We quantify the mechanisms for manganese (Mn) diffusion through graphene in Mn/graphene/Ge (001) and Mn/graphene/GaAs (001) heterostructures for samples prepared by graphene layer transfer versus graphene growth directly on the semiconductor substrate. These heterostructures are important for applications in spintronics; however, challenges in synthesizing graphene directly on technologically important substrates such as GaAs necessitate layer transfer and anneal steps, which introduce defects into the graphene. \textit{In-situ} photoemission spectroscopy measurements reveal that Mn diffusion through graphene grown directly on a Ge (001) substrate is 1000 times lower than Mn diffusion into samples without graphene ($D_{gr,direct} \sim 4\times10^{-18}$cm$^2$/s, $D_{no-gr} \sim 5 \times 10^{-15}$ cm$^2$/s at 500$^\circ$C). Transferred graphene on Ge suppresses the Mn in Ge diffusion by a factor of 10 compared to no graphene ($D_{gr,transfer} \sim 4\times10^{-16}cm^2/s$). For both transferred and directly-grown graphene, the low activation energy ($E_a \sim 0.1-0.5$ eV) suggests that Mn diffusion through graphene occurs primarily at graphene defects. This is further confirmed as the diffusivity prefactor, $D_0$, scales with the defect density of the graphene sheet. Similar diffusion barrier performance is found on GaAs substrates; however, it is not currently possible to grow graphene directly on GaAs. Our results highlight the importance of developing graphene growth directly on functional substrates, to avoid the damage induced by layer transfer and annealing.
Graphene layers grown by chemical vapour deposition (CVD) method and transferred from Cu-foils to the oxidized Si-substrates were investigated by spectroscopic ellipsometry (SE), Raman and X-Ray Photoelectron Spectroscopy (XPS) methods. The optical properties of transferred CVD graphene layers do not always correspond to the ones of the exfoliated graphene due to the contamination from the chemicals used in the transfer process. However, the real thickness and the mean properties of the transferred CVD graphene layers can be found using ellipsometry if a real thickness of the SiO2 layer is tak…
Improved topological conformity enhances heat conduction across metal contacts on transferred graphene
转移的石墨烯（trG）上的金属接触的热导率可以显着降低从原生石墨烯（grG）上的类似接触的固有值，由于增加的粗糙度，残留物，氧化物和空隙的额外电阻。在本文中，我们比较了Al/trG/Cu界面的热导率（G）与Al/grG/Cu界面的热导率，以了解转移石墨烯上金属接触的热传递。我们的样品是通过化学气相沉积（CVD）在Cu箔上生长的多晶石墨烯和CVD生长的石墨烯转移到蒸发的Cu薄膜上。我们发现，对于生长的CVD石墨烯的Al/grG/Cu界面，在室温下G = 31 MW m ^{-2} K ^{-1}，比Al/Cu界面低两个数量级。对于大多数在Cu膜上转移的石墨烯，G = 20 MW m ^{-2} K ^{-1}，比生长的CVD石墨烯低35%。我们仔细排除了残留物，原生氧化物和界面粗糙度的贡献，并将生长和转移的CVD石墨烯的热导率的差异归因于石墨烯对Cu衬底的不同程度的一致性。我们发现，50%的接触面积仅使热导率降低了35%，这表明在石墨烯界面处的空隙中发生了少量的热传递。我们通过在300 ° C下退火样品成功地改善了转移石墨烯与衬底的一致性，从而将转移石墨烯的热导率提高到本征值。从Al/trG/Cu和Al/grG/Cu界面的G的温度依赖性测量，我们还证实了声子是金属/石墨烯/金属界面上的主要热载体，尽管石墨烯中诱导的载流子浓度为3 × 10 ^{12} cm ^{-2}。
We report high room-temperature mobility in single layer graphene grown by Chemical Vapor Deposition (CVD) after wet transfer on SiO$_2$ and hexagonal boron nitride (hBN) encapsulation. By removing contaminations trapped at the interfaces between single-crystal graphene and hBN, we achieve mobilities up to$\sim70000cm^2 V^{-1} s^{-1}$ at room temperature and$\sim120000cm^2 V^{-1} s^{-1}$ at 9K. These are over twice those of previous wet transferred graphene and comparable to samples prepared by dry transfer. We also investigate the combined approach of thermal annealing and encapsulation in po…
The defect-free transfer of chemical vapour deposition (CVD) grown monolayer MoS2 is important for both fabrication of 2D devices and fundamental point of view for various studies where substrate effects need to be minimized. Among many transfer techniques, two well-known techniques that use the polymer as carriers are wet-transfer technique and the surface-energy-assisted transfer technique. In this work, we transferred a single CVD grown monolayer MoS2 by these two transfer methods on a similar substrate, and the intervention of strain and defects in the transfer process is probed by Raman a…
High Quality, Transferable Graphene Grown on Single Crystal Cu(111) Thin Films on Basal-Plane Sapphire
目前在Cu表面（多晶箔和薄膜）上生长大面积石墨烯并将其转移到任意衬底的方法在技术上是有吸引力的。然而，石墨烯的质量可以通过在单晶Cu表面上生长而显著提高。在这里，我们表明，高质量，大面积的石墨烯可以生长在外延单晶Cu（111）薄膜上的可重复使用的基面蓝宝石（α-Al 2 O 3（0001））衬底，然后转移到另一个基板。在使石墨烯能够在Cu单晶表面上生长的同时，该方法具有避免与在石墨烯转移期间牺牲体单晶Cu相关联的高成本和对石墨烯的广泛损害的潜力。
We report an investigation of the graphene/substrate interface morphology in large-area polycrystalline graphene grown by chemical-vapour deposition and wet-transferred onto Si wafers. We combined spectroscopic ellipsometry, X-ray photoelectron spectroscopy and atomic-force microscopy in order to yield morphological and chemical information about the system. The data showed that wet-transferred samples may randomly exhibit nanosized relief patterns indicative of small water nanopockets trapped between graphene and the underlying substrate. These pockets affect the adhesion of graphene to the s…
We report on the fabrication and characterization of high-quality chemical vapor-deposited (CVD) bilayer graphene (BLG). In particular, we demonstrate that CVD-grown BLG can mechanically be detached from the copper foil by an hexagonal boron nitride (hBN) crystal after oxidation of the copper-to-BLG interface. Confocal Raman spectroscopy reveals an AB-stacking order of the BLG crystals and a high structural quality. From transport measurements on fully encapsulated hBN/BLG/hBN Hall bar devices we extract charge carrier mobilities up to 180,000 cm$^2$/(Vs) at 2 K and up to 40,000 cm$^2$/(Vs) at…
Through a combination of monitoring the Raman spectral characteristics of 2D materials grown on copper catalyst layers, and wafer scale automated detection of the fraction of transferred material, we reproducibly achieve transfers with over 97.5% monolayer hexagonal boron nitride and 99.7% monolayer graphene coverage, for up to 300 mm diameter wafers. We find a strong correlation between the transfer coverage obtained for graphene and the emergence of a lower wavenumber 2D- peak component, with the concurrent disappearance of the higher wavenumber 2D+ peak component during oxidation of the cat…
We report on preparation dependent properties observed in monolayer WS2 samples synthesized via chemical vapor deposition (CVD) on a variety of common substrates (Si/SiO2, sapphire, fused silica) as well as samples that were transferred from the growth substrate onto a new substrate. The as-grown CVD materials (as-WS2) exhibit distinctly different optical properties than transferred WS2 (x-WS2). In the case of CVD growth on Si/SiO2, following transfer to fresh Si/SiO2 there is a ~50 meV shift of the ground state exciton to higher emission energy in both photoluminescence emission and optical r…
Thin films are ubiquitous, with uses ranging from optoelectronics to antibacterial coatings. Unfortunately, precisely quantifying how the choice of substrate influences epitaxial growth remains an unsolved problem. Here, a novel thin film of holmium oxide with record-high paramagnetic saturation was grown on a variety of substrates. Conventional attempts to extract epitaxial information to characterize the growth mechanism were ineffective, due to the unique size regime of the product. Instead, a signal-processing inspired Fourier method was used to elucidate information on epitaxial ordering …
Crystal orientation relation and macroscopic surface roughness in hetero-epitaxially grown graphene on Cu/mica
石墨烯电子产品对衬底上的清洁、平坦和取向识别的石墨烯有很高的需求。在这项研究中，异质外延石墨烯生长Cu（111）/云母（001）的化学气相沉积进行了研究，以检查的适用性，顶栅绝缘体的石墨烯的研究，以及石墨烯沟道的研究，通过转移到SiO2/Si衬底。在调整石墨烯生长条件后，石墨烯/Cu/云母衬底的表面粗糙度和平均光滑面积分别为~0.34 nm和~100 um 2。石墨烯/Cu/云母衬底中石墨烯的取向可以通过Cu的六方空隙形态来识别。此外，我们证明了相对较高的迁移率~4500 cm ~ 2 V-1 s-1的石墨烯转移到SiO2/Si衬底上。这些结果表明，本发明的石墨烯/Cu/云母衬底可用于石墨烯上的顶栅绝缘体研究。
We show the emergence of fractional quantum Hall states in dry-transferred chemical vapor deposition (CVD) derived graphene assembled into heterostructures for magnetic fields from below 3 T to 35 T. Effective composite-fermion filling factors up to $ν^* = 4$ are visible and higher order composite-fermion states (with four flux quanta attached) start to emerge at the highest fields. Our results show that the quantum mobility of CVD-grown graphene is comparable to that of exfoliated graphene and, more specifically, that the $p/3$ fractional quantum Hall states have energy gaps of up to 30 K, we…
Vertical graphene nanosheets (VGNs) are the material of choice for next-generation electronic device applications. The growing demand for flexible devices in electronic industry brings in restriction on growth temperature of the material of interest. However, VGNs with better structural quality is usually achieved at high growth temperatures. The difficulty associated with the direct growth on flexible substrates can overcome by adopting an effective strategy of transferring the well grown VGNs onto arbitrary flexible substrates through soft chemistry route. Hence, we demonstrated a simple, in…
The transfer of graphene grown by chemical vapor deposition (CVD) using amorphous polymers represents a widely implemented method for graphene-based electronic device fabrication. However, the most commonly used polymer, poly(methyl methacrylate) (PMMA), leaves a residue on the graphene that limits the mobility. Here we report a method for graphene transfer and patterning that employs a perfluoropolymer---Hyflon---as a transfer handle and to protect graphene against contamination from photoresists or other polymers. CVD-grown graphene transferred this way onto LaAlO$_3$/SrTiO$_3$ heterostructu…
We report the synthesis of single and bi layer graphene films by low pressure chemical vapor deposition technique on Cu and Au substrates. The as grown films were characterized by transmission electron microscopy, scanning electron microscopy and Raman spectroscopy techniques. The large lateral area graphene deposited on Cu can easily be transferred on Si SiO2. In the case of Au substrate both the adsorption and diffusion-precipitation leads to the growth of graphene.
We demonstrate rapid deterministic (seeded) growth of large single-crystals of graphene by chemical vapour deposition (CVD) utilising pre-patterned copper substrates with chromium nucleation sites. Arrays of graphene single-crystals as large as several hundred microns are grown with a periodicity of up to 1 mm. The graphene is transferred to target substrates using aligned and contamination-free semi-dry transfer. The high quality of the synthesised graphene is confirmed by Raman spectroscopy and transport measurements, demonstrating room-temperature carrier mobility of 21 000 cm2 / V s when t…
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）
Layer transfer offers enormous potential for the industrial implementation of 2D material technology platforms. However, the transfer method used must retain as-grown uniformity and cleanliness in the transferred films for the fabrication of 2D material-based. Additionally, the method used must be capable of large-area transfer to maintain wafer-scale fabrication standards. Here, a facile route to transfer centimeter-scale synthesized 2D TMDCs (3L MoS2, 1L WS2) onto various substrates such as sapphire, SiO2/Si, and flexible substrates (mica, polyimide) has been developed using a water-soluble …
Uniform, mostly single-layer graphene with enhanced stability is demonstrated over Co film. The polycrystalline Co film deposited on a SiO2/Si substrate gives a continuous graphene layer that is easily transferred without the aid of any polymeric support, but preserving the material quality, as evidenced by Raman analysis. Great stability to the damaging action of the laser beam, as compared to the Cu-grown material is also observed. The better structural and electrical properties of the material are interpreted in terms of thermodynamics of the cooling-down process. It is suggested that the r…
The recent progress in the growth of large-area boron nitride epilayers opens up new possibilities for future applications. However, it remains largely unclear how weakly attached two-dimensional BN layers interact with their substrate and how their properties are influenced by defects. In this work, we investigate hBN layers grown by Metal Organic Vapor Phase Epitaxy (MOVPE) using Fourier-transform Infrared (FTIR) spectroscopy in the temperature range of 160-540 K. Our measurements reveal strong differences in the character of layer-substrate interaction for as-grown and delaminated epitaxial…
The resistivity of different films and structures containing fluorinated graphene (FG) flakes and chemical vapor deposition (CVD) grown graphene of various fluorination degrees under tensile and compressive strains due to bending deformations was studied. Graphene and multilayer graphene films grown by means of the CVD method were transferred onto the flexible substrate by laminating and were subjected to fluorination. They demonstrated a weak fluorination degree (F/C lower 20%). Compressive strains led to a strong (one-two orders of magnitude) decrease in the resistivity in both cases, which …
We report a technique for transferring large areas of the CVD-grown, few-layer MoS2 from the original substrate to another arbitrary substrate and onto holey substrates, in order to obtain free-standing structures. The method consists of a polymer- and residue-free, surface-tension-assisted wet transfer, in which we take advantage of the hydrophobic properties of the MoS2. The methods yields better quality transferred layers, with fewer cracks and defects, and less contamination than the widely used PMMA-mediated transfer and allows fabrication of few-layer, fee-standing structures with diamet…
Mechanical transfer of high performing thin film devices onto arbitrary substrates represents an exciting opportunity to improve device performance, explore non-traditional manufacturing approaches, and paves the way for soft, conformal, and flexible electronics. Using a two-dimensional (2D) boron nitride (BN) release layer, we demonstrate the transfer of AlGaN/GaN high-electron mobility transistors (HEMTs) to arbitrary substrates through both direct van der Waals (vdW) bonding and with a polymer adhesive interlayer. No device degradation was observed due to the transfer process, and a signifi…
The combination of two-dimensional (2D) materials into heterostructures enabled the formation of atomically thin devices with designed properties. To achieve a high density, bottom-up integration, the growth of these 2D heterostructures via van der Waals epitaxy (vdWE) is an attractive alternative to the currently mostly employed mechanical transfer, which is still problematic in terms of scaling and reproducibility. However, controlling the location of the nuclei formation remains a key challenge in vdWE. Here, we use a focused He ion beam for a deterministic placement of defects in graphene …
Two-dimensional (2D) bismuth oxyselenide (Bi2O2Se) with high electron mobility is advantageous in future high-performance and flexible electronic and optoelectronic devices. However, transfer of thin Bi2O2Se flakes is rather challenging, restricting measurements of its mechanical properties and application exploration in flexible devices. Here, we develop a reliable and effective polydimethylsiloxane (PDMS)-mediated method that allows transferring thin Bi2O2Se flakes from grown substrates onto target substrates like micro-electro-mechanical system substrates. The high fidelity of the transferr…
Rhombohedral-stacked few-layer graphene (FLG) has been receiving an ever-increasing attention owing to its peculiar electronic properties that could lead to enticing phenomena such as superconductivity and magnetic ordering. Up to now, experimental studies on such material have been mainly limited by the difficulty in isolating it in thickness exceeding 3 atomic layers with device-compatible size. In this work, rhombohedral graphene with thickness up to 9 layers and areas up to ~50 micrometers square is grown via chemical vapor deposition (CVD) on suspended Cu foils and transferred onto target…
There is a substantial interest in the heterostructures of semiconducting transition metal dichalcogenides (TMDCs) amongst each other or with arbitrary materials, through which the control of the chemical, structural, electronic, spintronic, and optical properties can lead to a change in device paradigms. A critical need is to understand the interface between TMDCs and insulating substrates, for example high-$κ$ dielectrics, which can strongly impact the electronic properties such as the optical gap. Here we show that the chemical and electronic properties of the single-layer (SL) TMDC, WS$_2$…
Recent progress in the on-surface synthesis of graphene nanoribbons (GNRs) has given access to atomically precise narrow GNRs with tunable electronic band gaps that makes them excellent candidates for room-temperature switching devices such as field-effect transistors (FET). However, in spite of their exceptional properties, significant challenges remain for GNR processing and characterization. This contribution addresses some of the most important challenges, including GNR fabrication scalability, substrate transfer, long-term stability under ambient conditions and ex situ characterization. W…
The epitaxial growth of functional materials using a substrate with a graphene layer is a highly desirable method for improving structural quality and obtaining free-standing epitaxial nano-membranes for scientific study, applications, and economical reuse of substrates. However, the aggressive oxidizing conditions typically employed to grow epitaxial perovskite oxides can damage graphene. Here, we demonstrate a technique based on hybrid molecular beam epitaxy that does not require an independent oxygen source to achieve epitaxial growth of complex oxides without damaging the underlying graphe…
Interface-induced superconductivity and strain-dependent spin density wave in FeSe/SrTiO3 thin films
铁基高温超导体（Fe-HTS's）的超导转变温度（Tc）一直保持在56 K。最近，在SrTiO_3衬底上生长的单层FeSe薄膜中，有新的65 K Tc记录的迹象。在这里，与原位光电子能谱测量，我们证实了自旋密度波（SDW）在FeSe薄膜，Fe-HTS的一个关键成分，在FeSe之前，这是错过了减弱与厚度增加或应变减少。我们表明，超导性发生时，从氧空位基板转移的电子抑制，否则最明显的SDW在单层FeSe。除了提供对FeSe薄膜的全面理解和进一步提高其Tc的方向外，我们还建立了FeSe与晶格常数的相图，其中包含了Fe-HTS的所有基本物理特性。它具有结构最简单、成分最纯净、调谐参数单一等优点，是铁基高温超导理论测试的理想设备。
