterojunction In2O3/ZnO thin-film transistors (TFTs) aimed at exploiting the quantum confinement effect to enhance device performance. By systematically optimizing the thickness of the crystalline In2O3 (c-In2O3) layer to create a narrow quantum well, we observed a significant increase in saturation mobility (μSAT) from 12.76 to 97.37 cm2 V-1 s-1. This enhancement, attributed to quantum confinement, was achieved through the deposition of a 3 nm c-In2O3 semiconductor via spray pyrolysis. Various In2O3 layer thicknesses (2-5 nm) were obtained by adjusting precursor solution concentration, flow rate, and number of spray cycles. Post annealing treatments were employed to reduce the defects at the interface and within the oxide film, enhancing device stability and performance. Transmission electron microscopy (TEM) confirmed the uniformity of the c-In2O3 film thickness, while variations in thickness significantly influenced TFT performance, particularly the turn-on voltage (VGS) due to changes in the carrier concentration. Ultraviolet photoelectron spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS) supported the formation of a potential well with a two-dimensional electron gas (2DEG). The study of single and multiple superlattice structures of consecutive c-In2O3 and c-ZnO layers provided insights into the effects of multiple quantum wells on the TFT performance. This research presents an advanced approach to TFT optimization, highlighting high reliability, and environmental and bias stabilities. These lead to enhanced mobility and performance uniformity through the precise control of c-In2O3 layer thickness for the quantum confinement effect.

Strain-Engineered Ferroelectricity in 2H Bilayer MoS2.

The exploration of two-dimensional (2D) materials exhibiting out-of-plane ferroelectric and piezoelectric properties through interlayer twist/translation or strain, known as sliding ferroelectricity, has become a focal point in the quest for low-power electronic devices, capitalizing on weak van der Waals interactions. Herein, we delve into the behavior of strained bilayer molybdenum disulfide (2L-MoS2) transferred onto a nanocone-patterned substrate. An intriguing observation is the emergence of unexpected vertical ferroelectricity in MoS2, irrespective of whether it was prepared using chemical vapor deposition or mechanical exfoliation from the bulk crystal. Such an observation underscores the versatility and reproducibility of the emerging ferroelectricity across different preparation methods. Furthermore, the piezoelectric coefficients recorded are exceptionally high, with the values of 37.54 and 24.80 pm V-1 for monolayer and bilayer MoS2, respectively, outperforming most currently discovered 2D piezoelectrics. The presence of room-temperature out-of-plane ferroelectricity in strained 2L-MoS2 is confirmed through first-principles calculations and piezoresponse force microscopy. This ferroelectric behavior can be attributed to the symmetry breaking and interlayer sliding within the strained 2L-MoS2 structure. Our findings not only deepen the understanding of ferroelectricity in 2D materials but also offer insights for the design of 2D ferroelectrics, thereby enabling diverse functionalities and applications in ferroelectricity.

Growth of zinc oxide nanowires by a hot water deposition method.

Recently, various methods have been developed for synthesizing zinc oxide (ZnO) nanostructures, including physical and chemical vapor deposition, as well as wet chemistry. These common methods require either high temperature, high vacuum, or toxic chemicals. In this study, we report the growth of zinc oxide ZnO nanowires by a new hot water deposition (HWD) method on various types of substrates, including copper plates, foams, and meshes, as well as on indium tin oxide (ITO)-coated glasses (ITO/glass). HWD is derived from the hot water treatment (HWT) method, which involves immersing piece(s) of metal and substrate(s) in hot deionized water and does not require any additives or catalysts. Metal acts as the source of metal oxide molecules that migrate in water and deposit on the substrate surface to form metal oxide nanostructures (MONSTRs). The morphological and crystallographic analyses of the source-metals and substrates revealed the presence of uniformly crystalline ZnO nanorods after the HWD. In addition, the growth mechanism of ZnO nanowires using HWD is discussed. This process is simple, inexpensive, low temperature, scalable, and eco-friendly. Moreover, HWD can be used to deposit a large variety of MONSTRs on almost any type of substrate material or geometry.