金刚石薄膜在多晶铜和磷脱氧铜基片上的生长

分别采用99.99%的多晶铜片和99.95%的磷脱氧铜片作为沉积金刚石薄膜的基片，通过热丝化学汽相沉积法在两种基片上都获得了大面积、自支撑的多晶金刚石膜.使用高分辨率光学显微镜、扫描电子显微镜、Raman光谱和X射线衍射比较分析了两种铜基片上的金刚石膜.脱氧铜上的金刚石膜质量并不亚于多晶铜上的金刚石膜，而且它的成核密度、生长速率以及应力都高于多晶铜上金刚石膜的同类参数.特别采用了退火工艺和优化的生长条件来获得大面积的连续金刚石膜. 关键词：     

不同衬底条件下石墨烯结构形核过程的晶体相场法研究

利用可描述气-固转变的三模晶体相场模型,在原子尺度上研究了不同衬底条件下石墨烯结构的形核过程.结果表明:无论衬底存在与否,气态原子均是先聚集为无定形过渡态团簇,随着气态原子的不断堆积和固相团簇中原子位置的不断调整,过渡态团簇逐渐转变为有序的石墨烯晶核,在此过程中,五元环结构具有重要的过渡作用;石墨烯在结构匹配较好的衬底(如面心立方(face-centered cubic,FCC)结构(111)和(110))上生长时,可形成几乎没有结构缺陷单晶石墨烯岛;在无衬底或结构匹配性较差的衬底(如FCC结构(100)面)上生长时,形成的石墨烯岛结构缺陷和晶界较多,不利于高质量石墨烯的制备.     

Influence of copper crystal surface on the CVD growth of large area monolayer graphene

We study the influence of the surface structure of copper single crystals on the growth of large area monolayer graphene by chemical vapor deposition (CVD) in ultra-high vacuum (UHV). Using atomic-resolution scanning tunneling microscopy (STM), we find that graphene grows primarily in registry with the underlying copper lattice for both Cu(111) and Cu(100). The graphene has a hexagonal superstructure on Cu(111) with a significant electronic component,whereas it has a linear superstructure on Cu(100). Graphene on Cu(111) forms a microscopically uniform sheet, the quality of which is determined by the presence of grain boundaries where graphene grains with different orientations meet. Graphene grown on Cu(100) under similar conditions does not form a uniform sheet and instead displays exposed nanoscale edges. Our results indicate the importance of the copper crystal structure on the microstructure of graphene films produced by CVD.     

化学气相沉积法制备石墨烯的铜衬底预处理研究

铜作为一种在化学气相沉积法制备石墨烯中被广泛采用的衬底材料,其表面形貌和质量对石墨烯的品质有较大的影响.提出了一种简单有效的铜衬底预处理方法,在生长石墨烯前,将铜衬底在浓度为1 mol/L的硝酸铁水溶液中进行预刻蚀,研究了不同刻蚀时间的影响.发现当预刻蚀时间为90 s时,经石墨烯生长后得到了相对平整且无杂质颗粒的表面;与盐酸预刻蚀及电化学抛光方法进行了比较,实验结果表明,硝酸铁溶液预刻蚀的效果优于盐酸处理,可与电化学抛光效果比拟,且操作更为简单快捷.经过不同型号铜衬底实验验证,此方法具有普遍适用性.     

Electronic properties of grains and grain boundaries in graphene grown by chemical vapor deposition

We synthesize hexagonal shaped single-crystal graphene, with edges parallel to the zig-zag orientations, by ambient pressure CVD on polycrystalline Cu foils. We measure the electronic properties of such grains as well as of individual graphene grain boundaries, formed when two grains merged during the growth. The grain boundaries are visualized using Raman mapping of the D band intensity, and we show that individual boundaries between coalesced grains impede electrical transport in graphene and induce prominent weak localization, indicative of intervalley scattering in graphene.     

Thin-film polycrystalline Si solar cells on foreign substrates: film formation at intermediate temperatures (700–1300 °C)

We give an overview and analysis of research on thin-film polycrystalline Si solar cells on foreign substrates, with layers formed at intermediate temperatures (700–1300 °C), covering substrates, deposition techniques and solar cell processing. The main deposition techniques that have been investigated are solution growth (SG) and chemical vapour deposition (CVD). Insufficient nucleation on foreign substrates is an important problem with SG, which could be solved with appropriate surface preparation techniques and growth conditions. With CVD, continuous layers are achieved routinely, but the electronic quality of the material is usually very low. Solar cell performance appears to be limited by a very large recombination activity of grain boundaries. Improvement can be achieved reducing the grain boundary density and recombination activity, and experimental examples are given. Devices have been demonstrated with efficiencies up to 5.5%. PACS 73.40.Lq; 73.50.Gr; 84.60.It     

Fabrication of particular structures of hexagonal boron nitride and boron–carbon–nitrogen layers by anisotropic etching

Anisotropic etching of hexagonal boron nitride (h-BN) and boron–carbon–nitrogen (BCN) basal plane can be an exciting platform to develop well-defined structures with interesting properties. Here, we developed an etching process of atomically thin h-BN and BCN layers to fabricate nanoribbons (NRs) and other distinct structures by annealing in H₂ and Ar gas mixture. BCN and h-BN films are grown on Cu foil by chemical vapor deposition (CVD) using solid camphor and ammonia borane as carbon, nitrogen and boron source, respectively. Formation of micron size well-defined etched holes and NRs are obtained in both h-BN and BCN layers by the post growth annealing process. The etching process of h-BN and BCN basal plane to fabricate NRs and other structures with pronounced edges can open up new possibilities in 2D hybrid materials.     

Graphene growth process modeling: a physical–statistical approach

As a zero-band semiconductor, graphene is an attractive material for a wide variety of applications such as optoelectronics. Among various techniques developed for graphene synthesis, chemical vapor deposition on copper foils shows high potential for producing few-layer and large-area graphene. Since fabrication of high-quality graphene sheets requires the understanding of growth mechanisms, and methods of characterization and control of grain size of graphene flakes, analytical modeling of graphene growth process is therefore essential for controlled fabrication. The graphene growth process starts with randomly nucleated islands that gradually develop into complex shapes, grow in size, and eventually connect together to cover the copper foil. To model this complex process, we develop a physical–statistical approach under the assumption of self-similarity during graphene growth. The growth kinetics is uncovered by separating island shapes from area growth rate. We propose to characterize the area growth velocity using a confined exponential model, which not only has clear physical explanation, but also fits the real data well. For the shape modeling, we develop a parametric shape model which can be well explained by the angular-dependent growth rate. This work can provide useful information for the control and optimization of graphene growth process on Cu foil.     

Strain-induced pseudo-magnetic fields and charging effects on CVD-grown graphene

Atomically resolved imaging and spectroscopic characteristics of graphene grown by chemical vapor deposition (CVD) on copper are investigated by means of scanning tunneling microscopy and spectroscopy (STM/STS). For CVD-grown graphene remaining on the copper substrate, the monolayer carbon structures exhibit ripples and appear strongly strained, with different regions exhibiting different lattice structures and electronic density of states (DOS). In particular, ridges appear along the boundaries of different lattice structures, which exhibit excess charging effects. Additionally, the large and non-uniform strain induces pseudo-magnetic field up to ~ 50 T, as manifested by the DOS peaks at quantized energies that correspond to pseudo-magnetic field-induced integer and fractional Landau levels. In contrast, for graphene transferred from copper to SiO₂ substrates after the CVD growth, the average strain on the whole diminishes, so do the corresponding charging effects and pseudo-magnetic fields except for sample areas near topological defects. These findings suggest feasible nano-scale “strain engineering” of the electronic states of graphene by proper design of the substrates and growth conditions.     

化学气相沉积法制备的石墨烯晶畴的氢气刻蚀

利用化学气相沉积法在抛光铜衬底上制备出六角形石墨烯晶畴, 并且在高温条件下对石墨烯晶畴进行氢气刻蚀, 利用光学显微镜和扫描电子显微镜对石墨烯晶畴进行观测, 发现高温条件下石墨烯晶畴表面能够被氢气刻蚀出网络状和线状结构的刻蚀条纹. 通过电子背散射衍射测试证明了刻蚀条纹的形态、密度与铜衬底的晶向有密切关系. 通过对比实验证明了石墨烯表面上的刻蚀条纹是由于石墨烯和铜衬底的热膨胀系数不同, 在降温过程中, 石墨烯表面形成了褶皱, 褶皱在高温氢气气氛下发生氢化反应形成的. 对转移到二氧化硅衬底的石墨烯晶畴进行原子力显微镜测试, 测试结果表明刻蚀条纹的形貌、密度与石墨烯表面褶皱的形貌、密度十分相似. 进一步证明了刻蚀条纹是由于褶皱结构被氢气刻蚀引起的. 实验结果表明, 即使在六角形石墨烯晶畴表面也存在褶皱和点缺陷. 本文提供了一种便捷的方法来观察铜衬底上石墨烯褶皱的分布与形态; 同时, 为进一步提高化学气相沉积法制备石墨烯的质量提供了更多参考.     

ESR and X-ray diffraction studies of the CVD diamond films

Thin polycrystalline, diamond films were prepared by thermal decomposition of hydrocarbon and hydrogen in the presence of a hot tungsten filament (HF CVD technique). Electron Spin Resonance (ESR) spectroscopy investigations were carried out and correlated to diamond microcrystal size estimated on the basis of X-ray diffraction (XRD) measurements. It was shown that both ESR signal and average crystal size of the thin CVD diamond films depend strongly on the ratio of hydrocarbon/hydrogen concentrations in the CVD reactor. XRD spectra indicate the presence of fullerence and, graphitic polytypes in most studied samples, independent of growth conditions. Observed reciprocal proportionality of the ESR signal intensity versus diamond grain size suggests that the above mentioned carbon phases are mainly dispersed at the grain boundaries.     

Scalable synthesis of graphene on single crystal Ir(111) films

We have investigated single crystal Ir(111) films grown heteroepitaxially on Si(111) wafers with yttria-stabilized zirconia (YSZ) buffer layers as possible substrates for an up-scalable synthesis of graphene. Graphene was grown by chemical vapor deposition (CVD) of ethylene. As surface analytical techniques we have used scanning tunneling microscopy (STM), low-energy electron diffraction, scanning electron microscopy, and atomic force microscopy. The mosaic spread of the metal films was below 0.2° similar to or even below that of standard Ir bulk single crystals, and the films were basically twin-free. The film surfaces could be improved by annealing so that they attained the perfection of bulk single crystals. Depending on the CVD conditions a lattice-aligned graphene layer or a film consisting of different rotational domains were obtained. STM data of the non-rotated phase and of the phases rotated by 14° and 19° were acquired. The quality of the graphene was comparable to graphene grown on bulk Ir(111) single crystals.     

Studies of iron and iron oxide layers by electron spectroscopes

Thin iron oxide layers prepared “in situ” in the ultra high vacuum on polycrystalline iron substrate were investigated by electron spectroscopy methods—X-ray photoelectron spectroscopy (XPS) and elastic peak electron spectroscopy (EPES), using spectrometer ADES-400. The texture and the average grain size of the iron substrate foil have been examined by glancing angle X-ray diffraction (XRD). Qualitative and quantitative estimation of investigated oxide layers was made using (i) the relative sensitivity factor XPS method, (ii) comparison of binding energy shifts of Fe 2p photoelectron line and (iii) non-linear fitting procedure of Fe 2p photoelectron lines.Both, sputter-clean polycrystalline iron substrate and finally grown Fe_2.2O₃ layer, were investigated by the EPES method to measure the electron transport parameters used for quantitative electron spectroscopy, such as the electron inelastic mean free path (IMFP) values. The IMFPs were measured in the electron kinetic energy range 200-1000 eV with the Cu standard. The surface excitation parameters using Chen and Werner et al. approaches were evaluated and applied for correcting these IMFPs. The discrepancies between the evaluated parameters obtained using the above quantitative and qualitative approaches for characterising the iron oxide layers were discussed.     

Synthesis of high-quality monolayer graphene by low-power plasma

The growth of high-quality graphene on copper substrates has been intensively investigated using chemical vapor deposition (CVD). It, however, has been considered that the growth mechanism is different when graphene is synthesized using a plasma CVD. In this study, we demonstrate a dual role of hydrogen for the graphene growth on copper using an inductively coupled plasma (ICP) CVD. Hydrogen activates surface-bound carbon for the growth of high-quality monolayer graphene. In contrast, the role of an etchant is to manipulate the distribution of the graphene grains, which significantly depends on the plasma power. Atomic-resolution transmission electron microscopy study enables the mapping of graphene grains, which uncovers the distribution of grains and the number of graphene layers depending on the plasma power. In addition, the variation of electronic properties of the synthesized graphene relies on the plasma power.     

Preparation of graphene on Cu foils by ion implantation with negative carbon clusters

We report on few-layer graphene synthesized on Cu foils by ion implantation using negative carbon cluster ions,followed by annealing at 950?C in vacuum.Raman spectroscopy reveals IG/I2Dvalues varying from 1.55 to 2.38 depending on energy and dose of the cluster ions,indicating formation of multilayer graphene.The measurements show that the samples with more graphene layers have fewer defects.This is interpreted by graphene growth seeded by the first layers formed via outward diffusion of C from the Cu foil,though nonlinear damage and smoothing effects also play a role.Cluster ion implantation overcomes the solubility limit of carbon in Cu,providing a technique for multilayer graphene synthesis.     

铜箔上生长的六角氮化硼薄膜的扫描隧道显微镜研究

利用扫描隧道显微镜研究了采用化学气相沉积法在铜箔表面生长出的高质量的六角氮化硼薄膜. 大范围的扫描隧道显微镜图像显示出该薄膜具有原子级平整的表面, 而扫描隧道谱则显示, 扫描隧道显微镜图像反映出的是该薄膜样品的隧穿势垒空间分布. 极低偏压的扫描隧道显微镜图像呈现了氮化硼薄膜表面的六角蜂窝周期性原子排列, 而高偏压的扫描隧道显微镜图像则呈现出无序和有序排列区域共存的电子调制图案. 该调制图案并非源于氮化硼薄膜和铜箔衬底的面内晶格失配, 而极有可能来源于两者界面处的氢、硼和/或氮原子在铜箔表面的吸附所导致的隧穿势垒的局域空间分布.     

Graphene growth on h-BN by molecular beam epitaxy

The growth of single layer graphene nanometer size domains by solid carbon source molecular beam epitaxy on hexagonal boron nitride (h-BN) flakes is demonstrated. Formation of single-layer graphene is clearly apparent in Raman spectra which display sharp optical phonon bands. Atomic-force microscope images and Raman maps reveal that the graphene grown depends on the surface morphology of the h-BN substrates. The growth is governed by the high mobility of the carbon atoms on the h-BN surface, in a manner that is consistent with van der Waals epitaxy. The successful growth of graphene layers depends on the substrate temperature, but is independent of the incident flux of carbon atoms.     

Influence of the electrical parameters on the fabrication of copper nanowires into anodic alumina templates

Metallic copper nanowires have been grown into the pores of alumina membranes by electrodeposition from an aqueous solution containing CuSO₄^.and H₃BO₃ at pH 3. In order to study the influence of the electrical parameters on growth and structure of nanowires, different deposition potentials (both in the region where hydrogen evolution reaction is allowed or not) and voltage perturbation modes (constant potential or unipolar pulsed depositions) were applied. In all cases, pure polycrystalline Cu nanowires were fabricated into template pores, having lengths increasing with the total deposition time. These nanowires were self-standing, because they retain their vertical orientation and parallel geometry even after total template dissolution.However, the electrical parameters influence the growth rate, length uniformity and crystal size of the nanowires. Continuous electrodeposition resulted in higher growth rates but less uniform lengths of nanowires grown inside different membrane pores, whilst a square pulse deposition produced a slower growth but quite uniform lengths. Also the grain size, of the order of 50 nm, was slightly influenced by the potential perturbation mode.     

Comparison of the formation epitaxial graphenes on Si- and process and properties of C-face 6H-SiC substrates

In this paper,the epitaxial graphene layers grown on Si-and C-face 6H-SiC substrates are investigated under a low pressure of 400 Pa at 1600 C.By using atomic force microscopy and Raman spectroscopy,we find that there are distinct differences in the formation and the properties between the epitaxial graphene layers grown on the Si-face and the C-face substrates,including the hydrogen etching process,the stacking type,and the number of layers.Hopefully,our results will be useful for improving the quality of the epitaxial graphene on SiC substrate.     

Raman analysis of bilayer graphene film prepared on commercial Cu(0.5 at% Ni) foil

This study reports the Raman analysis of bilayer graphene films prepared on commercial dilute Cu(0.5 at% Ni) foils using atmospheric pressure chemical vapor deposition. A bilayer graphene film obtained on Cu foil is known to have small areas of bilayer (islands) with a significant fraction of non‐Bernal stacking, while that obtained on Cu/Ni is known to grow over a large area with Bernal stacking. In the Raman optical microscope images, a wafer‐scale monolayer and large‐area bilayer graphene films were distinguished and confirmed with Raman spectra intensities ratios of 2D to G peaks. The large‐area part of bilayer graphene film obtained was assisted by Ni surface segregation because Ni has higher methane decomposition rate and carbon solubility compared with Cu. The Raman data suggest a Bernal stacking order in the prepared bilayer graphene film. A four‐point probe sheet resistance of graphene films confirmed a bilayer graphene film sheet resistance distinguished from that of monolayer graphene. A relatively higher Ni surface concentration in Cu(0.5 at% Ni) foil was confirmed with time‐of‐flight secondary ion mass spectrometry. The inhomogeneous distribution of Ni in a foil and the diverse crystallographic surface of a foil (confirmed with proton‐induced X‐ray emission and electron backscatter diffraction, respectively) could be a reason for incomplete wafer‐scale bilayer graphene film. The Ni surface segregation in dilute Cu(0.5 at% Ni) foil has a potential to impact on atmospheric pressure chemical vapor deposition growth of large‐area bilayer graphene film. Copyright © 2015 John Wiley & Sons, Ltd.