铜基石墨烯的CVD法制备工艺参数研究

采用乙炔作为碳源,分析了碳源浓度、生长时间等参数对铜基石墨烯成核密度、生长速率及单层覆盖率的影响,通过热氧化法系统展示了石墨烯形核、长大、生长结束的全过程.研究发现;碳源浓度较小时成核密度较低,所得石墨烯晶粒更大,但单个多层点的面积较大,且多以双层为主;在石墨烯生长过程中,氢气既可辅助碳氢化合物分解,同时也会刻蚀部分成核点,从而促进石墨烯质量的提高;基于单层率与晶粒尺寸之间的平衡,采用乙炔与氢氩混合气(体积比为1∶9)流速比为5∶100作为生长石墨烯的气体工艺参数,获得了透过率约为97.1%,缺陷较少且以单层为主的大面积石墨烯.     

石墨烯基TiO_2复合材料的表征及其可见光催化活性研究

以氧化石墨烯与石墨烯为碳源,在熔盐介质中与钛粉反应原位生成石墨烯基TiC中间产物,并通过后续控制氧化制得石墨烯基TiO_2复合光催化剂,结合FTIR、XRD、Raman、SEM等手段,对两种石墨烯材料的结构及形貌差异进行表征,并分析了其对所制复合材料结构、形貌及可见光催化活性的影响。结果表明,所制复合材料仍保持碳源的层片状结构,TiC和TiO_2颗粒均匀包覆在碳源表面;以石墨烯为碳源更有利于表面原位生成TiC晶粒的生长,其晶体结构更为完善;两种结构的石墨烯基TiO_2复合材料均对目标污染物亚甲基蓝有较强的吸附能力和可见光降解能力。     

单双层石墨烯的制备及电导特性调控

石墨烯二维材料有着优异的物理、化学特性,在多个科学领域展现出广阔的应用前景.采用化学气相沉积方法在Cu-Ni合金表面制备了二维石墨烯薄膜并揭示其生长机制;研究生长时间、温度等对石墨烯覆盖度和晶格质量的影响.通过优化生长条件,成功制备了大面积单层及具有强烈层间耦合作用的AB堆叠双层石墨烯薄膜.进一步运用表面沉积技术在单层石墨烯上构建零维Au团簇和二维Au薄膜,研究其对石墨烯电导特性的影响;并结合第一性原理计算,揭示Au的形态及覆盖度影响石墨烯电导特性的规律.据此制作了石墨烯场效应晶体管器件,通过精确控制Au的覆盖度,实现石墨烯电导类型和载流子浓度的有效调控,拓展了其在微电子领域的应用.     

三维自组装石墨烯的细胞相容性研究

针对石墨烯的二维平面结构不利于细胞在材料上延伸生长和黏附的问题,通过水热法合成自组装石墨烯,搭建利于细胞生长和黏附的三维结构.利用扫描电子显微镜、透射电子显微镜、傅里叶红外光谱、拉曼光谱、X线光电子能谱和接触角测试仪对样品的表面形貌、微观结构、化学键、原子组态和亲水性能进行测试,并通过形体外细胞实验研究了L929小鼠肺部成纤维细胞在材料上的黏附和增殖生长等行为.实验结果表明:自组装石墨烯具有孔径为1~3μm的孔洞,材料整体呈网状结构,为多层石墨烯片层的堆叠;样品中部分C元素分别与H和O元素结合生成多种官能团;三维自组装石墨烯的亲水性和表面细胞增殖生长情况均优于二维石墨烯,更适于作为组织支架促进细胞生长.     

石墨烯薄膜的生长及结构表征研究

在常压条件下,以铜箔为基底、CH4为碳源,通过化学气相沉积法(CVD)生长出了石墨烯薄膜。利用拉曼光谱、扫描电子显微镜、四探针电导率仪表征分析了产物。结果表明:生长温度为1 000℃,H2流量为60mL/min,CH4流量为2.5mL/min,Ar流量为80mL/min时,在基底表面生长出了连续分布的石墨烯薄膜,且大部分区域为单层,同时结晶程度高缺陷小;转移后的石墨烯薄膜面积大、透光性良好,兼具有良好的导电性,其薄层电阻为1 822Ω。     

热解-模板法制备石墨烯的分子动力学模拟探究

提出一种以废弃塑料热解产物为碳源,以石墨微片为模板,通过石墨微片的生长来制备石墨烯的设想。为了探索该设想的可行性和反应机理,以聚乙烯为例,采用反应分子动力学模拟方法从原子尺度对热解-模板法制备石墨烯的过程进行了研究。结果表明,在一定的温度条件下,聚乙烯分解产生具有高反应活性的乙烯基自由基和甲基自由基,这些自由基在降温过程中会接枝到石墨微片的边缘从而生长石墨烯。这说明以废弃塑料为碳源,加热分解后在石墨微片上生长石墨烯的设想具有可行性。分析了加热时间、冷却时间等条件对石墨烯生长过程的影响,可为实验制备石墨烯提供理论指导和参考。     

碳/氧化锌纳米线阵列/泡沫石墨烯电化学检测叶酸

通过化学气相沉积法制备三维(3D)泡沫石墨烯(GF),然后利用水热合成法在泡沫石墨烯表面生长氧化锌纳米线阵列(ZnO NWAs),再利用化学气相沉积法在其表面沉积碳(C),得到碳/氧化锌纳米线阵列/泡沫石墨烯(C/ZnO NWAs/GF)复合材料.用该复合材料做电极,采用电化学方法检测叶酸(FA).结果表明,三维泡沫石墨烯具有和模板泡沫镍一样的三维孔状结构,ZnO NWAs均匀且垂直地生长在泡沫石墨烯表面,碳沉积在ZnO NWAs表面.在线性范围为0~60 μmol·L-1内,C/ZnO NWAs/GF电极检测FA时,灵敏度为0.13 μA·μmol-1·L,且在尿酸(UA)干扰下检测 FA具有良好的选择性.C/ZnO NWAs/GF电极有良好的稳定性和重复性.     

电沉积铜箔CVD工艺生长缺陷可控少层石墨烯

通过气相化学沉积(CVD)工艺生长的石墨烯薄膜具有缺陷程度低且可实现层数可控等优良特点。基于硫酸铜酸性镀铜工艺,在不同的电流密度条件下采用电沉积技术制备超薄铜箔,并用作CVD工艺的基体,合成高品质少层石墨烯。采用X线衍射仪(XRD)、扫描电子显微镜(SEM)及多测试位置拉曼光谱技术对不同电沉积铜箔结构、表面形貌及其上生长的石墨烯进行分析。结果表明:电沉积铜箔的结构具有很强的择优晶面取向性,且其取向晶面与沉积的电流密度有关,在高温、H_2气氛退火处理后拥有比商业冷轧铜箔更有利于石墨烯生长的平整表面及连续滑移台阶;通过调控铜箔基体电沉积过程的电流密度及其厚度、反应前驱体气体H_2与CH_4流速比、CVD沉积时间以及铜箔退火时间等工艺参数,实现在电沉积铜箔表面生长出缺陷程度可控的少层石墨烯薄膜。     

制备超级电容器氧化石墨烯的MPCVD方法

以氢气、甲酸甲酯为原料,泡沫镍为基底,通过微波等离子体增强化学气相沉积(MPCVD)法,在450℃反应合成氧化石墨烯,将其作为超级电容器活性物质,在三电极体系下研究其电化学性能.使用场发射扫描电子显微镜(FE-SEM)、X射线衍射仪(XRD)、拉曼光谱仪、X射线光电子能谱仪(XPS)和电化学测试等手段,对样品的形貌、结构以及电化学性能进行表征.结果显示:MPCVD法可以合成氧化石墨烯,合成过程不会产生有毒气体,并且合成时间短,生长的氧化石墨烯的形貌结构与传统化学氧化法合成的氧化石墨烯相似.电化学测试表明:氧化石墨烯的比电容在1 A/g具有197 F/g,将电流密度提高到100 A/g,比电容仍有134 F/g,在5 A/g下循环充放电2 000圈,容量保持率为94%.     

表面修饰双层石墨烯高压拉曼研究

拉曼光谱是表征石墨烯结构和性质的有效方法.高压环境会显著改变双层石墨烯的层间相互作用,进而改变其结构及物理性质.但是高压环境比较复杂,双层石墨烯的拉曼行为受传压介质、衬底、电子掺杂等多重因素的影响,这些因素对高压下双层石墨烯结构及拉曼光谱的影响机制与过程仍有待明确.为此研究了双层石墨烯在金刚石压砧中受到压力时,甲醇、甲醇/乙醇混合、氢气等传压介质对双层石墨烯拉曼光谱的影响,石墨烯悬空于金网衬底和生长于铜镍合金衬底上的不同,以及预先氟化对于拉曼光谱的影响.研究发现以悬空金网为衬底,在预先氟化条件下,氢气等单一传压介质做修饰时有助于双层石墨烯在高压下发生层间sp³杂化,有利于促进少层石墨烯到超薄金刚石薄膜的相变.此研究为高压下构建新型碳结构材料提供了更多有利的指引.     

Atomic-scale imaging of carbon nanofibre growth

The synthesis of carbon nanotubes with predefined structure and functionality plays a central role in the field of nanotechnology, whereas the inhibition of carbon growth is needed to prevent a breakdown of industrial catalysts for hydrogen and synthesis gas production. The growth of carbon nanotubes and nanofibres has therefore been widely studied. Recent advances in in situ techniques now open up the possibility of studying gas-solid interactions at the atomic level. Here we present time-resolved, high-resolution in situ transmission electron microscope observations of the formation of carbon nanofibres from methane decomposition over supported nickel nanocrystals. Carbon nanofibres are observed to develop through a reaction-induced reshaping of the nickel nanocrystals. Specifically, the nucleation and growth of graphene layers are found to be assisted by a dynamic formation and restructuring of mono-atomic step edges at the nickel surface. Density-functional theory calculations indicate that the observations are consistent with a growth mechanism involving surface diffusion of carbon and nickel atoms. The finding that metallic step edges act as spatiotemporal dynamic growth sites may be important for understanding other types of catalytic reactions and nanomaterial syntheses.     

晶圆级二维单晶材料生长的研究进展

低维材料因其原子级的物理尺寸而拥有独特的物理化学性质. 以石墨烯为代表的二维材料具有优越的光学、电学、力学及热学性能,在电子、光电、能源、催化等领域具有巨大的应用潜力. 大尺寸、高质量的单晶材料是大规模高端器件的应用基础. 为此,研究者们致力于实现晶圆级二维单晶材料的制造研究. 利用化学气相沉积法(CVD)制备二维材料具有薄膜质量高、可控性强、均匀性好等优点,因此,CVD成为制备高质量二维单晶材料的首选. 文章从二维导电石墨烯、绝缘氮化硼和半导体过渡金属硫族化合物入手,总结了近年来利用CVD技术外延制造二维单晶薄膜的研究进展,讨论了大面积二维单晶材料的制备策略与生长机理,指出了目前存在的问题,对未来高质量二维单晶薄膜的制备方法进行了展望. 该综述为进一步推动二维单晶材料的规模化应用提供借鉴.     

碳离子注入辅助在6H-SiC表面制备石墨烯

为了寻找一种更便捷、更经济的在半导体SiC基底上直接生长石墨烯的方法,将5 keV C离子注入商用6H-SiC(0001)单晶,通过拉曼光谱、扫描电子显微镜(SEM)和原子力显微镜(AFM)表征研究石墨烯质量和生长过程.实验中还研究了不同降温速率以及石墨舟的封闭环境对石墨烯生长的影响,并基于Si原子的蒸发提出一个可能的...     

Direct evidence for atomic defects in graphene layers

Atomic-scale defects in graphene layers alter the physical and chemical properties of carbon nanostructures. Theoretical predictions have recently shown that energetic particles such as electrons and ions can induce polymorphic atomic defects in graphene layers as a result of knock-on atom displacements. However, the number of experimental reports on these defects is limited. The graphite network in single-walled carbon nanotubes has been visualized by transmission electron microscopy (TEM) and their chiral indices have been determined. But the methods used require a long image acquisition time and intensive numerical treatments after observations to find an 'average' image, which prevents the accurate detection and investigation of defect structures. Here we report observations in situ of defect formation in single graphene layers by high-resolution TEM. The observed structures are expected to be of use when engineering the properties of carbon nanostructures for specific device applications.     

Heteroatom-doped graphene for electrochemical energy storage

The increasing energy consumption and envi- ronmental concerns due to burning fossil fuel are key drivers for the development of effective energy storage systems based on innovative materials. Among these materials, graphene has emerged as one of the most promising due to its chemical, electrical, and mechanical properties. Heteroatom doping has been proven as an effective way to tailor the properties of graphene and render its potential use for energy storage devices. In this view, we review the recent developments in the synthesis and applications of heteroatom-doped graphene in supercapacitors and lithium ion batteries.     

降解苯酚细菌的分离及其生理特性研究

从工业废水中分离到两株可以降解苯酚的细菌，初步确定为假单胞菌属(Pseudomonas)和芽孢杆菌属(Bacillus),分别命名为C1和C2，菌株C1和C2都能在以苯酚为唯一碳源的无机盐培养基中生长，并且确立了它们的最适培养条件。在苯酚浓度适宜的条件下，不同氮源对于苯酚的降解效率有一定的影响．     

Chemical vapor deposition growth behavior of graphene

The optimized growth parameters of graphene with different morphologies,such as dendrites,rectangle,and hexagon,have been obtained by low-pressure chemical vapor deposition on polycrystalline copper substrates.The evolution of fractal graphene,which grew on the polycrystalline copper substrate,has also been observed.When the equilibrium growth state of graphene is disrupted,its intrinsic hexagonal symmetry structure will change into a non-hexagonal symmetry structure.Then,we present a systematic and comprehensive study of the evolution of graphene with different morphologies grown on solid copper as a function of the volume ratio of methane to hydrogen in a controllable manner.Moreover,the phenomena of stitching snow-like graphene together and stacking graphene with different angles was also observed.     

High-frequency, scaled graphene transistors on diamond-like carbon

Owing to its high carrier mobility and saturation velocity, graphene has attracted enormous attention in recent years. In particular, high-performance graphene transistors for radio-frequency (r.f.) applications are of great interest. Synthesis of large-scale graphene sheets of high quality and at low cost has been demonstrated using chemical vapour deposition (CVD) methods. However, very few studies have been performed on the scaling behaviour of transistors made from CVD graphene for r.f. applications, which hold great potential for commercialization. Here we report the systematic study of top-gated CVD-graphene r.f. transistors with gate lengths scaled down to 40 nm, the shortest gate length demonstrated on graphene r.f. devices. The CVD graphene was grown on copper film and transferred to a wafer of diamond-like carbon. Cut-off frequencies as high as 155 GHz have been obtained for the 40-nm transistors, and the cut-off frequency was found to scale as 1/(gate length). Furthermore, we studied graphene r.f. transistors at cryogenic temperatures. Unlike conventional semiconductor devices where low-temperature performance is hampered by carrier freeze-out effects, the r.f. performance of our graphene devices exhibits little temperature dependence down to 4.3 K, providing a much larger operation window than is available for conventional devices.