Chemical Vapor Deposition Growth Research Articles

Bio-inspired transparent and antibiofouling diamond films via layer-by-layer self-assembly seeding

Bio-inspired diamond nanostructures featuring high transparency and anti-bacterial adhesion were constructed via layer-by-layer (LbL) self-assembly seeding and chemical vapor deposition growth. The topography of the diamond nanofilms was determined by initial nanodiamond seeds distribution, which was adjusted by nanodiamond colloidal stability. With increasing number of LbL bilayers, the bulge size and roughness of the deposited films increased. With increasing number of bilayers from 1 to 5, UV–Vis transmittance slightly decreased from max. 90 %–83 %, while the contact angle increased from 90° to 130°. All the nanostructured diamond films possess very high IR transmittance between 85% and 90%, which is close to the bare quartz (95%). Compared with conventional flat diamond films, nanostructured diamond films repelled most of the bacteria, suggesting excellent anti-biofouling property. With increasing seeding bilayer number, more bacteria were repelled. The highest bacterial reduction was achieved to 99% by diamond film seeded with 5 bilayers. The bio-mimicking nanostructured diamond film represent a potent solution for achieving highly transparent, anti-biofouling and highly durable optical coatings for biomedical and marine optical instrument.

Single-walled carbon nanotube synthesis with RuRhPdIrPt high entropy alloy catalysts

Using high-entropy alloy nanoparticles (HEA NPs) composed of five platinum-group metals (5PGM), Ru, Rh, Pd, Ir, and Pt, as catalysts, we succeeded in growing single-walled carbon nanotubes (SWCNTs) via chemical vapor deposition (CVD). After CVD growth with C2H2 feedstock at 750 ℃ for 10 min, high-density SWCNTs were grown from 5PGM HEA NPs. The diameters of most SWCNTs were in the range of 0.83–1.1 nm, exhibiting the growth of small-diameter SWCNTs. Compared with monometal PGM catalysts, the SWCNT yield with the 5PGM HEA NP catalysts was much higher and was compatible even with those with Fe and Co.

The effect of nickel oxide in the direct growth of MnOx on Ni foam by chemical vapor deposition

Manganese oxide has emerged as a promising material for use as a charge storage electrode material. In this work, we demonstrate the low-pressure chemical vapour deposition (CVD) growth of manganese oxide conformal coatings on Ni-foams utilising an MnCl2 solid source precursor, utilising an oxide formed on the surface of the Ni-foam as an oxygen reservoir for the synthesis of a predominantly MnO x layer. The resulting MnO x layer is highly dependent on sample pre-treatment, owing to modifications in the Ni oxide layer. The phase structure, electronic states, morphology, and electrochemical analysis were determined by x-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning-electron microscopy (FE-SEM), and capacitance–voltage (CV) measurements. The importance of the oxide layer is demonstrated by modifying the thickness of the NiO layer over the Ni foam, with clear changes in the resultant structure, morphology, and areal capacitance, with the highest performance MnO x coating found to be obtained without any oxide removal from the Ni foam substrate.

First-principles investigation of hydrogen-related reactions on (100)–(2 × 1)[formula omitted]H diamond surfaces

Hydrogen radical attacks and subsequent hydrogen migrations are considered to play an important role in the atomic-scale mechanisms of diamond chemical vapour deposition growth. We perform a comprehensive analysis of the reactions involving H-radical and vacancies on H-passivated diamond surfaces exposed to hydrogen radical-rich atmosphere. By means of first principles calculations—density functional theory and climbing image nudged elastic band method—transition states related to these mechanisms are identified and characterised. In addition, accurate reaction rates are computed using variational transition state theory. Together, these methods provide—for a broad range of temperatures and hydrogen radical concentrations—a picture of the relative likelihood of the migration or radical attack processes, along with a statistical description of the hydrogen coverage fraction of the (100) H-passivated surface, refining earlier results via a more thorough analysis of the processes at stake. Additionally, the migration of H-vacancy is shown to be anisotropic, and occurring preferentially across the dimer rows of the reconstructed surface. The approach used in this work can be generalised to other crystallographic orientations of diamond surfaces or other semiconductors.

Toward Controlled Synthesis of 2D Crystals by CVD: Learning from the Real-Time Crystal Morphology Evolutions.

The rich morphology of 2D materials grown through chemical vapor deposition (CVD), is a distinctive feature. However, understanding the complex growth of 2D crystals under practical CVD conditions remains a challenge due to various intertwined factors. Real-time monitoring is crucial to providing essential data and enabling the use of advanced tools like machine learning for unraveling these complexities. In this study, we present a custom-built miniaturized CVD system capable of observing and recording 2D MoS2 crystal growth in real time. Image processing converts the real-time footage into digital data, and machine learning algorithms (ML) unveil the significant factors influencing growth. The machine learning model successfully predicts CVD growth parameters for synthesizing ultralarge monolayer MoS2 crystals. It also demonstrates the potential to reverse engineer CVD growth parameters by analyzing the as-grown 2D crystal morphology. This interdisciplinary approach can be integrated to enhance our understanding of controlled 2D crystal synthesis through CVD.

Observation of band gap bowing effect vanishing in graded-composition monolayer Mo1−xWxS2 alloy

Over the past decade, tremendous effort has been put into developing 2D semiconductor materials with a tunable bandgap by alloying different individual components. However, the bandgap bowing effect has hindered the ability to arbitrary control the emission of these alloys. In this study, we report the chemical vapor deposition growth of a graded-composition Mo1−xWxS2 monolayer alloy, in which the photoluminescence emission energy exhibits nearly linear variation in the bandgap, indicating the vanishing of the bandgap bowing effect. Polarized Raman measurements show that the polarization is composition dependent, and a large symmetry breaking occurs at the point where the bandgap bowing effect vanishes. This suggests that the vanishing of the bowing effect may be attributed to the symmetry breaking induced by compressive strain. Our findings demonstrate a significant advancement in the synthesis of alloys for future use.

Ti-B-O System for Catalyzing Boron Nitride Nanotube Growth.

Chemical vapor deposition (CVD) stands out as the most promising method for cost-effective production of high-quality boron nitride nanotubes (BNNTs). Catalysts play a crucial role in BNNT synthesis. This work delves into the impact of oxygen (O) on Ti-based catalysts during the CVD growth of BNNTs. In contrast to the B/TiB2 nanoparticles (NPs) and B/TiN NPs systems, the oxygen-containing precursor B/TiO2 NPs remarkably catalyzes the growth of high-quality and high-purity BNNTs across a wider range of synthesis parameters. Subsequent analyses reveal that TiBO3 acts as an active catalyst, facilitating BNNT growth in Ti-based catalyst systems. Moreover, the nanocomposite film synthesized from BNNTs and PVDF-HFP exhibits excellent mechanical properties and heat dissipation capabilities. Utilizing the nanocomposite film as a thermal interface material effectively enhances the heat dissipation for a 5 W light-emitting diode (LED) chip. Consequently, our research confirms the effectiveness of the Ti-B-O system in catalyzing BNNT growth.

High yield and wide lateral size growth of α-Mo2C: exploring the boundaries of CVD growth of bare MXene analogues

Synthesis of Mo2C bare MXenes, without surface terminations groups, via chemical vapor deposition (CVD) on metal foils is scientifically a very intriguing crystal growth process, and there are still challenges and limited fundamental understanding to overcome to obtain high yield and wide crystal size lateral growth. Achieving large area coverage via direct growth is scientifically vital to utilize the full potential of their unique properties in different applications. In this study, we sought to expand the boundaries of the current CVD growth approach for Mo2C MXenes and gain insights into the possibilities and limitations of large area growth, with a particular focus on controlling Mo concentration. We report a facile modification of their typical CVD growth protocol and show its influence on the Mo2C synthesis, with growth times spanning up to 3 h. Specifically, prior to initiating the CVD growth process, we introduced a holding step in temperature at 1095 °C. This proved to be beneficial in increasing the Mo concentration on the liquid Cu growth surface. We achieved an average Mo2C crystals coverage of approximately 50% of the growth substrate area, increased tendency of coalescence and merging of individual flakes, and lateral flake sizes up to 170 μm wide. To gain deeper understanding into their CVD growth behavior, we conducted a systematic investigation of the effect of several factors, including (i) a holding step time on Mo diffusion rate through molten Cu, (ii) the Cu foil thickness over the Mo foil, and (iii) the CVD growth time. Phase, chemical and microstructural characterization by x-ray diffraction, x-ray photon spectroscopy, SEM and scanning/transmission electron microscopy revealed that the grown crystals are single phase α-Mo2C. Furthermore, insights gained from this study sheds light on crucial factors and inherent limitations that are essential to consider and may help guide future research progress in CVD growth of bare MXenes.

Reconfiguring nucleation for CVD growth of twisted bilayer MoS2 with a wide range of twist angles

Twisted bilayer (TB) transition metal dichalcogenides (TMDCs) beyond TB-graphene are considered an ideal platform for investigating condensed matter physics, due to the moiré superlattices-related peculiar band structures and distinct electronic properties. The growth of large-area and high-quality TB-TMDCs with wide twist angles would be significant for exploring twist angle-dependent physics and applications, but remains challenging to implement. Here, we propose a reconfiguring nucleation chemical vapor deposition (CVD) strategy for directly synthesizing TB-MoS2 with twist angles from 0° to 120°. The twist angles-dependent Moiré periodicity can be clearly observed, and the interlayer coupling shows a strong relationship to the twist angles. Moreover, the yield of TB-MoS2 in bilayer MoS2 and density of TB-MoS2 are significantly improved to 17.2% and 28.9 pieces/mm2 by tailoring gas flow rate and molar ratio of NaCl to MoO3. The proposed reconfiguring nucleation approach opens an avenue for the precise growth of TB-TMDCs for both fundamental research and practical applications.

Low-temperature synthesis of uniform monolayer molybdenum disulfide films

Monolayer molybdenum disulfide (MoS2) has garnered significant attention owing to its potential applications in electronics and optoelectronics. Nevertheless, existing methods for the chemical vapor deposition growth of MoS2 demand elevated synthesis temperatures and involve transfer procedures, thereby restricting its effectiveness in device manufacturing. In this study, we present the direct growth of 1-in. (∼25 mm) monolayer MoS2 films on SiO2 and other substrates under low-temperature conditions (360 °C). We employed a highly reactive substance, MoO2Cl2, as the molybdenum source for growth, which significantly reduces the growth temperature of MoS2. Simultaneously, a transitional temperature zone was implemented to further lower the growth temperature of MoS2. Experimental results from multiple tests on the produced MoS2 films indicated excellent uniformity and relatively large grain size (∼5 μm) at the low growth temperature, ensuring its promising applicability Furthermore, we fabricated field-effect transistors on the SiO2, achieving a mobility of 14.3 cm2 V−1 s−1 and an Ion/Ioff ratio exceeding 105. Our method offers a versatile approach for the low-temperature growth of MoS2, paving the way for future developments in silicon process-compatible applications.

Chemical vapor deposition growth of graphene and other nanomaterials with 3D architectures towards electrocatalysis and secondary battery-related applications.

Recently, two-dimensional (2D) layered materials, such as graphene and transition metal dichalcogenides (TMDCs), have garnered a lot of attention in energy storage/conversion-related fields due to their novel physical and chemical properties. Constructing flat graphene and TMDCs nanosheets into 3D architectures can significantly increase their exposed surface area and prevent the restacking of adjacent 2D layers, thus dramatically promoting their applications in various energy-related fields. Chemical Vapor Deposition (CVD) is a low-cost, facile, and scalable method, which has been widely employed to produce high-quality graphene and TMDCs nanosheets with 3D architectures. During the CVD process, the morphologies and properties of the 3D architectures of such 2D materials can be designed by selecting substrates with different compositions, stacking geometries, and micro-structures. In this review, we focus on the recent advances in the CVD synthesis of graphene, TMDCs, and their hybrids with 3D architectures on different 3D-structured substrates, as well as their applications in the electrocatalytic hydrogen evolution reaction (HER) and various secondary batteries. In addition, the challenges and future prospects for the CVD synthesis and energy-related applications of these unique layered materials will also be discussed.

Recent trends in the transfer of graphene films.

Recent years have witnessed advances in chemical vapor deposition growth of graphene films on metal foils with fine scalability and thickness controllability. However, challenges for obtaining wrinkle-free, defect-free and large-area uniformity remain to be tackled. In addition, the real commercial applications of graphene films still require industrially compatible transfer techniques with reliable performance of transferred graphene, excellent production capacity, and suitable cost. Transferred graphene films, particularly with a large area, still suffer from the presence of transfer-related cracks, wrinkles and contaminants, which would strongly deteriorate the quality and uniformity of transferred graphene films. Potential applications of graphene films include moisture barrier films, transparent conductive films, electromagnetic shielding films, and optical communications; such applications call different requirements for the performance of transferred graphene, which, in turn, determine the suitable transfer techniques. Besides the reliable transfer process, automatic machines should be well developed for the future batch transfer of graphene films, ensuring the repeatability and scalability. This mini-review provides a summary of recent advances in the transfer of graphene films and offers a perspective for future directions of transfer techniques that are compatible for industrial batch transfer.

Atomic insight into the effects of precursor clusters on monolayer WSe2.

Two-dimensional (2D) transition metal dichalcogenides (TMDCs) have been attracting much attention due to their rich physical and chemical properties. At the end of the chemical vapor deposition growth of 2D TMDCs, the adsorption of excess precursor clusters onto the sample is unavoidable, which will have significant effects on the properties of TMDCs. This is a concern to the academic community. However, the structures of the supported precursor clusters and their effects on the properties of the prepared 2D TMDCs are still poorly understood. Herein, taking monolayer WSe2 as the prototype, we investigated the structure and electronic properties of SeN, WN (N = 1-8), and W8-NSeN (N = 1-7) clusters adsorbed on monolayer WSe2 to gain atomic insight into the precursor cluster adsorption. In contrast to W clusters that tightly bind to the WSe2 surface, Se clusters except for Se1 and Se2 are weakly adsorbed onto WSe2. The interaction between W8-NSeN (N = 1-7) clusters and the WSe2 monolayer decreases with the increase in the Se/W ratio and eventually becomes van der Waals interaction for W1Se7. According to the phase diagram, increasing the Se/W ratio by changing the experimental conditions will increase the ratio of SeN and W1Se7 clusters in the precursor, which can be removed by proper annealing after growth. W clusters induce lots of defect energy levels in the band gap region, while the adsorption of W1Se7 and SeN clusters (N = 3-6, 8) promotes the spatial separation of photo generated carriers at the interface, which is important for optoelectronic applications. Our results indicate that by controlling the Se/W ratio, the interaction between the precursor clusters and WSe2 as well as the electronic properties of the prepared WSe2 monolayer can be effectively tuned, which is significant for the high-quality growth and applications of WSe2.

Growth of Single-Walled Carbon Nanotubes from Solid Supported Heterogeneous Catalysts: Achievements and Challenges

Single-walled carbon nanotubes (SWNTs) have gained worldwide attention because of their exceptional electronic, optical, and mechanical properties, which are contingent on their structures denoted by chiral indices (n, m). To fully harness the extraordinary properties and advance SWNT-based technology, large scale synthesis of SWNTs with a narrow chirality distribution or even a specific (n, m) is highly demanded. Among various SWNT preparation techniques, chemical vapor deposition growth from solid supported heterogeneous catalysts has emerged as a promising approach in terms of large yield and (n, m) structure control. In this review, we provide an overview of the progress in developing heterogeneous catalysts for bulk synthesis of SWNTs. Firstly, the advantages and disadvantages of using solid supported catalysts for chemical vapor deposition growth of SWNTs are discussed. Secondly, the key components in supported catalysts, including the metallic component and the nature of support material, as well as their respective roles in affecting the catalyst performances and SWNT chirality distribution, are highlighted. Finally, the current challenges and future directions in the field of SWNT synthesis from solid supported catalysts are proposed.

Effect of substrate roughness on the nucleation and growth behaviour of microwave plasma enhanced CVD diamond films – a case study

The influence of substrate surface roughness on the nucleation and growth of diamond films by chemical vapour deposition (CVD) is investigated. Silicon substrates were grinded with six different grit sizes of abrasive papers with a rotating wheel. Si was also etched by Ar+ ions to produce average surface roughness Ra = 11.29 nm on the mirror polished side (Ra = 1.17 nm). A comparison of the results of the effect of substrate roughness, on the growth behaviour of nanocrystalline diamond (NCD) films, by using both the resonant cavity and the linear antenna CVD systems, are presented here. Scanning electron microscopy (SEM) images and Raman spectroscopy reveal that under both the linear antenna and the resonant cavity microwave plasma CVD conditions, grown films are NCD. The diamond nanocrystals sizes vary from 80 to 180 nm, grown by both the reactors after few hours of deposition, irrespective of the substrate roughness, whereas their quality (defined by the relative percentage ratios of the Raman sp3 peak intensity to the non-sp3 peak intensity) varies from 33% to 45%, depending on the substrate surface roughness. Such nanocrystals grew into plate-like flat 1–6 μm size diamond grains after prolonged hours (64–69 h) of CVD growth. It is found specifically that the roughness created by the argon plasma treatment of the silicon substrate surfaces effectively enhances the nucleation and growth behaviour of the diamond films.

Probing and controlling oxygen impurity diffusion in h-BN semi-bulk crystals

Combining its unique features of ultrawide bandgap (UWBG) and two-dimensional nature, h-BN has been explored for emerging applications such as deep ultraviolet optoelectronic devices and single photon emitters. One of the unusual applications of h-BN is for solid-state neutron detectors by utilizing the property of high thermal neutron capture cross section of B-10 as well as its UWBG properties. Although a record high detection efficiency of 59% has been attained by h-BN detectors, the understanding/minimization of defects and impurities is still needed to further advance the h-BN material and detector technologies. We report metal organic chemical vapor deposition growth and oxygen (O) impurity diffusion in thick h-BN. The diffusion coefficient (D) of O impurities has been measured via the evolution of an oxygen related emission with the etching depth, providing a value of D of ∼ 2 × 10−13 cm2/s at 1450 °C and supporting the interpretation that oxygen in h-BN is a substitutional donor. A multiple-buffer-layer approach was employed to mitigate to a certain degree the issue of oxygen diffusion from sapphire substrate during growth. It was demonstrated that the performance of h-BN neutron detectors fabricated from the wafer incorporating multiple buffer layers was significantly improved, as manifested by the enhanced thermal neutron detection efficiency. The advancement of the crystal growth technology of h-BN semi-bulk crystals creates applications in optoelectronic and power electronic devices utilizing the UWBG semiconductor properties of h-BN, while high efficiency h-BN neutron detectors have the potential to supplant the traditional He-3 gas detectors in various application areas by offering the obvious advantages of UWBG semiconductor technologies.

In Situ Growth of High-Quality Single-Crystal Twisted Bilayer Graphene on Liquid Copper.

Twisted bilayer graphene (TBG) generates significant attention in the fundamental research of 2D materials due to its distinct twist-angle-dependent properties. Exploring the efficient production of TBG with a wide range of twist angles stands as one of the major frontiers in moiré materials. Here, the local space-confined chemical vapor deposition growth technique for high-quality single-crystal TBG with twist angles ranging from 0° to 30° on liquid copper substrates is reported. The clean surface, pristine interface, high crystallinity, and thermal stability of TBG are verified by using comprehensive characterization techniques including optical microscopy, electron microscopy, and secondary-ion mass spectrometry. The proportion of TBG in bilayer graphene reaches as high as 89%. In addition, the stacking structure and growth mechanism of TBG are investigated, revealing that the second graphene layer develops beneath the first one. A series of comparative experiments illustrates that the liquid copper surface, with its excellent fluidity, promotes the growth of TBG. Electrical measurements show the twist-angle-dependent electronic properties of as-grown TBG, achieving a room-temperature carrier mobility of 26640 cm2 V-1 s-1 . This work provides an approach for the in situ preparation of 2D twisted materials and facilitates the application of TBG in the fields of electronics.

Growth of 2D Cr2 O3 -CrN Mosaic Heterostructures with Tunable Room-Temperature Ferromagnetism.

2D magnets have generated much attention due to their potential for spintronic devices. Heterostructures of 2D magnets are interesting platforms for exploring physical phenomena and applications. However, the controlled growth of 2D room-temperature ferromagnetic heterostructures is challenging. Here, one-pot chemical vapor deposition growth of stable 2D Cr2 O3 -CrN mosaic heterostructures (MHs) is reported with a controlled ratio of components that possess robust room-temperature ferromagnetism. The 2D MHs consist of Cr2 O3 flakes with embedded CrN subdomains and the CrN:Cr2 O3 ratio can be tuned from 0% to 100% during growth. By changing the CrN:Cr2 O3 ratio, the ferromagnetism of the MHs (e.g., saturation magnetization, coercive field), which originates from the interfacial coupling between Cr2 O3 and CrN, can be controlled. Importantly, the obtained Cr2 O3 -CrN MHs are stable in air at elevated temperatures and have robust ferromagnetism with Curie temperature >400K. This work presents a facile method for fabricating 2D MHs with tunable magnetism which will benefit high-temperature spintronics.

A systematic study on the efficacy of low-temperature GaN regrown on p-GaN to suppress Mg out-diffusion

Embedding p-type gallium nitride (p-GaN) in AlxGa1-xN-based thin films has garnered significant interest as a versatile structure for bandgap engineering such as tunnel/super-junctions or current blocking/guiding functions in electronic devices. However, Mg, a p-GaN dopant, has an undesirable diffusive capacity into the nearby thin films at a high growth temperature (>1,000°C), resulting in structural challenges in device design. This study systematically investigated the low-temperature GaN (LT-GaN) layer regrown on p-GaN that suppresses Mg diffusion according to metal–organic chemical vapor deposition growth conditions. Prototype Al0.3Ga0.7N (40 nm)/GaN (140 nm) high-electron-mobility transistors (HEMTs) were regrown with LT-GaN on p-GaN (300 nm), and a high two-dimensional electron gas (2DEG) density of 3.13E12 cm−2 was achieved by inserting a 100-nm-thick LT-GaN layer grown at 750°C; in contrast, only 1.76E10 cm−2 2DEG density was obtained from Al0.3Ga0.7N/GaN HEMTs regrown directly on p-GaN (Mg: 4.0E19 cm−3). The fabricated Al0.3Ga0.7N/GaN HEMTs with 100-nm-thick LT-GaN demonstrated a high drain current density of 84.5 mA/mm with a low on-state resistance of 31 Ω·mm. The AlxGa1-xN/LT-GaN/p-GaN platform demonstrated here paves the way for various III-nitride-based structures with embedded p-GaN.

Chemical vapor deposition growth of [formula omitted] on Si- and C- face off-axis 4H–SiC at high temperature

Realization of β‐Ga2O3 on a high-thermal-conductivity substrate is crucial to overcome the poor thermal conductivity of β‐Ga2O3 which is one of the major roadblocks against its era in power electronics. We investigated low-pressure chemical vapor deposition (LPCVD) growth on both Si and C- face (0001) 4H–SiC at a high growth temperature of 925 °C using Ga metal and O2 gas source. Growths on C-face 4H–SiC resulted polycrystalline β‐Ga2O3 for the entire O2-flow range, whereas under optimized O2-flow conditions, step flow growth of (−201) β‐Ga2O3 was achieved on Si-face 4H–SiC with 3.7 nm rms surface roughness and rocking curve FWHM of 0.54° at a growth rate reaching 2.48 μm/h 4° off-axis nature of the substrate promoted the growth of some of the in-plane rotational domains while suppressing others. Raman measurements further verified the pure β‐Ga2O3 nature of the grown films. Using a customized LPCVD with solid source Ga, a cost-effective, safe and industrially scalable method was shown to pave the way to enable β‐Ga2O3 heteroepitaxy on 4H–SiC for high-power electronics.