蓝宝石衬底上化学气相沉积法生长石墨烯

化学气相沉积(CVD)法是制备大面积、高质量石墨烯材料的主要方法之一,但存在衬底转移和碳固溶等问题,本文选用蓝宝石衬底弥补了传统CVD法的不足。利用CVD法在蓝宝石衬底上生长石墨烯材料,研究生长温度对石墨烯表面形貌和晶体质量的影响。原子力显微镜(AFM)、光学显微镜(OM)、拉曼光谱和霍尔测试表明,低温生长有利于保持材料表面的平整度,高温生长有利于提高材料的晶体质量。研究氢气和碳源对蓝宝石衬底表面刻蚀作用机理,发现氢气对蓝宝石衬底有刻蚀作用,而单纯的碳源不能对衬底产生刻蚀效果。在1200 ℃下,直径为50 mm的晶圆级衬底上获得平整度和质量相对较好的石墨烯材料,室温下载流子迁移超过1000 cm²·V^-1·s^-1。     

Surface‐Confined Single‐Layer Covalent Organic Framework on Single‐Layer Graphene Grown on Copper Foil

The integration of 2D covalent organic frameworks (COFs) with atomic thickness with graphene will lead to intriguing two‐dimensional materials. A surface‐confined covalently bonded Schiff base network was prepared on single‐layer graphene grown on copper foil and the dynamic reaction process was investigated with scanning tunneling microscopy. DFT simulations provide an understanding of the electronic structures and the interactions between the surface COF and graphene. Strong coupling between the surface COF and graphene was confirmed by the dispersive bands of the surface COF after interaction with graphene, and also by the experimental observation of tunneling condition dependent contrast of the surface COF.     

Photocurrent generation in multilayer organic-inorganic thin films with cascade energy architectures

Zirconium organobisphosphonate multilayer thin films of viologen derivatives were grown on copper dithiolate multilayers of 5,15-di(p-thiolphenyl)-10,20-di(p-tolyl)porphyrin (POR) and 5,15-di(p-thiolphenyl)-10,20-di(p-tolyl)porphyrinzinc (ZOR) on a variety of substrates (e.g. Au, SiO(2)), using solution depositions methods. The multilayer structures were studied by atomic force microscopy, UV-vis spectroscopy, and ellipsometry. In the case of copper dithiolate thin films, layer-by-layer lamellar growth with low surface roughness resulted, while higher surface roughness was observed in the growth of Zr viologen bisphosphonate films. Gold electrodes modified with zirconium bisphosphonate multilayers of viologen on top of copper dithiolate multilayers of porphyrin derivatives (ZOR or POR) were photoelectroactive and produced efficient and stable photocurrents using visible light. By arranging the zinc-porphyrin (ZOR) and the free base porphyrin (POR) donors in an energetically favorable fashion, according to their redox potentials and optical energy gaps, the photoinduced charge separation was improved, and higher photocurrent quantum yields ( approximately 4%) and fill factor ( approximately 50%) of the photoelectrode were achieved.     

Influence of different substrates on ZnO nanorod arrays properties

Zinc Oxide (ZnO) nanorod arrays were grown on different substrates by hydrothermal method. The crystallinity of ZnO nanorod was regularly investigated by X-ray diffraction (XRD). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to examine morphology of the ZnO nanorods. The results indicate that the nanorods grow along [002] orientation. SEM and TEM images and XRD patterns show that the growth of ZnO nanorods on graphene/Quartz substrate is better than the other substrates due to the number and size of the nanorods which are highly affected through the properties of ZnO seed layers and it has lower defects than the other substrates. PL spectra ZnO would have a higher concentration of oxygen vacancy.     

Epitaxial growth on porous GaAs substrates

We report on the electrochemical preparation of porous GaAs substrates in fluoride-iodide aqueous electrolytes for the lattice mismatched epitaxial growth from the vapor phase. The aim is to gain control over the uniformity of the pore nucleation layer and pore branching below this layer to achieve structures with a high degree of porosity and periodicity while leaving minimum damage on the substrate surface. Layers of In_xGa_1-xAs with varying In content are grown on GaAs substrates with different pore geometries and depths. Substantial differences in the surface morphology and photoluminescence efficiency of the layers grown on porous and conventional substrates are observed.     

Molecular-dynamics-based study of the collisions of hyperthermal atomic oxygen with graphene using the ReaxFF reactive force field

In this work, we have investigated the hyperthermal collisions of atomic oxygens with graphene through molecular dynamics simulations using the ReaxFF reactive force field. First, following Paci et al. (J. Phys. Chem. A 2009, 113, 4677 - 4685), 5-eV energetic collisions of atomic oxygen with a 24-atom pristine graphene sheet and a sheet with a single vacancy defect, both functionalized with oxygen atoms in the form of epoxides, were studied. We found that the removal of an O(2) molecule from the surface of the graphene sheet occurs predominantly through an Eley-Rideal-type reaction mechanism. Our results, in terms of the number of occurrences of various reactive events, compared well with those reported by Paci et al. Subsequently, energetic collisions of atomic oxygen with a 25-times-expanded pristine sheet were investigated. The steady-state oxygen coverage was found to be more than one atom per three surface carbon atoms. Under an oxygen impact, the graphene sheet was always found to buckle along its diagonal. In addition, the larger sheet exhibited trampoline-like behavior, as a result of which we observed a much larger number of inelastic scattering events than those reported by Paci et al. for the smaller system. Removal of O(2) from the larger sheet occurred strictly through an Eley-Rideal-type reaction. Investigation of the events leading to the breakup of a pristine unfunctionalized graphene sheet and the effects of the presence of a second layer beneath the graphene sheet in an AB arrangement was done through successive impacts with energetic oxygen atoms on the structures. Breakup of a graphene sheet was found to occur in two stages: epoxide formation, followed by the creation and growth of defects. Events leading to the breakup of a two-layer graphene stack included epoxide formation, transformation from an AB to an AA arrangement as a result of interlayer bonding, defect formation and expansion in the top layer, and finally erosion of the bottom layer. We observed that the breakup of the two-layer stack occurred through a sequential, layer-by-layer, erosion process.     

X-ray studies of self-assembled organic monolayers grown on hydrogen-terminated Si(111)

The structure of self-assembled monolayers (SAMs) of undecylenic acid methyl ester (SAM-1) and undec-10-enoic acid 2-bromo-ethyl ester (SAM-2) grown on hydrogen-passivated Si(111) were studied by X-ray reflectivity (XRR), X-ray standing waves (XSW), X-ray fluorescence (XRF), atomic force microscopy, and X-ray photoelectron spectroscopy (XPS). The two different SAMs were grown by immersion of H-Si(111) substrates into the two different concentrated esters. UV irradiation during immersion was used to create Si dangling bond sites that act as initiators of the surface free-radical addition process that leads to film growth. The XRR structural analysis reveals that the molecules of SAM-1 and SAM-2 respectively have area densities corresponding to 50% and 57% of the density of Si(111) surface dangling bonds and produce films with less than 4 angstroms root-mean-square roughness that have layer thicknesses of 12.2 and 13.2 angstroms. Considering the molecular lengths, these thicknesses correspond to a 38 degrees and 23 degrees tilt angle for the respective molecules. For SAM-2/Si(111) samples, XRF analysis reveals a 0.58 monolayer (ML) Br total coverage. Single-crystal Bragg diffraction XSW analysis reveals (unexpectedly) that 0.48 ML of these Br atoms are at a Si(111) lattice position height that is identical to the T1 site that was previously found by XSW analysis for Br adsorbed onto Si(111) from a methanol solution and from ultrahigh vacuum. From the combined XPS, XRR, XRF, and XSW evidence, it is concluded that Br abstraction by reactive surface dangling bonds competes with olefin addition to the surface.     

Cobalt alters the growth of a manganese oxide film

The mobility of dissolved heavy metals in natural waters is partially regulated by interactions with manganese oxide films. In the current work, the effects of aqueous cobalt(II) on manganese oxide film growth are studied by atomic force microscopy. The film is grown on the (104) surface of rhodochrosite (MnCO3). In the presence of O2(aq) and at circumneutral pH, film growth begins as manganese oxide islands that expand laterally across the surface. Addition of Co2+(aq) leads to the partial or complete dissolution of the manganese oxide film. Simultaneously, there is growth of new islands having multilayer structures that are unrestrained in the z-direction. The chemical composition of these new islands appears to include both Co and Mn ions. Empirical rules governing the growth of the two types of islands can be developed for the absence and the presence of Co2+(aq). In the absence of Co2+(aq), islands grow as flat two-dimensional rhombohedral islands of nearly uniform height (2.4 +/- 0.3 nm). These islands do not cross over steps on the substrate. The growth rules change markedly in the presence of Co2+(aq). The islands grow indefinitely in the z-direction as strata structures of polydisperse thickness and rounded tops. The islands readily grow over steps. Cobalt ions, therefore, relieve the two-dimensional restriction on layer formation and allow three-dimensional growth. Moreover, the shape of the dissolution pits on the surface of MnCO3 changes from rhombohedral in the absence of cobalt to partially rounded in the presence of cobalt. The rounding occurs for the obtuse edges of the pit. Direct microscopic observations of the interactions of cobalt with manganese oxide films provide new mechanistic insights that are important in the quantitative modeling of the mobility of heavy metals in the environment.     

Effect of growth conditions on the structure of two-dimensional latex crystals: experiment

The growth kinetics and structure of two-dimensional crystals of fine latex particles on solid substrates have been studied using a variety of microscopic techniques: optical microscopy, surface plasmon resonance microscopy, transmission electron microscopy, scanning electron microscopy and atomic force microscopy. A circular-shaped crystal is grown from a thin layer of a latex suspension by a two-step mechanism: nucleation and crystal growth. Here we report an experimental study of the factors influencing the crystallization process, especially focusing on the water evaporation rate, the liquid meniscus at the crystal boundary, the particle size and concentration, the substrate, etc. Crystals of good quality and structure are grown at a high evaporation rate (low humidity) favoring a convection-dominated influx of particles from the suspension. The particle diffusion plays a role at suppressed evaporation thus causing an increase in the number of crystal defects. The dynamics of the meniscus slope leads to growth instability resulting in a sequence of multilayer rings. A hexagonal lattice prevails in the final crystal whereas a square lattice is observed in the transition regions between two different hexagonal multilayers. These general trends of the crystallization process are the same for different particle diameters (19 nm, 55 nm, 144 nm and 1.696 μm), volume fractions (0.001–0.01) and substrates (bare and metal-coated glass and mica). Received: 8 February 1999 Accepted in revised form: 12 May 1999     

Toward clean and crackless polymer-assisted transfer of CVD-grown graphene and its recent advances in GFET-based biosensors

Ever since the more than decade-old discovery of the mechanical exfoliation method for graphene isolation, this miraculous 2-dimensional material is still widely used in various applications because of its exceptional electron mobility and thermal conductivity. Graphene, commonly grown on a metallic substrate using chemical vapor deposition (CVD), needs to be transferred onto dielectric substrates compatible with complementary metal oxide–semiconductor (CMOS) technology for various electronic and optical applications. However, the ultra-clean transfer of graphene with defect-free is still crucial for large-area graphene devices' efficiency. This review introduces a comprehensive and up-to-date account of the transfer of the most attention kinds of CVD-grown graphene on copper substrates. The advances and main challenges of both wet and dry transfer methods are also carefully described. Particular emphasis is also given on graphene-based BioFET devices, revising their sensing mechanism and the optimum operational conditions toward high specificity and sensitivity. The authors have been convinced that upgrading the transfer process to accomplish the cleanest graphene surface and exploiting the optimum operating conditions will undoubtedly be of considerable significance to fabricate graphene-based devices.     

单晶硅上化学气相沉积铜薄膜的机理研究

A versatile metal-organic chemical vapor deposition (MOCVD) system was designed and constructed. Copper films were deposited on silicon (100) substrates by chemical vapor deposition (CVD) using Cu(hfac)2 as a precursor. The growth of Cu nucleus on silicon substrates by H2 reduction of Cu(hfac)2 was studied by atomic force microscopy and scanning electron microscopy. The growth mode of Cu nucleus is initially Volmer-Weber mode (island), and then transforms to Stranski-Rastanov mode (layer-by-layer plus island).The mechanism of Cu nucleation on silicon (100) substrates was further investigated by X-ray photoelectron spectroscopy. From Cu2p, O1s, F1s, Si2p patterns, the observed C=O, OH and CF3/CF2 should belong to Cu(hfac) formed by the thermal dissociation of Cu(hfac)2. H2 reacts with hfac on the surface, producing OH. With its accumulation, OH reacts with hfac, forming HO-hfac, and desorbs, meanwhile, the copper oxide is reduced, and thus the redox reaction between Cu(hafc)2 and H2 occurs.     

Controllable synthesis of submillimeter single-crystal monolayer graphene domains on copper foils by suppressing nucleation

Submillimeter single-crystal monolayer and multilayer graphene domains were prepared by an atmospheric pressure chemical vapor deposition method with suppressing nucleation on copper foils through an annealing procedure. A facile oxidation visualization method was applied to study the nucleation density and morphology of graphene domains on copper foils. Scanning electron microscopy, transmission electron microscopy, atomic force microscopy, polarized optical microscopy, and Raman spectra showed that the submillimeter graphene domains were monolayer single crystals.     

Electronic and structural properties of Ti vacancies on the (001) surface of TiS2: theoretical scanning tunneling microscopy images

Various defects--either bright or dark triangular defects--are observed on the (001) titanium disulfide surface by ultrahigh vacuum scanning tunneling microscopy. The experimental interpretations of the images available in the literature suggest that a fraction of Ti atoms could be displaced from the octahedral site they occupied to vacant sites of the crystal structure, leading to more or less correlated defects. In this paper, the authors have performed ab initio periodic linear combination of atomic orbitals-generalized gradient approximation (LCAO-GGA) calculations on (5x5) and (4x4) biperiodic supercells to model the electronic and geometrical involvements of Ti vacancy. The relaxed atomic structures of each system and the wave-function character of the defect states are carefully analyzed before the theoretical scanning tunneling microscopy images are generated within the Tersoff-Hamann approximation. The relaxed structure of the Ti vacancy shows an inward movement of the neighboring sulfur atoms at the surface. However, the occupied electronic states of the vacancy at the Fermi level are mainly developed on the atomic orbitals of the first sulfur neighbors at the surface, leading to bright triangular zones on the simulated image.     

Effect of doping on photovoltaic characteristics of graphene

Chemical doping of CVD grown graphene by introducing PTSA (n-type) and NBD (p-type) dopants is explored. This type of doping is key building block for photovoltaic and optoelectronic devices. Doped graphene samples display (1) high transmittance in the visible and near-infrared spectrum and (2) tunable graphene sheet resistance and work function. Large area and uniform graphene films were produced by chemical vapor deposition on copper foils and transferred onto quartz as transparent substrates. For n doping, a solution of p-toluenesulfonic acid (PTSA) was first dropped and spin-coated on the graphene/quartz and then annealed at 100°C for 10 min to make graphene uniformly n-type. Subsequently, a bare graphene was transferred on another quartz substrate, a solution of 4-nitrobenzenediazonium tetrafluoroborate (NBD) was dropped and spin-coated on the surface of graphene and similarly annealed. As a result, the graphene was p and n doped on the different quartz substrates. Doped graphene samples were characterized by different techniques. Experimental results suggested that doped graphene sheets with tunable electrical resistance and high optical transparency can be incorporated into photovoltaics and optoelectronics devices.     

氧化石墨烯的可控还原及结构表征

采用氧化还原法, 通过控制还原时间制备了不同还原程度的石墨烯; 用红外光谱、 紫外光谱、 拉曼光谱、 X射线衍射、 热重分析、 电导率测量等多种手段系统研究了不同还原程度石墨烯的结构与性能; 采用透射电子显微镜、 扫描电子显微镜和原子力显微镜比较了氧化石墨烯和石墨烯的形貌. 结果表明, 随着还原程度的增加, 石墨烯中含氧基团减少, 紫外吸收峰逐渐红移, D带与G带的强度比增加, 热稳定性和导电性提高. 微观结构表征说明石墨烯比氧化石墨烯片的厚度增加, 褶皱增多.     

Ir(111)表面石墨烯中缺陷的原子结构确认

识别和解析石墨烯中缺陷的精确原子结构是研究不同类型缺陷的物化特性, 实现石墨烯物性调控的前提, 可以为在原子尺度研究石墨烯缺陷的构效关系提供重要的实验依据. 本文结合扫描隧道显微镜(STM)和原子力显微镜(AFM)确认了在Ir(111)表面生长的石墨烯中自发形成的缺陷, 以及通过离子轰击方法在石墨烯中引入的多种缺陷结构, 包括单空位缺陷、 非六元环拓扑结构以及石墨烯层下的基底缺陷.     

Growth morphology and properties of metals on graphene

Graphene, a single atomic layer of graphite, has been the focus of recent intensive studies due to its novel electronic and structural properties. Metals grown on graphene also have been of interest because of their potential use as metal contacts in graphene devices, for spintronics applications, and for catalysis. All of these applications require good understanding and control of the metal growth morphology, which in part reflects the strength of the metal–graphene bond. Also of importance is whether the interaction between graphene and metal is sufficiently strong to modify the electronic structure of graphene. In this review, we will discuss recent experimental and computational studies related to deposition of metals on graphene supported on various substrates (SiC, SiO₂, and hexagonal close-packed metal surfaces). Of specific interest are the metal–graphene interactions (adsorption energies and diffusion barriers of metal adatoms), and the crystal structures and thermal stability of the metal nanoclusters.     

Selective nucleation and discovery of organic polymorphs through epitaxy with single crystal substrates.

Crystallization of 5-methyl-2-[(2-nitrophenyl)amino]-3-thiophenecarbonitrile (1), previously found to produce six conformational polymorphs from solution, on single-crystal pimelic acid (PA) substrates results in selective and oriented growth of the metastable "YN" (yellow needle) polymorph on the (101)(PA) faces of the substrate. Though the freshly cleaved substrate crystals expose (101)(PA) and (111)(PA) faces, which are both decorated with [101](PA) ledges that could serve as nucleation sites, crystal growth of YN occurs on only (101)(PA). Goniometry measurements performed with an atomic force microscope reveal that the (001)(YN) plane contacts (101)(PA) with a crystal orientation [100](YN)//[010](PA) and [010](YN)//[101](PA). A geometric lattice analysis using a newly developed program dubbed GRACE (geometric real-space analysis of crystal epitaxy) indicates that this interfacial configuration arises from optimal two-dimensional epitaxy and that among the six polymorphs of 1, only the YN polymorph, in the observed orientation, achieves reasonable epitaxial match to (101)(PA). The geometric analysis also reveals that none of the polymorphs, including YN, can achieve comparable epitaxial match with (111)(PA), consistent with the absence of nucleation on this crystal face. In contrast, sublimation of 1 on cleaved succinic acid (SA) substrates, which expose large (010)(SA) faces decorated with steps along [101](SA), affords growth of several polymorphs, each with multiple orientations, as well as oriented crystals of a new metastable polymorph on the (010)(SA) surfaces. The lack of polymorphic selectivity on (010)(SA) can be explained by the geometric lattice analysis, which reveals low-grade epitaxial matches between (010)(SA) and several polymorphs of 1 but no inherent selectivity toward a single polymorph. These observations demonstrate the sensitivity of crystal nucleation to substrate surface structure, the potential of crystalline substrates for selective nucleation and discovery of polymorphs, and the utility of geometric lattice modeling for screening of substrate libraries for controlling polymorphism.     

Diffusion and elementary atomic processes at steeped surfaces

The mobility of atoms at and near lattice step edges plays an important role in epitaxial growth and surface morphology of thin films, and the dynamic behavior of surfaces at elevated temperature. We summarize our recent FIM studies on how atoms move and bind at step edges, how atoms can descend and ascend lattice steps, how in-layer atoms can move up to the upper terrace, and how these atomic processes are related to various growth structures in thin film epitaxy.     

Fast growth of graphene on SiO2/Si substrates by atmospheric pressure chemical vapor deposition with floating metal catalysts

Graphene on dielectric substrates is essential for its electronic applications. Graphene is typically synthesized on the surface of metal and then transferred to an appropriate substrate for fabricating device applications. This post growth transfer process is detrimental to the quality and performance of the as-grown graphene. Therefore, direct growth of graphene films on dielectric substrates without any transfer process is highly desirable. However, fast growth of graphene on dielectric substrates remains challenging. Here, we demonstrate a transfer-free chemical vapor deposition (CVD) method to directly grow graphene films on dielectric substrates at fast growth rate using Cu as floating catalyst. A large area (centimeter level) graphene can be grown within 15 min using this CVD method, which is increased by 500 times compared to other direct CVD growth on dielectric substrate in the literatures. This research presents a significant progress in transfer-free growth of graphene and graphene device applications.