Herein we review the remarkable range of modifications to materials properties associated with photoexcitation of the growth surface during physical vapor epitaxy of semiconductors. We concentrate on mechanisms producing measureable, utilizable changes in crystalline perfection, phase, composition, doping, and defect distribution. We outline the relevant physics of different mechanisms, concentrating on those yielding effects orthogonal to the primary growth variables of temperature and atomic or molecular fluxes and document the phenomenological effects reported. Based on experimental observations from a range of semiconductor systems and growth conditions, the primary effects include enhanced anion desorption, molecular dissociation, increased doping efficiency, modification to defect populations and improvements to the crystalline quality of epilayers grown at low temperatures. Future research directions and technological applications are also discussed.
A comparative study of the structural, microstructural and magnetic properties of CrO$_2$ thin films grown onto (110) and (100) TiO$_2$ rutile single crystal substrates by chemical vapor deposition (CVD), using CrO$_3$ as chromium precursor and either oxygen or argon as carrier gas is presented. Our results show that growth under argon carrier gas leads to high quality CrO$_2$ epilayers with structural and magnetic properties similar to those obtained using the more standard oxygen carrier gas. Furthermore, we interpret the larger magnetic coercivity observed for the (110) oriented films in te…
Epitaxial (111) Films of Cu, Ni, and Cu$_xNi$_y$ on α-Al$_2$O$_3$(0001) for Graphene Growth by Chemical Vapor Deposition
评价（111）织构化的Cu、Ni和Cu $_x$ Ni $_y$的膜作为石墨烯的化学气相沉积的基底。在250 ℃至650 ℃的温度下，将400 nm至700 nm的金属厚度溅射到$α-$ Al $_2$ O $_3$（0001）的衬底上。然后将膜在管式炉中在1000 ℃下退火。X射线和电子背散射衍射测量表明，所有的薄膜具有（111）织构，但具有面内取向不同的晶粒$60^{\circ}$。所有薄膜的面内外延关系均为$[110]_{metal}$|| $[10\bar{1}0]_{{Al}_{2}{O}_{3}}$。在金属沉积之前在O $_2$中反应溅射Al导致超过97%的Ni膜的单一面内取向，但对Cu晶粒结构没有显著影响。透射电子显微镜显示干净的Ni/Al $_2$ O $_3$界面，确认了外延关系，并显示$60^{\circ}$孪晶晶粒的形成与Al $_2$ O $_3$表面上的特征相关。在退火过程中增加总压和Cu蒸气压降低了Cu和Cu $_x$ Ni $_y$薄膜的粗糙度。在Ni（111）膜上生长的石墨烯比在多晶Ni/SiO $_2$膜上生长的石墨烯更均匀，但仍然显示出在比晶粒之间的距离小得多的长度尺度上的厚度变化。
Spot Profile Analysis Low Energy Electron Diffraction of Plasma-Enhanced Chemical Vapor Deposition Grown Epitaxial Few-Layer Graphene on Sapphire
University of Duisburg-Essen（杜伊斯堡-埃森大学）；Faculty of Engineering, University of Duisburg-Essen（杜伊斯堡-埃森大学工程学院）；Department of Chemistry and Waterloo Institute for Nanotechnology（化学系与滑铁卢纳米技术研究所）；Center for Nanointegration (CENIDE)（纳米集成中心）
The vapor phase synthesis of two-dimensional transition-metal dichalcogenides (MX2) and their heterostructures is often poorly reproducible and sensitive to uncontrolled environmental humidity. It was recently realized that water vapor can play important roles in the growth of MX2 by reacting with MX2 at high temperature to form volatile metal oxyhydroxide (MOx(OH)y) and hydrogen chalcogenides (H2X) that dramatically change the growth processes. Here we report the controllable synthesis of WS2, MoS2, and their heterostructures using water-assisted chemical vapor transport (CVT). The water vapo…
Transition metal dichalcogenide (TMD) monolayers and heterostructures have emerged as a compelling class of materials with transformative new science that may be harnessed for novel device technologies. These materials are commonly fabricated by exfoliation of flakes from bulk crystals, but wafer-scale epitaxy of single crystal films is required to advance the field. This article reviews the fundamental aspects of epitaxial growth of van der Waals bonded crystals specific to TMD films. The structural and electronic properties of TMD crystals are initially described along with sources and metho…
This paper reports on the epitaxial growth of hexagonal boron nitride (hBN) films on sapphire substrates in a cold wall chemical vapor deposition (CVD) system where different sapphire nitridation and hBN growth temperatures were employed. A thin and amorphous nitridated layer was formed at a low temperature (850 C), which enabled subsequent epitaxial hBN growth at 1350 C. The influences of the sapphire nitridation temperature and the growth temperature on the film quality were analyzed by X-ray diffraction (XRD) measurements. Higher than optimum nitridation and growth temperatures improve the …
Phosphorene, a single layer of black phosphorous (BLK-P), has a significant potential for flexible and tunable electronics, but attempts to grow it epitaxially have been unsuccessful to date. Meanwhile, hexagonal blue phoshorous (BL-P) has been achieved on closed-packed (111) metal surfaces in special growth conditions of high vapor pressure and high reactivity of phosphorous. The (111) surfaces favors BL-P over BLK-P due to its hexagonal symmetry. Here, we investigate computationally the alternative offered by stepped substrates. Using the Cu(311) surface as a model, we find that surface step…
Atomically thin MoS2/graphene heterostructures are promising candidates for nanoelectronic and optoelectronic technologies. Among different graphene substrates, epitaxial graphene (EG) on SiC provides several potential advantages for such heterostructures including high electronic quality, tunable substrate coupling, wafer-scale processability, and crystalline ordering that can template commensurate growth. Exploiting these attributes, we demonstrate here the thickness-controlled van der Waals epitaxial growth of MoS2 on EG via chemical vapor deposition, giving rise to transfer-free synthesis …
We have developed an incandescent Mo source to fabricate large-area single-crystalline MoSe2 thin films. The as-grown MoSe2 thin films were characterized using transmission electron microscopy, energy dispersive X-ray spectroscopy, atomic force microscopy, Raman spectroscopy, photoluminescence, reflection high energy electron diffraction (RHEED) and angular resolved photoemission spectroscopy (ARPES). A new Raman characteristic peak at 1591 cm-1 was identified. Results from Raman spectroscopy, photoluminescence, RHEED and ARPES studies consistently reveal that large-area single crystalline mon…
Molecular-beam epitaxy (MBE) provides a simple but powerful way to synthesize large-area high-quality thin films and heterostructures of a wide variety of materials including accomplished group III-V and II-VI semiconductors as well as newly-developing oxides and chalcogenides, leading to major discoveries in condensed-matter physics. For two-dimensional (2D) materials, however, main fabrication routes have been mechanical exfoliation and chemical-vapor deposition by making good use of weak van der Waals bonding nature between neighboring layers, and MBE growth of 2D materials, in particular o…
The formation of various uncommon shaped voids along with regular triangular and square voids in the epitaxial 3C-SiC films on Si has been investigated by optical microscopy and atomic force microscopy. Heteroepitaxial growth of 3C-SiC films on Si (001) and (111) substrates has been performed using hexamethyldisilane in a resistance-heated chemical vapor deposition reactor. The influence of the orientation of the Si substrate in determining the shape of the voids has clearly been observed. In addition, the growth period and the growth-temperature have been considered as the major parameters to…
Graphene, consisting of an inert, thermally stable material with an atomically flat, dangling bond-free surface is by essence an ideal template layer for van der Waals heteroepitaxy of two-dimensional materials such as silicene. However, depending on the synthesis method and growth parameters, graphene (Gr) substrates could exhibit, on a single sample, various surface structures, thicknesses, defects, and step heights. These structures noticeably affect the growth mode of epitaxial layers, e.g. turning the layer-by-layer growth into the Volmer-Weber growth promoted by defect-assisted nucleatio…
The growth of large crystallite continuous monolayer materials like molybdenum disulfide (MoS$_2$) with desired morphology via chemical vapor deposition (CVD) remains a challenge. In CVD, the complex interplay of various factors like growth temperature, precursors, and nature of the substrate decides the crystallinity, crystallite size, and coverage area of the grown MoS$_2$ monolayer. In the present work, we report about the role of weight fraction of molybdenum trioxide (MoO$_3$), Sulfur, and carrier gas flow rate towards nucleation and monolayer growth. The concentration of MoO$_3$ weight f…
Nano selective area growth of GaN by MOVPE on 4H-SiC using epitaxial graphene as a mask: towards integrated III-nitride / graphene / SiC electronics and optoelectronics
Realization of wafer-scale single-crystal films of transition metal dichalcogenides (TMDs) such as tungsten sulfide requires epitaxial growth and coalescence of oriented domains to form a continuous monolayer. The domains must be oriented in the same crystallographic direction on the substrate to avoid the formation of metallic inversion domain boundaries (IDBs) which are a common feature of layered chalcogenides. Here we demonstrate fully-coalesced single orientation tungsten sulfide monolayers on 2-inch diameter c-plane sapphire by metalorganic chemical vapor deposition using a multi-step gr…
$β-Ga_2O_3$ has drawn significant attention for power electronics and deep ultraviolet (UV) photodetectors owing to its wide bandgap of ~ 4.4 - 4.9 eV and high electric breakdown strength ~7-8 MV/cm. Growth of $β-Ga_2O_3$ epitaxial thin films with high growth rate has been recently reported using low pressure chemical vapor deposition (LPCVD) technique. In this work, we have investigated the effect of growth temperature on $β-Ga_2O_3$ films grown on c-plane sapphire substrates using LPCVD. We performed growths by varying temperatures from 800$^°$C to 950$^°$C while keeping all other growth par…
Low-temperature epitaxial growth of refractory transition-metal nitride thin films by means of physical vapor deposition has been a recurring theme in advanced thin-film technology for several years. In the present study, 150-nm-thick epitaxial HfN layers are grown on MgO(001) by reactive high-impulse magnetron sputtering (HiPIMS) with no external substrate heating. Maximum film growth temperatures Ts due to plasma heating range from 70-150 °C, corresponding to Ts/Tm = 0.10-0.12 (in which Tm is the HfN melting point in K). During HiPIMS, gas and sputtered-metal ion fluxes incident at the growi…
Ge-on-Si structures in-situ doped with phosphorus or arsenic via metal organic chemical vapor deposition (MOCVD) were investigated. Surface roughness, strain, threading dislocation desnity, Si-Ge interdiffusion, dopant diffusion, and photoluminescence were characterized to study the impacts of defect annealing and Si substrate offcut effects on the Ge film quality and most importantly, the light emission properties. All samples have a smooth surface (roughness < 1.5 nm), and the Ge films have a small tensile strain of 0.2%. As-grown P and As-doped Ge films have threading dislocaiton densities …
Understanding the growth mechanisms of two-dimensional (2D) van der Waals (vdW) heterostructures is of great importance in exploring their functionalities and device applications. A custom-built system integrating physical vapor deposition and optical microscopy/Raman spectroscopy was employed to study the dynamic growth processes of 2D vdW heterostructures in situ. This allows us to identify a new growth mode with a distinctly different growth rate and morphology from those of the conventional linear growth mode. We propose a model that explains the difference in morphologies and quantifies t…
In this work, we use photoluminescence spectroscopy (PL) to monitor changes in the UV, UV', blue, and green emission bands from n-type (010) Ga2O3 films grown by metalorganic vapor phase epitaxy (MOVPE) induced by annealing at different temperatures under O2 ambient. Annealing at successively higher temperatures decreases the overall PL yield and UV intensity at nearly the same rates, indicating the increase in formation of at least one non-radiative defect type. Simultaneously, the PL yield ratios of blue/UV and green/UV increase, suggesting that defects associated with these emissions increa…
Uniform and large area synthesis of bulk insulating ultrathin films is an important subject toward applications of a surface of three dimensional topological insulators (3D-TIs) in various electronic devices. Here we report epitaxial growth of bulk insulating three dimensional topological insulator (3D-TI) Bi2-xSbxTe3-ySey (BSTS) ultrathin films, ranging from a few quintuple to several hundreds of layaers, on mica in a large-area (1 cm2) via catalyst free physical vapor deposition. These films can nondestructively be exfoliated using deionized water and transferred to various kinds of substrat…
We report the synthesis of SrMnO$_{3-δ}$F$_{γ}$ perovskite oxyfluoride thin films using a vapor transport method to fluorinate as-grown SrMnO$_{2.5}$ epitaxial thin films. The influence of the fluoropolymer, which acts as a fluorine vapor source, was investigated by utilizing polyvinyl fluoride (PVF), polyvinylidene difluoride (PVDF) and polytetrafluoroethylene (PTFE) in the reaction. The same process was carried out with polyethylene (PE) to isolate the role of carbon in the vapor transport process. The F distribution was probed by X-ray photoemission spectroscopy, which confirmed the incorpo…
