Thermal Chemical Vapor Deposition Research Articles

Self-powered visible-blind ultraviolet photodetectors based on SnO2 nanowire cotton synthesized using thermal chemical vapor deposition

Self-powered visible-blind ultraviolet photodetectors based on SnO2 nanowire cotton synthesized using thermal chemical vapor deposition

Effect of nickel catalyst thickness on growth of carbon nanotubes on glass nonwoven mat using thermal chemical vapor deposition method

This study aimed to explore how varying the thickness of nickel catalyst affects the synthesis of carbon nanotubes on glass mats using the thermal chemical vapor deposition (TCVD) method. Nickel served as the catalyst, with acetylene as the hydrocarbon source and argon as the carrier gas. Initially, different thicknesses of nickel catalyst were applied to the glass mat via plasma-enhanced chemical vapor deposition (PECVD). Subsequently, these samples underwent TCVD plasma treatment. Electrical resistance measurements were conducted, and scanning electron microscopy (SEM), Raman spectroscopy, and transmission electron microscopy (TEM) were employed to analyze the presence, surface morphology, and quality of the nanotubes. The research revealed that the thickness of the nickel catalyst significantly influences the nanotube synthesis process on glass mat substrates. An optimal thickness of nickel catalyst yielded a glass mat with an electrical resistance of 2 Ω per unit area post-TCVD treatment.

A metallic lithium anode for solid-state batteries with low volume change by utilizing a modified porous carbon host

Lithium metal is a promising negative electrode material for solid-state batteries (SSBs). However, uncontrolled lithium deposition and stripping cause several issues during cycling. Herein, the microporous carbon YP-50F and its modifications obtained by thermal ethene-based chemical vapor deposition (CVD) are investigated as 3D host to accommodate and control the deposition of metallic lithium. In half-cells vs. lithium, the CVD-YP composite electrode with Li6PS5Cl electrolyte shows significantly higher initial coulombic efficiency (79.5 %) than the pristine carbon (55.3 %) due to the reduction of side reactions. The metallic character of the deposited lithium is evidenced by 7Li Nuclear Magnetic Resonance spectroscopy. However, full cells with nickel-rich NCM (LiNi0.9Co0.05Mn0.05O2) positive electrode and CVD-YP composite negative electrode show reasonable performance over 50 cycles without occurrence of (micro-) short-circuits (in contrast to 2D reference electrodes). In addition, small prototype pouch cells are investigated and the thickness change during (dis)charging is less than one third compared to a bare lithium metal electrode. This demonstrates low breathing behavior of the CVD-YP electrode and confirms the reversible storage of metallic lithium within the 3D carbon-based composite electrode.

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.

Observation of novel carbon nanocorals during the synthesis of graphene and investigations on their composition, morphological and structural properties

Novel carbon nanocorals (CNCs) are observed during the synthesis of graphene on copper substrates by thermal chemical vapor deposition, using precursor gas acetylene (C2H2) and carrier gas argon (Ar). CNCs have unique structure and investigations are carried out on structural and elemental compositions by X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray excited Auger electron spectroscopy (XAES), energy dispersive X-ray spectroscopy (EDS), field emission scanning electron microscopy (FESEM), and high resolution transmission electron microscopy (HRTEM). The graphitic nature of the CNCs is evident from characteristic D, G, and 2D bands obtained from Raman spectrum. Elemental composition analysis by XPS shows presence of sp2 and sp3 hybridized carbon whereas XAES quantifies percentage of sp2 and sp3 hybridized carbon. FESEM micrographs show a uniform distribution of densely packed CNCs throughout the sample, and formation of groups of CNCs with distinct contours on the surface. The cross-sectional FESEM shows stacking of large number of graphene layers with dendrites. HRTEM analysis further supports observations of FESEM and elaborates structural morphology of the CNCs. Synthesis, characterization and analysis of the properties of carbon nanocorals are reported here, for the first time.

Image Sensors and Photodetectors Based on Low‐Carbon Footprint Solution‐Processed Semiconductors

AbstractThis mini‐review explores the evolution of image sensors, essential electronic components increasingly integrated into daily life. Traditional manufacturing methods for image sensors and photodetectors, employing high carbon footprint techniques like thermal evaporation and chemical vapor deposition, are being replaced by environmentally conscious solution processing. Organic and Colloidal Quantum Dot‐based image sensors emerge as promising candidates, aligning with the shift toward solution‐based device integration. This review provides insights into the working principles of photodetectors and image sensors, summarizing relevant materials and fabrication approaches. Additionally, it delves into the detailed exploration of pixelated patterning techniques and their potential applications in the realm of solution‐processed image sensor fabrication.

Preparation and properties of sustainable superhydrophobic cotton fabrics modified with lignin nanoparticles, tannic acid and methyltrimethoxysilane

Functional superhydrophobic cotton fabrics find extensive applications in both textile and non-textile domains. Nonetheless, fabric treatment typically relies on fluorine-containing compounds, inorganic nanoparticles and potentially hazardous organic solvents, posing environmental risks during fabrication and disposal. To address this issue, endeavours are underway to develop environmentally sustainable and cost-effective methods and materials for imparting superhydrophobic properties to cotton fabric surfaces. Here, we prepared lignin nanoparticles (LNP) utilising deep eutectic solvents and facilitated their surface adhesion to cotton fabrics through the self-polymerisation of tannic acid (TA) under alkaline conditions for the construction of micro-/nanostructures on the fabric surface. Subsequently, methyltrimethoxysilane (MTMS) was employed to confer superhydrophobic properties to the fabrics using a combination of thermal chemical vapour deposition techniques, resulting in a contact angle of approximately 164.3° and a sliding angle of 8.52°. Owing to the combined effect of TA and LNP, the modified fabrics exhibited excellent ultraviolet (UV) shielding ability (UV transmittance < 1 %, UV protection factor = 50 + ) and photothermal conversion (54.2 °C in 150 s). In short, micro-/nanostructures with surface hydrophilicity were constructed on the surface of cotton fabrics using two hydrophilic biomaterials, i.e. TA, which is similar to polydopamine but lighter in colour and less expensive, and LNP as sustainable colloidal particles. Subsequently, their surface roughness was further enhanced, and superhydrophobic properties were imparted through modification with the low surface energy substance MTMS. This method not only promotes the high-value utilisation of lignin but also serves as a reference for constructing superhydrophobic structures using biomass hydrophilic materials on cellulose substrates. The prepared superhydrophobic fabric suggests potential applications in water and stain repellence, self-cleaning, outdoor UV protection and the management of marine oil spill pollution.

Galling-Free Forging of Titanium Using Carbon-Supersaturated SiC Coating Dies

The thermal chemical vapor deposition (CVD) process was utilized to fabricate 6H-structured SiC coating dies with carbon control. The carbon-rich clusters along the SiC grain boundaries acted as a pinning site to suppress irregular crystal growth and to homogenize the fine-grained structure. These massive carbon-supersaturated (MCSed) SiC dies with a thickness of 4 mm were utilized for upsetting pure titanium bars in dry and cold conditions. Under a stress gradient from the contact interface to the depth of the SiC coating, the carbon solute isolated from these carbon clusters diffused through the grain boundaries and formed free carbon agglomerates on the contact interface to the pure titanium bars. These in situ-formed free carbon agglomerates acted as a solid lubricant to sustain the friction coefficient at 0.09 at the hot spots on the contact interface and to protect the dies and bars from severe adhesive wearing.

Influence of the Acetylene Flow Rate and Process Pressure on the Carbon Deposition Behavior by Thermal Chemical Vapor Deposition Process

We used the chemical vapor deposition process to deposit carbon film at a high temperature (900 °C). The carbon films were deposited on AISI 1006 foils using an acetylene gas. We analyzed the carbon film deposited on the surface using Raman spectroscopy, scanning electron microscopy, and high-resolution transmission electron microscopy to define changes in the bonding structure of the carbon film. The results of Raman spectroscopy and high-resolution transmission electron microscopy revealed that as the acetylene flow rate increased, the shape of the deposited carbon film changed from graphene to graphite. In addition, in order to compare the quality of the carbon film in terms of mechanical and electrical properties, carbon films treated under various conditions were closely analyzed using nano-indenter and a sheet resistance meter. Therefore, the optimal condition (1 Torr-50 sccm) was selected in which graphene was uniformly deposited and had the lowest electrical resistance (500 Ω/sq) and highest hardness (12 GPa).

Interplay of physical and textural properties in porous, nanostructured hard‑carbons as electrode materials for non-Faradic energy storage devices

This work presents a systematic investigation on the non-Faradic energy storage ability of non-graphitizable, porosity engineered hard‑carbon nanostructures as electrode materials. The persistent challenge of inducing and tuning porosity in hard‑carbon nanostructures is overcome here, by utilizing dendritic fibrous nano silica (DFNS) as a sacrificial template for uniform and conformal deposition of carbon through thermal chemical vapor deposition, leading to the formation of porosity tuned, nanostructured hard‑carbon florets (NCF). This strategy enables precisely crafted six varieties of NCF with varying yet monodisperse dimensions (NCF 90, NCF 350, NCF 366, NCF 430, NCF 540 and NCF 600), SSA (494–719 m2/g) and textural features such as pore volume (0.67–1.24 cm3/g) and pore diameter (3.83–5.65 nm). In contrast to current understanding, NCF 366 with defect length of 16 nm, defect density of 2.65 × 1011 cm−2, micro- to mesoscale pore ratio of 0.16 and specific surface area of 535 m2/g achieves the highest energy density of 14.6 Wh/kg and power density 10.0 kW/kg, when compared to NCF 90 with higher SSA (719 m2/g) and pore volume (1.24 cm3/g). Thus, this work manifests the critical contributions of tuning the pore structures and optimizing the relative contributions from multi-scale pore structures to achieve high-performing energy storage devices.

Calcium Carbonate Nanocrystal Growth and Formation on Substrate by Thermal Chemical Vapor Deposition at Different Pre‐Cursor Concentration

Calcium Carbonate Nanocrystal Growth and Formation on Substrate by Thermal Chemical Vapor Deposition at Different Pre‐Cursor Concentration

Order-of-Magnitude Increase in Carbon Nanotube Yield Based on Modeling Transient Diffusion and Outgassing of Water From Reactor Walls

Abstract While reactor wall preconditioning was previously shown to influence the yield in chemical vapor deposition (CVD), especially for the growth of carbon nanotubes (CNTs), it was limited to studying accumulating carbonaceous deposits over a number of runs. However, the effects of temperature and duration as the reactor walls are exposed to hot humidity for extended periods between growth runs were not previously studied systematically. Here, we combine experimental measurements with a mathematical model to elucidate how the thermochemical history of reactor walls impacts growth yield, especially knowing that only a specific range of humidity promotes growth. Importantly, we demonstrate a one-order-of-magnitude higher CNT yield by increasing the interim, i.e., the time between runs. We explain the results based on previously unexplored process sensitivity to trace amounts of oxygen-containing species in the reactor. In particular, we model the effect of small amounts of water vapor being desorbed from reactor walls during growth. Our results reveal the outgassing dynamics and show the underlying mechanism of generating growth-promoting molecules. By installing a humidity sensor in our custom-designed multizone rapid thermal CVD reactor, we are able to uniquely correlate the amount of moisture within the reactor to real-time measurements of growth kinetics, as well as ex situ characterization of CNT alignment and atomic defects. Our findings enable a scientifically grounded approach toward both boosting growth yield and improving its consistency by reducing run-to-run variations. Accordingly, engineered dynamics recipes with added preprocessing steps can be envisioned to leverage this phenomenon for improving manufacturing process scalability and robustness.

Morphology-Controlled ZnO@ZnWO4 Hetero-Nanostructures for Efficient Photooxidation of Water in Near-Neutral pH.

One-dimensional ZnO nanorods (NRs) have been extensively studied as photoanodes because of their unique optical properties, high electron mobility, and suitable band positions for water oxidation. However, their practical efficiency is often compromised by chemical instability during water oxidation and high carrier recombination rates. To overcome this issue, precise morphological control of ZnO@ZnWO4 core-shell structured photoanodes, featuring a ZnO core and a ZnWO4 shell was used. This was accomplished by depositing WO3 onto hydrothermally grown ZnO NRs using the thermal chemical vapor deposition process. The photoelectrochemical performance of ZnO@ZnWO4 with an optimized morphology outperforms that of pristine ZnO NRs. Systematic optical and electrochemical analyses of ZnO@ZnWO4 demonstrated that the enhancement is attributed to the enhanced charge transfer efficiency facilitated by the optimized ZnWO4 shells.

Graphene nanowalls formation investigated by Electron Energy Loss Spectroscopy

The properties of layered materials are significantly dependent on their lattice orientations. Thus, the growth of graphene nanowalls (GNWs) on Cu through PECVD has been increasingly studied, yet the underlying mechanisms remain unclear. In this study, we examined the GNWs/Cu interface and investigated the evolution of their microstructure using advanced Scanning transmission electron microscopy and Electron Energy Loss Spectroscopy (STEM-EELS). GNWs interface and initial root layers of comprise graphitic carbon with horizontal basal graphene (BG) planes that conform well to the catalyst surface. In the vertical section, the walls show a mix of graphitic and turbostratic carbon, while the latter becomes more noticeable close to the top edges of the GMWs film. Importantly, we identified growth process began with catalysis at Cu interface forming BG, followed by defect induction and bending at ‘coalescence points’ of neighboring BG, which act as nucleation sites for vertical growth. We reported that although classical thermal CVD mechanism initially dominates, growth of graphene later deviates a few nanometers from the interface to form GNWs. Nascent walls are no longer subjected to the catalytic action of Cu, and their development is dominated by the stitching of charged carbon species originating in the plasma with basal plane edges.

Highly enhanced and stable field emission performance of CNT – Dielectric (Si3N4) hybrids

In the present study, vertically aligned carbon nanotubes (CNTs) were grown onto Si substrates using a simple thermal chemical vapour deposition (TCVD) technique. Subsequently, the dielectric layer of Si3N4 was coated over the pristine CNTs using the Plasma Enhanced CVD (PECVD) method. Various characterizations were carried out on the as-deposited samples to study the structural properties, surface morphology, elemental composition, and electronic structure. The field emission measurements executed on CNT – Si3N4 samples showed an enhanced current density of 8.28 mA/cm2 compared to the 2.85 mA/cm2 current density of the pristine CNTs. A detailed study reveals that, apart from the basic conventional field emission parameters, the electronic structure of the CNTs, along with the presence of disordered carbon atoms and the presence of the dielectric material, are responsible for enhancing the current density and temporal stability of the CNT – Si3N4 hybrids. The study aids in exploring CNT-dielectric hybrids for better field emission properties with improved stability for field emission applications.

Evaluation of vertical alignment in carbon nanotubes: A quantitative approach

An automated quantitative study of the alignment of vertically aligned carbon nanotubes (VA-CNTs) from scanning electron microscopy (SEM) images has been demonstrated. It is based on the fact that the image gradient (directional change in intensity or color) at every pixel in the image contains the information about the anisotropy at that particular pixel i.e., the local alignment is maintained in the orthogonal direction to the gradient. Structure tensor metrics are formulated demonstrating to be able to summarize the distribution of gradient directions within the neighborhood of any pixel within a two-dimensional domain (surface). An image analysis is presented that evaluates the alignment in desired regions of interest (ROIs) in SEM images of VA-CNTs. This method has been exploited to study the alignment of two different kinds of VA-CNTs: one grown via the thermal chemical vapor deposition (T-CVD) method and the second synthesized via the plasma enhanced chemical vapor deposition (PE-CVD) method.

Enhanced electrical properties of amorphous In-Sn-Zn oxides through heterostructuring with Bi2Se3 topological insulators

Amorphous indium tin zinc oxide (a-ITZO)/Bi2Se3 nanoplatelets (NPs) were fabricated using a two-step procedure. First, Bi2Se3 NPs were synthesized through thermal chemical vapor deposition at 600 °C on a glass substrate, and then a-ITZO was deposited on the surface of the Bi2Se3 NPs via magnetron sputtering at room-temperature. The crystal structures of the a-ITZO/Bi2Se3 NPs were determined via X-ray diffraction spectroscopy and high-resolution transmission electron microscopy. The elemental vibration modes and binding energies were measured using Raman spectroscopy and X-ray photoelectron spectroscopy. The morphologies were examined using field-emission scanning electron microscopy. The electrical properties of the a-ITZO/Bi2Se3 NPs were evaluated using Hall effect measurements. The bulk carrier concentration of a-ITZO was not affected by the heterostructure with Bi2Se3. In the case of the Bi2Se3 heterostructure, the carrier mobility and conductivity of a-ITZO were increased by 263.6% and 281.4%, respectively, whereas the resistivity of a-ITZO was reduced by 73.57%. This indicates that Bi2Se3 significantly improves the electrical properties of a-ITZO through its heterostructure, expanding its potential applications in electronic and thermoelectric devices.

Modified 3D Graphene for Sensing and Electrochemical Capacitor Applications.

Less defective, nitrogen-doped 3-dimensional graphene (N3DG) and defect-rich, nitrogen-doped 3-dimensional graphene (N3DG-D) were made by the thermal CVD (Chemical Vapor Deposition) process via varying the carbon precursors and synthesis temperature. These modified 3D graphene materials were compared with pristine 3-dimensional graphene (P3DG), which has fewer defects and no nitrogen in its structure. The different types of graphene obtained were characterized for morphological, structural, and compositional assessment through Scanning Electron Microscopy (SEM), Raman Spectroscopy, and X-ray Photoelectron Spectroscopy (XPS) techniques. Electrodes were fabricated, and electrochemical characterizations were conducted to evaluate the suitability of the three types of graphene for heavy metal sensing (lead) and Electric Double-Layer Capacitor (EDLC) applications. Initially, the various electrodes were treated with a mixture of 2.5 mM Ruhex (Ru (NH3)6Cl3 and 25 mM KCl to confirm that all the electrodes underwent a reversible and diffusion-controlled electrochemical process. Defect-rich graphene (N3DG-D) revealed the highest current density, followed by pristine (P3DG) and less-defect graphene (N3DG). Further, the three types of graphene were subjected to a sensing test by square wave anodic stripping voltammetry (SWASV) for lead detection. The obtained preliminary results showed that the N3DG material provided a great lead-sensing capability, detecting as little as 1 µM of lead in a water solution. The suitability of the electrodes to be employed in an Electric Double-Layer Capacitor (EDLC) was also comparatively assessed. Electrochemical characterization using 1 M sodium sulfate electrolyte was conducted through cyclic voltammetry and galvanostatic charge-discharge studies. The voltammogram and the galvanostatic charge-discharge (GCD) curves of the three types of graphene confirmed their suitability to be used as EDLC. The N3DG electrode proved superior with a gravimetric capacitance of 6.1 mF/g, followed by P3DG and N3DG, exhibiting 1.74 mF/g and 0.32 mF/g, respectively, at a current density of 2 A/g.

Preparation of vertically oriented aromatic polyester thin films by thermal chemical vapor deposition

Aromatic polyesters exhibit high thermal conductivity and large nonlinear optical effects by controlling the orientation of their main chains. Especially in recent years, with the development of flexible optical and electronic devices utilizing polymer thin films, out-of-plane orientation control in thin films on the order of several hundred nm is required. However, due to the rigidity of aromatic polyesters, it is difficult to control vertical orientation in thin film growth from melt or solution. In this study, we attempted to control the vertical orientation of aromatic polyester thin films from the vapor phase using a thermal CVD. From a single head-to-tail type monomer, aromatic polyester thin films with the most primitive structure, whose mp exceeds 500 °C, were successfully grown. Furthermore, it was found that the vertical orientation of the main chains was enhanced by substrate surface treatment.

Interaction of graphene and WS2 with neutrophils and mesenchymal stem cells: implications for peripheral nerve regeneration.

Graphene and bidimensional (2D) materials have been widely used in nerve conduits to boost peripheral nerve regeneration. Nevertheless, the experimental and commercial variability in graphene-based materials generates graphene forms with different structures and properties that can trigger entirely diverse biological responses from all the players involved in nerve repair. Herein, we focus on the graphene and tungsten disulfide (WS2) interaction with non-neuronal cell types involved in nerve tissue regeneration. We synthesize highly crystalline graphene and WS2 with scalable techniques such as thermal decomposition and chemical vapor deposition. The materials were able to trigger the activation of a neutrophil human model promoting Neutrophil Extracellular Traps (NETs) production, particularly under basal conditions, although neutrophils were not able to degrade graphene. Of note is that pristine graphene acts as a repellent for the NET adhesion, a beneficial property for nerve conduit long-term applications. Mesenchymal stem cells (MSCs) have been proposed as a promising strategy for nerve regeneration in combination with a conduit. Thus, the interaction of graphene with MSCs was also investigated, and reduced viability was observed only on specific graphene substrates. Overall, the results confirm the possibility of regulating the cell response by varying graphene properties and selecting the most suitable graphene forms.