Rapid Characterization of Ultrathin Layers of Chalcogenides on SiO2/Si Substrates

There has been emerging interest in exploring single‐sheet 2D layered structures other than graphene to explore potentially interesting properties and phenomena. The preparation, isolation and rapid unambiguous characterization of large size ultrathin layers of MoS₂, GaS, and GaSe deposited onto SiO₂/Si substrates is reported. Optical color contrast is identified using reflection optical microscopy for layers with various thicknesses. The optical contrast of these thin layers is correlated with atomic force microscopy (AFM) and Raman spectroscopy to determine the exact thickness and to calculate number of the atomic layers present in the thin flakes and sheets. Collectively, optical microscopy, AFM, and Raman spectroscopy combined with Raman imaging data are analyzed to determine the thickness (and thus, the number of unit layers) of the MoS₂, GaS, and GaSe ultrathin flakes in a fast, non‐destructive, and unambiguous manner. These findings may enable experimental access to and unambiguous determination of layered chalcogenides for scientific exploration and potential technological applications.     

Improving Graphene Diffusion Barriers via Stacking Multiple Layers and Grain Size Engineering

It is shown that the performance of graphene diffusion barriers can be enhanced by stacking multiple layers of graphene and increasing grain size. The focus is on large‐area barriers of graphene grown by chemical vapor deposition (CVD) in the context of passivating an underlying Cu substrate from oxidation in air at 200 °C and use imaging Raman spectroscopy as a tool to temporally and spatially map the barrier performance and to guide barrier design. At 200 °C in air, Cu oxidation proceeds in multiple regimes: first slowly via transport through atomic‐scale grain boundary defects inherent to CVD‐graphene and then more rapidly as the graphene itself degrades and new defects are formed. In the initial regime, the graphene passivates better than previously reported. Whereas oxidation through single sheets primarily occurs through grain boundaries, oxidation through multiple sheets is spatially confined to their intersection. Performance further increases with grain‐size. The degradation of the graphene itself at 200 °C ultimately limits high temperature but suggests superior low temperature barrier performance. This study is expected to improve the understanding of mass transport through CVD‐graphene materials and lead to improved large area graphene materials for barrier applications.     

低功率CO2激光辐照对多层石墨烯结构的影响

在真空环境下使用不同功率密度的CO2激光对化学气相沉积法(CVD)生长的石墨烯进行辐照,通过研究辐照前后的拉曼光谱变化考察了激光功率密度及辐照时间对多层石墨烯结构的影响。结果表明,当功率密度较低(13W/cm2)时,石墨烯拉曼光谱中的D峰降低,2D峰增强,石墨烯内的掺杂、缺陷减少。随着功率密度的增加,石墨烯的缺陷增多,部分缺陷连接形成晶界,使石墨烯分解为纳米晶。在58 W/cm2的功率密度下,当作用时间为120s时,在石墨烯表面产生非晶碳。研究表明,适当参数的CO2激光辐照能改善石墨烯的内在性能。     

Bottom-Up Synthesized Nanoporous Graphene Transistors

Nanoporous graphene (NPG) can exhibit a uniform electronic band gap and rationally-engineered emergent electronic properties, promising for electronic devices such as field-effect transistors (FETs), when synthesized with atomic precision. Bottom-up, on-surface synthetic approaches developed for graphene nanoribbons (GNRs) now provide the necessary atomic precision in NPG formation to access these desirable properties. However, the potential of bottom-up synthesized NPG for electronic devices has remained largely unexplored to date. Here, FETs based on bottom-up synthesized chevron-type NPG (C-NPG), consisting of ordered arrays of nanopores defined by laterally connected chevron GNRs, are demonstrated. C-NPG FETs show excellent switching performance with on–off ratios exceeding 10⁴, which are tightly linked to the structural quality of C-NPG. The devices operate as p-type transistors in the air, while n-type transport is observed when measured under vacuum, which is associated with reversible adsorption of gases or moisture. Theoretical analysis of charge transport in C-NPG is also performed through electronic structure and transport calculations, which reveal strong conductance anisotropy effects in C-NPG. The present study provides important insights into the design of high-performance graphene-based electronic devices where ballistic conductance and conduction anisotropy are achieved, which could be used in logic applications, and ultra-sensitive sensors for chemical or biological detection.     

Symmetric and Asymmetric Decoration of Graphene: Bimetal‐Graphene Sandwiches

Low‐dimensional carbon materials, i.e., graphene and its functionalization with a number of semiconductor or conductor materials, such as noble metal nanostructures, have primary importance for their potential exploitation as electro‐active materials, i.e., as new generation catalysts. Here, low‐cost, solution chemistry‐based, two‐step functionalization of an individual, free‐standing, chemical vapor‐deposited graphene monolayer is reported, with noble metal (Au, Pt, Pd) nanoparticles to build up two‐side decorated graphene‐based metal nanoclusters. Either the same metal (symmetric decoration) or different metals (asymmetric decoration) are used for the preparation of bimetal graphene sandwiches, which are adsorbed at the liquid/liquid (organic/water) interface. The successful fabrication of such dual‐decorated graphene‐based metal nanocomposites is confirmed using various microscopic techniques (scanning electron and atomic force microscopies) and several spectroscopic methods (x‐ray photoelectron, energy dispersive x‐ray, mapping mode Raman spectroscopy, and electron energy loss spectroscopy). Taken together, it is inferred from these techniques that the location of deposited metal nanoparticles is on opposite sides of the graphene.     

Facile Synthesis of Graphene Quantum Dots from 3D Graphene and their Application for Fe3+ Sensing

Owing to their small size, biocompatibility, unique and tunable photoluminescence, and physicochemical properties, graphene quantum dots (GQDs) are an emerging class of zero‐dimensional materials promising a wide spectrum of novel applications in bio‐imaging, optical, and electrochemical sensors, energy devices, and so forth. Their widespread use, however, is largely limited by the current lack of high yield synthesis methods of high‐quality GQDs. In this contribution, a facile method to electrochemically exfoliate GQDs from three‐dimensional graphene grown by chemical vapor deposition (CVD) is reported. Furthermore, the use of such GQDs for sensitive and specific detection of ferric ions is demonstrated.     

缺陷对石墨烯电子结构的影响

基于第一性原理计算方法,通过密度泛函理论（DFT）和广义梯度近似（GGA）对本征及含有缺陷的石墨烯超晶胞进行了电子结构的计算,研究了多种缺陷对石墨烯电子结构的影响。研究发现,多种缺陷均使石墨烯能带在费米能级附近出现缺陷态对应的能带,并导致其能隙有不同程度的增大,而且与之对应的态密度也随之发生相应的变化。其中,Stone...     

CO2‐Laser‐Induced Growth of Epitaxial Graphene on 6H‐SiC(0001)

The thermal decomposition of SiC surface provides, perhaps, the most promising method for the epitaxial growth of graphene on a material useful in the electronics platform. Currently, efforts are focused on a reliable method for the growth of large‐area, low‐strain epitaxial graphene that is still lacking. Here, a novel method for the fast, single‐step epitaxial growth of large‐area homogeneous graphene film on the surface of SiC(0001) using an infrared CO₂ laser (10.6 μm) as the heating source is reported. Apart from enabling extreme heating and cooling rates, which can control the stacking order of epitaxial graphene, this method is cost‐effective in that it does not necessitate SiC pre‐treatment and/or high vacuum, it operates at low temperature and proceeds in the second time scale, thus providing a green solution to EG fabrication and a means to engineering graphene patterns on SiC by focused laser beams. Uniform, low–strain graphene film is demonstrated by scanning electron microscopy, X‐ray photoelectron spectroscopy, secondary ion‐mass spectroscopy, and Raman spectroscopy. Scalability to industrial level of the method described here appears to be realistic, in view of the high rate of CO₂‐laser‐induced graphene growth and the lack of strict sample–environment conditions.     

Unraveling the Sinuous Grain Boundaries in Graphene

Grain boundaries (GBs) in graphene are stable strings of pentagon‐heptagon dislocations. The GBs have been believed to favor an alignment of dislocations, but increasing number of experiments reveal diversely sinuous GB structures whose origins have long been elusive. Based on dislocation theory and first‐principles calculations, an extensive analysis of the graphene GBs is conducted and it is revealed that the sinuous GB structures, albeit being longer than the straight forms, can be energetically optimal once the global GB line cannot bisect the tilt angle. The unusually favorable sinuous GBs can actually decompose into a series of well‐defined bisector segments that effectively relieve the in‐plane stress of edge dislocations, and the established atomic structures closely resemble recent experimental images of typical GBs. In contrast to previously used models, the sinuous GBs show improved mechanical properties and are distinguished by a sizable electronic transport gap, which may open potential applications of polycrystalline graphene in functional devices.     

FeCl3‐Based Few‐Layer Graphene Intercalation Compounds: Single Linear Dispersion Electronic Band Structure and Strong Charge Transfer Doping

Graphene has attracted much attention since its first discovery in 2004. Various approaches have been proposed to control its physical and electronic properties. Here, it is reported that graphene‐based intercalation is an efficient method to modify the electronic properties of few‐layer graphene (FLG). FeCl₃ intercalated FLGs are successfully prepared by the two‐zone vapor transport method. This is the first report on full intercalation for graphene samples. The features of the Raman G peak of such FLG intercalation compounds (FLGIC) are in good agreement with their full intercalation structures. The FLGICs present single Lorentzian 2D peaks, similar to that of single‐layer graphene, indicating the loss of electronic coupling between adjacent graphene layers. First principle calculations further reveal that the band structure of FLGIC is similar to single‐layer graphene but with a strong doping effect due to the charge transfer from graphene to FeCl₃. The successful fabrication of FLGIC opens a new way to modify properties of FLG for fundamental studies and future applications.     

Confocal Microscopy for In Situ Multi-Modal Characterization and Patterning of Laser-Reduced Graphene Oxide (Adv. Funct. Mater. 30/2023)

Graphene oxide (GO) films can be readily prepared at wafer scale, then reduced to form graphene-based conductive circuits relevant to a range of practical device applications. Among a variety of reduction methods, laser processing has emerged as an important technique for localized reduction and patterning of GO films. In this study, the novel use of confocal microscopy is demonstrated for high-resolution characterization, in situ laser reduction, and versatile patterning of GO films. Multi-modal imaging and real-time tracking are performed with 405 and 488 nm lasers, enabling large-area direct observation of the reduction progress. Using image analysis to cluster flake types, the different stages of reduction can be attributed to thermal transfer and accumulation. Delicate control of the reduction process over multiple length scales is illustrated using millimeter-scale stitched patterns, micropatterning of single flakes, and direct writing conductive 2D wires with sub-micrometer resolution (530 nm). The general applicability of the technique is shown, allowing fabrication of both conductive reduced graphene oxide (rGO) films (sheet resistance: 2.5 kOhm sq⁻¹) and 3D microscale architectures. This simple and mask-free method provides a valuable tool for well-controlled and scalable fabrication of reduced GO structures using compact low-power lasers (< 5 mW), with simultaneous in situ monitoring and quality control.     

Direct Graphene Transfer and Its Application to Transfer Printing Using Mechanically Controlled,Large Area Graphene/Copper Freestanding Layer

Direct graphene transfer is an attractive candidate to prevent graphene damage, which is a critical problem of the conventional wet transfer method. Direct graphene transfer can fabricate the transferred graphene film with fewer defects by using a polymeric carrier. Here a unique direct transfer method is proposed using a 300 nm thick copper carrier as a suspended film and a transfer printing process by using the polydimethylsiloxane (PDMS) stamp under controlled peeling rate and modulus. Single and multilayer graphene are transferred to flat and curved PDMS target substrate directly. With the transfer printing process, the transfer yield of a trilayer graphene with 1000 µm s^?1 peeling rate is 68.6% of that with 1 µm s^?1 peeling rate. It is revealed that the graphene transfer yield is highly related to the storage modulus of the PDMS stamp: graphene transfer yield decreases when the storage modulus of the PDMS stamp is lower than a specific threshold value. The relationship between the graphene transfer yield and the interfacial shear strain of the PDMS stamp is studied by finite‐element method simulation and digital image correlation.     

激光拉曼光谱法无损鉴别三七及其伪品

应用激光拉曼光谱技术准确无损鉴别三七及其伪品菊三七、藤三七和姜黄。采集了三七及其伪品的拉曼光谱图,并结合二阶导数拉曼图谱对其进行定性鉴别。四种药材的图谱中均出现了1330、1040、943、310 cm-1糖类碳水化合物的拉曼特征峰。三七的谱图中出现了1080 cm-1和1120 cm-1皂苷类化合物的拉曼振动峰;菊三七的谱图中出现了820、899、1144、2935 cm-1b-谷甾醇、吡咯里西啶类生物碱及长链脂肪烃的拉曼特征峰;藤三七的谱图中出现了1462 cm-1和1695 cm-1的腺苷类和尿嘧啶类化合物的拉曼振动峰;姜黄的谱图中出现了962、1187、1433、1596、1630 cm-1等姜黄素类化合物的拉曼振动峰。以上专属特征峰的差异可将三七及其伪品进行很好的区分,并据谱图信息可建立四味中药的拉曼指纹图谱。二阶导数拉曼光谱图可以对三七及其伪品的鉴别结果进行进一步补充验证说明。此方法可准确直接、快速鉴别三七及其伪品。     

退火时间对SiC热解法制备石墨烯薄膜的影响

利用水平热壁式CVD外延炉开展了SiC热分解法制备石墨烯薄膜的实验,主要研究了不同的真空热处理时间对石墨烯薄膜生长的影响。SiC衬底的氢气在线刻蚀处理和热分解在同一炉次进行,高温时反应室释放出之前吸附的氢气不能有效地被分子泵抽除,SiC衬底的有效碳化时间有限,实验发现热处理时间超过30min之后,石墨烯层数并无明显变化。进一步加长热处理时间,石墨烯样品中出现局部氢插入层。     

激光偏振拉曼的CVD多晶石墨烯表征

石墨烯具有优异的物理化学性质,在MEMS器件、光电检测材料、柔性显示屏、新能源电池、复合材料等方面成为研究热点。目前大面积石墨烯制备主要依赖于化学气相沉积技术(chemical vapor deposition, CVD),但其生长的晶体质量直接影响到电化学特性和实际应用,因此需要一种快速而准确的表征方法。实验利用背向散射的偏振激光散射装置测量CVD生长的石墨烯拉曼光谱。通过分析实验获得的300 nm SiO2/Si基底上的单层、五层和十层左右的石墨烯角分辨偏振拉曼光谱,发现单层生长的石墨烯偏振特性与机械剥离单晶石墨烯一致;随着层数的增加,G峰偏振响应差异更加明显,表现出明显的椭圆特性;在不同石墨烯层数上的D峰也呈现出一定的偏振响应差异性。偏振拉曼测试结果表明目前CVD生长的缺陷和多晶特性与石墨烯层数呈现正相关特征。     

SiO2/Si上石墨烯薄膜的化学气相沉积法制备及其性能表征

以铜为催化剂,采用聚甲基丙烯酸甲酯(PMMA)和甲烷为碳源的化学气相沉积两步法,在SiO₂/Si衬底上制备了石墨烯薄膜。利用拉曼光谱分析了薄膜的层数和质量,利用光学显微镜(OM)和扫描电子显微镜(SEM)分析了薄膜的尺寸与表面形貌。实验探究了生长时间、氢气流量和气体总压强等工艺参数对石墨烯薄膜层数和质量的影响,最终在优化条件下制得10μm级质量较高的多层石墨烯薄膜。