高质量大面积石墨烯的化学气相沉积制备方法研究

石墨烯因其奇特的能带结构和优异的物理性能而成为近年来大家研究的热点, 但是目前单层石墨烯的质量与尺寸制约了其实际应用的发展. 本文采用常压化学气相沉积(CVD)方法, 基于铜箔衬底, 利用甲烷作为碳源制备了高质量大面积的单层与多层石墨烯. 研究发现: 高温度、稀薄的甲烷浓度、较短的生长时间以及合适的气体流速是制备高质量、大面积石墨烯的关键. Raman光谱, 扫描电子显微镜、透射电子显微镜等表征结果表明: 制备的石墨烯主要为单层, 仅铜箔晶界处有少量多层石墨烯. 电学测试表明CVD制备的石墨烯在低温时呈现出较明显的类半导体特性; 薄膜电阻随外界磁场的增大而减小.     

Direct growth of graphene on gallium nitride by using chemical vapor deposition without extra catalyst

Graphene on gallium nitride(GaN) will be quite useful when the graphene is used as transparent electrodes to improve the performance of gallium nitride devices. In this work, we report the direct synthesis of graphene on GaN without an extra catalyst by chemical vapor deposition. Raman spectra indicate that the graphene films are uniform and about 5–6 layers in thickness. Meanwhile, the effects of growth temperatures on the growth of graphene films are systematically studied, of which 950℃ is found to be the optimum growth temperature. The sheet resistance of the grown graphene is 41.1Ω/square,which is close to the lowest sheet resistance of transferred graphene reported. The mechanism of graphene growth on GaN is proposed and discussed in detail. XRD spectra and photoluminescence spectra indicate that the quality of GaN epi-layers will not be affected after the growth of graphene.     

化学气相沉积石墨烯薄膜的洁净转移

石墨烯因其优异的性能在很多领域具有广阔的应用前景.目前石墨烯薄膜主要是以铜作为催化基底,通过化学气相沉积法制备.这种方法制备的石墨烯薄膜需要被转移到目标基底上进行后续应用,而转移过程则会对石墨烯造成污染,进而影响石墨烯的性质及器件的性能.如何减少或避免污染,实现石墨烯的洁净转移,是石墨烯薄膜转移技术研究的重要课题,也是本综述的主题.本综述首先简单介绍了石墨烯的转移方法;进而重点讨论由于转移而引入的各种污染物及其对石墨烯性质的影响,以及如何抑制污染物的引入或如何将其有效地去除;最后总结了石墨烯洁净转移所存在的挑战,展望了未来的研究方向和机遇.本综述不仅有助于石墨烯薄膜转移技术的研究,对整个二维材料器件的洁净制备也将有重要参考价值.     

化学气相沉积法制备大尺寸单晶石墨烯的工艺参数研究

石墨烯作为一种二维sp2杂化碳的同素异形体,具有优良的电学、光学、热学及力学等性质.产业化应用石墨烯要求其具有大的尺寸且性质均一.化学气相沉积法(CVD)的出现为制备大尺寸、高质量的石墨烯提供了可能.本文结合近几年CVD法制备石墨烯的研究进展,综述了影响大尺寸、单晶石墨烯制备的工艺参数,包括衬底选择与预处理、碳源与辅助气体流量调控、腔体温度和压力控制、沉积时间以及降温速率设定等.最后展望了制备大尺寸单晶石墨烯的研究方向.     

双层石墨烯的化学气相沉积法制备及其光电器件

石墨烯是一种具有优异性质,在光电及能源领域具有巨大应用前景的二维材料.尽管单层石墨烯具有超高的迁移率,但是它的能带结构具有狄拉克锥(K点),即价带和导带并未有明显分离,所以在半导体器件方面的应用受到一定的限制.由双层石墨烯搭建而成的双门器件,在施加外加电场的情况下,它的带隙可以打开,并在一定范围内可调,这种性质赋予了双层石墨烯在半导体器件应用方面的前景.然而机械或者液相剥离石墨烯,在层数和大小方面可控性较差.如何通过化学气相沉积法可控制备双层石墨烯是目前研究的核心问题之一.本文主要综述了如何通过化学气相沉积法制备双层石墨烯和制备双层石墨烯器件的一系列工作,其中包括最新的研究进展,对生长机理的研究做了详细的介绍和讨论,并对该领域的发展进行了展望.     

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.     

Atmospheric pressure chemical vapor deposition (APCVD) grown bi‐layer graphene transistor characteristics at high temperature

We report the characteristics of atmospheric chemical vapor deposition grown bilayer graphene transistors fabricated on ultra‐scaled (10 nm) high‐κ dielectric aluminum oxide (Al₂O₃) at elevated temperatures. We observed that the drive current increased by >400% as temperature increased from room temperature to 250 °C. Low gate leakage was maintained for prolonged exposure at 100 °C but increased significantly at temperatures >200 °C. These results provide important insights for considering chemical vapor deposition graphene on aluminum oxide for high temperature applications where low power and high frequency operation are required. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

CuNi binary alloy catalyst for growth of nitrogen‐doped graphene by low pressure chemical vapor deposition

The CuNi binary alloy can be significant as a catalyst for nitrogen‐doped (N‐doped) graphene growth considering controllable solubility of both carbon and nitrogen atoms. Here, we report for the first time the possibility of synthesizing substitutional N‐doped bilayer graphene on the binary alloy catalyst. Raman spectroscopy, atomic force microscopy and transmission electron microscopy analysis confirm the growth of bilayer and few‐layer graphene domains. X‐ray photoelectron spectroscopy analysis shows the presence of around 5.8 at% of nitrogen. Our finding shows that large N‐doped bilayer graphene domains can be synthesized on the CuNi binary alloy.

     

Chemical vapor deposition of graphene on silver foil as a tarnish‐resistant coating

Here, we demonstrate the synthesis of graphene on Ag foil by an atmospheric‐pressure (AP) chemical vapor deposition (CVD) process as tarnish‐resistant coating. Synthesis of a continuous graphene film on Ag foil is achieved using the solid camphor as carbon precursor in a gas mixture of Ar and H₂. Tarnishing of the Ag surface through sulfidation is investigated with and without coating of the graphene film. It is observed that the bare Ag surface immediately reacts with sulfur vapor to turn black, whereas graphene coating passivates the Ag surface robustly and thereby restrains the sulfur reaction to preserve from tarnishing. Our findings show that a large‐area graphene film can be effectively grown on Ag surface by a CVD process as a tarnish and corrosion resistance barrier.

     

衬底对化学气相沉积法制备氧化硅纳米线的影响

通过化学气相沉积法在不同衬底上制备了大量的氧化硅纳米线.选用衬底为Si片、带有约100nm厚SiO2氧化层Si片和石英片.利用场发射扫描电子显微镜(SEM)和透射电镜(TEM，配备有能谱仪)对样品的表面形貌、结构和成分进行研究.结果表明：这些纳米线都为非晶态，但在不同衬底上生长的纳米线形貌、尺寸和化学成分不同.讨论了各种衬底对不同特征氧化硅纳米线生长的影响. 关键词： 化学气相沉积 纳米线 纳米颗粒     

Atmospheric pressure plasma treatment on graphene grown by chemical vapor deposition

We demonstrate the surface treatment of graphene using an atmospheric pressure plasma jet (APPJ) system. The graphene was synthesized by a thermal chemical vapor deposition with methane gas. A Mo foil and a SiO₂ wafer covered by Ni films were employed to synthesize monolayer and mixed-layered graphene, respectively. The home-built APPJ system was ignited using nitrogen gas to functionalize the graphene surface, and we studied the effect of different treatment times and interdistance between the plasma jet and the graphene surface. After the APPJ treatment, the hydrophobic character of graphene surface changed to hydrophilic. We found that the change is due to the formation of functionalities such as hydroxyl and carboxyl groups. Furthermore, it is worth noting that the nitrogen plasma treatment induced charge doping on graphene, and the pyridinic nitrogen component in the X-ray photoelectron spectroscopy spectrum was significantly enhanced. We conclude that the atmospheric pressure plasma treatment enables controlling the graphene properties without introducing surface defects.     

介电层表面直接生长石墨烯的研究进展

作为21世纪备受瞩目的材料,石墨烯兼具优异的电、热、光与力学性质,具有十分广阔的研究价值与应用价值.目前主要通过在金属基底上生长获得石墨烯,并将其转移至目标介电层基底上以构筑电子器件.转移过程不可避免地引入了褶皱、裂纹、破损以及聚合物/金属残留,严重损害了石墨烯的性能.因而直接在介电基底上制备高质量的石墨烯薄膜具有重要意义.本文总结了近年来在介电衬底上直接生长石墨烯的研究进展:阐述了金属辅助法、等离子体增强法以及热力学或动力学调控法等多种生长手段;介绍了多种介电/绝缘基底包括SiO_2/Si,Al_2O_3,SrTiO_3,h-BN,SiC,Si_3N_4以及玻璃表面生长石墨烯的特点与性能,分析了其可能的生长机理.根据拉曼谱图、薄层电阻、透光率、载流子迁移率等评估指标,将多种方法得到的石墨烯质量进行了总结与比较,并提出了直接在介电衬底上生成石墨烯的研究难点与趋势.     

化学气相沉积法制备定向碳纳米管阵列

以二茂铁和二甲苯分别作为催化剂和碳源，采用一种无模板的化学气相沉积法，使用单温炉设备，成功地制备了高度定向的碳纳米管阵列.分别用扫描电子显微镜、透射电子显微镜和电子能量散射谱、拉曼光谱对碳纳米管阵列进行形貌观察和表征, 并研究了不同工艺参数对碳纳米管阵列形貌的影响.结果表明：在生长温度为800℃，催化剂浓度为0.02g/mL，抛光硅片上容易获得高质量的定向碳纳米管阵列，在此优化条件下生长的定向碳纳米管的平均生长速率可达25μm/min.     

等离子体增强化学气相沉积法实现硅纳米线掺硼

用等离子体增强化学气相沉积(PECVD)方法成功实现硅纳米线的掺B.选用Si片作衬底，硅烷 （SiH4）作硅源，硼烷（B2H6）作掺杂气体， Au作催化剂，生长温度440℃.基于气-液-固(VLS)机制，探讨了掺B硅纳米线可能的生长机制.PECVD法化学成分配比更灵活，更容易实现纳米线掺杂，进一步有望生长硅纳米线pn结，为研制纳米量级器件提供技术基础. 关键词： 硅纳米线 化学气相沉积 纳米器件     

一种简单的化学气相沉积法制备大尺寸单层二硫化钼

最近单层二硫化钼以其直接带隙的性质及在电子器件、催化、光电等领域中的潜在应用而备受关注.化学气相沉积法能够制备出高质量、大尺寸且性能优良的单层二硫化钼,但其制备工艺比较复杂.本文采用简化的化学气相沉积法在蓝宝石衬底上制备出了大尺寸的单晶二硫化钼.清洗衬底时,只需要简单的清洁,不需要用丙酮、食人鱼溶液(H_2SO_4/H_2O_2=3:1)等处理,这样既减少了操作步骤,又避免了潜在的危险.升温时直接从室温加热到生长的温度,不必分段升温,并且采用常压化学气相沉积法,不需要抽真空等过程,使得实验可以快捷方便地进行.光学显微镜、拉曼光谱和光致发光谱的结果表明,生长的二硫化钼为规则的三角形单层,边长为50μm左右,远大于机械剥离的样品.     

等离子体增强热丝CVD生长碳纳米尖端的研究

用CH₄，NH₃和H₂为反应气体，利用等离子体增强热丝化学气相沉积系统在不同偏压电流的条件下制备了碳纳米尖端，并用扫描电子显微镜和显微Raman光谱仪对碳纳米尖端进行了研究.结果表明碳纳米尖端是石墨结构，随着偏压电流的增大，碳纳米尖端的顶角减小，生长速率增大.结合有关等离子体和溅射的理论，分析讨论了碳纳米尖端的形成和碳纳米尖端的生长随偏压电流的变化. 关键词： 碳纳米尖端 等离子体 化学气相沉积     

Synthesis of multi-walled carbon nanotubes using CoMnMgO catalysts through catalytic chemical vapor deposition

The Co Mg O and Co Mn Mg O catalysts are prepared by a co-precipitation method and used as the catalysts for the synthesis of carbon nanotubes（CNTs） through the catalytic chemical vapor deposition（CCVD）. The effects of Mn addition on the carbon yield and structure are investigated. The catalysts are characterized by temperature programmed reduction（TPR） and X-ray diffraction（XRD） techniques, and the synthesized carbon materials are characterized by transmission electron microscopy（TEM） and thermo gravimetric analysis（TG）. TEM measurement indicates that the catalyst Co Mg O enclosed completely in the produced graphite layer results in the deactivation of the catalyst. TG results suggest that the Co Mn Mg O catalyst has a higher selectivity for CNTs than Co Mg O. Meanwhile, different diameters of CNTs are synthesized by Co Mn Mg O catalysts with various amounts of Co content, and the results show that the addition of Mn avoids forming the enclosed catalyst, prevents the formation of amorphous carbon, subsequently promotes the growth of CNTs, and the catalyst with decreased Co content is favorable for the synthesis of CNTs with a narrow diameter distribution.The Co Mn Mg O catalyst with 40% Co content has superior catalytic activity for the growth of carbon nanotubes.     

Growth and characterization of AlN epilayers using pulsed metal organic chemical vapor deposition

We report the growth of Al N epilayers on c-plane sapphire substrates by pulsed metal organic chemical vapor deposition(MOCVD). The sources of trimethylaluminium(TMAl) and ammonia were pulse introduced into the reactor to avoid the occurrence of the parasitic reaction. Through adjusting the duty cycle ratio of TMAl to ammonia from 0.8 to 3.0, the growth rate of Al N epilayers could be controlled in the range of 0.24 m/h to 0.93 m/h. The high-resolution x-ray diffraction(HRXRD) measurement showed that the full width at half maximum(FWHM) of the(0002) and(10-12) reflections for a sample would be 194 arcsec and 421 arcsec, respectively. The step-flow growth mode was observed in the sample with the atomic level flat surface steps, in which a root-mean-square(RMS) roughness was lower to 0.2 nm as tested by atomic force microscope(AFM). The growth process of Al N epilayers was discussed in terms of crystalline quality, surface morphology,and residual stress.     

The influence of chemical solvents on the properties of CVD graphene

The ultra‐clean and defect‐free transfer of chemical vapor deposition (CVD) graphene is essential for its application in electronic devices. Here, we study the influence of commonly used etching solvents during the transfer process, i.e. ammonium persulfate, ferric chloride, and ferric nitrate, on the properties of CVD graphene by Raman spectroscopy. Obvious blue shift and broadening of Raman G and 2D peaks were observed for graphene transferred by ferric chloride and ferric nitrate, as compared to that transferred by ammonium persulfate. These changes are attributed to p‐doping as well as reduction of phonon lifetime of graphene in the presence of residue iron compounds during the transfer process. The latter would also introduce a great reduction of thermal conductivity of graphene, e.g. with 76% reduction for graphene transferred by ferric nitrate as compared to that transferred by ammonium persulfate. This work would provide valuable information for the transfer of high‐quality CVD graphene. Copyright © 2014 John Wiley & Sons, Ltd.