单层单晶石墨烯与柔性基底界面性能的实验研究

单晶石墨烯具有更优异的力学及电学性能,有望成为新一代柔性电子器件的核心材料.因此,有必要从实验的角度精细分析化学气相沉积法制得的大尺度单晶石墨烯与柔性基底复合结构的界面力学行为.本文通过显微拉曼光谱实验方法测量了不同长度的单层单晶石墨烯/PET(聚对苯二甲酸乙二醇酯)基底的界面力学性能参数及其在长度方向上界面边缘的尺度效应.实验给出了石墨烯在PET基底加载过程中与基底间黏附、滑移、脱黏三个界面状态的演化过程与应力分布规律.实验发现,单晶石墨烯与柔性基底间由范德瓦耳斯力控制的界面应变传递过程存在明显的边缘效应,并且与石墨烯的长度有关.界面的切应力具有尺度效应,其值随石墨烯长度的增加而减小,而石墨烯界面传递最大应变以及界面脱黏极限则不受试件尺度的影响.     

Comparative study of single and multi domain CVD graphene using large‐area Raman mapping and electrical transport characterization

We systematically investigate the impact of granularity in CVD graphene films by performing Raman mapping and electrical characterization of single (SD) and multi domain (MD) graphene. In order to elucidate the quality of the graphene film, we study its regional variations using large‐area Raman mapping and compare the G and 2D peak positions of as‐transferred chemical vapor deposited (CVD) graphene on SiO₂ substrate. We find a similar upshift in wavenumber in both SD and MD graphene in comparison to freshly exfoliated graphene. In our case, doping could play the dominant role behind the observation of such upshifts rather than the influence due to strain. Interestingly, the impact of the polymer‐assisted wet transfer process is the same in both the CVD graphene types. The electrical characterization shows that SD graphene exhibits a substantially higher (a factor 5) field‐effect mobility when compared to MD graphene. We attribute the low sheet resistance and mobility enhancement to a decrease in charge carrier scattering thanks to a reduction of the number of grain boundaries and defects in SD graphene.     

退火法制备石墨烯-银纳米粒子及其增强拉曼实验

针对目前SERS基底上金属颗粒制备过程中存在的分布不均匀、易氧化和稳定性差等缺点,通过热蒸镀和高温退火获得分布均匀的SERS基底;同时结合石墨烯优良的光学性能、化学惰性、荧光猝灭以及本身的SERS增强等优点,制备了稳定的石墨烯-银纳米颗粒（GE/AgNPs）复合结构SERS基底。通过GE/AgNPs复合结构的拉曼光谱稳定性试验证明了石墨烯在GE/AgNPs结构中起到隔绝银纳米颗粒与空气直接接触及催化氧化银脱氧的作用,有利于SERS基底的时间稳定性。(1) 石墨烯、Ag纳米颗粒及其复合结构的制备。首先采用热蒸镀和高温退火的方法使Ag纳米颗粒均匀地沉积在SiO₂/Si基底上,再采用化学气相沉积法在Cu箔上制备少层石墨烯,并用湿法转移法将石墨烯转移到目标基底上,并实验研究了以不同的退火顺序对GE/AgNPs基底造成的影响。(2) 石墨烯、Ag纳米颗粒及其复合基底的表征。分别采用光学显微镜、扫描电子显微镜和拉曼光谱进行表征,得到转移后的纯石墨烯较完整地覆盖在SiO₂/Si基底上面,表面比较平整,但在少数地方仍然存在褶皱和杂质;SEM表征结果表明对于不同制备流程的GE/AgNPs复合结构上的Ag纳米颗粒基本呈球形。基本符合Ostwald熟化理论,通过对退火温度和时间的控制能获得平均粒径在40~60 nm的银颗粒,且分布较均匀。此外,在不同退火顺序中,石墨烯的加入对银纳米颗粒的扩散形成扩散势垒,从而出现较大的不规则的颗粒。(3) 基底稳定性试验和仿真分析。通过基底本身的Raman mapping测试,分析了石墨烯拉曼特征峰峰值和半高宽的变化,得知基底对石墨烯本身的拉曼增强效果主要来源于银纳米颗粒间的电磁场增强。同时采用浓度为10-6 mol·L-1的罗丹明6G (R6G)水溶液作为探针分子,对转移了石墨烯的GE/AgNPs复合基底和未转移石墨烯的Ag纳米颗粒基底进行了SERS稳定性实验。结果表明GE/AgNPs复合基底在1~33 d内衰减较缓慢,30 d后仍能探测到拉曼信号约为原来信号的35.1%~40.6%;而纯Ag基底上随着Ag纳米颗粒在空气中迅速氧化,基底的SERS性能显著下降,在30 d后只有原来信号的5.9%~11.3%。此外,通过实验得到覆盖了石墨烯之后的增强因子约为6.05×105。最后采用时域有限差分算法（FDTD）计算了复合结构的电磁场分布和理论增强因子,其理论增强因子可以达到5.7×105。实验和仿真结果的差异,主要是源于石墨烯的化学增强作用。     

石墨烯/柔性基底复合结构双向界面切应力传递问题的理论研究

界面力学性能是影响石墨烯/柔性基底复合结构整体力学性能的关键因素,因此对该结构界面切应力传递机理的研究十分必要.考虑了石墨烯和基底泊松效应的影响,本文提出了二维非线性剪滞模型.对于基底泊松比相比石墨烯较大的情况,利用该模型理论研究了受单轴拉伸石墨烯/柔性基底结构的双向界面切应力传递问题.在弹性粘结阶段,导出了石墨烯双向正应变和双向界面切应力的半解析表达式,分析了不同位置处石墨烯正应变和界面切应力的分布规律.导出了石墨烯/柔性基底结构发生界面滑移的临界应变,结果表明该临界应变低于利用经典一维非线性剪滞模型得到的滑移临界应变,并且明显受到石墨烯宽度尺寸以及基底泊松比大小的影响.基于二维非线性剪滞模型建立有限元模型(FEM),研究了界面滑移阶段石墨烯双向正应变和双向界面切应力的分布规律.与一维非线性剪滞模型的结果对比表明,当石墨烯宽度较大时,二维模型和一维模型对石墨烯正应变、界面切应力以及滑移临界应变的计算结果均存在较大差别,但石墨烯宽度很小时,二维模型可近似被一维模型代替.最后,通过与拉曼实验结果的对比,验证了二维非线性剪滞模型的可靠性,并得到了石墨烯/聚对苯二甲酸乙二醇酯(PET)基底结构的界面刚度(100 TPa/m)和界面剪切强度(0.295 MPa).     

Enhanced Raman scattering of graphene on Ag nanoislands

The effect of Ag nanoislands on the Raman of graphene was investigated in this work. Compared with that on the bare silicon wafer, Raman enhancement was observed in the graphene film that covered on Ag/Si surface with nanoscale Ag islands, which would be induced by the localized plasmon resonance in Ag nanostructures. The interaction between the graphene sheet and Ag/Si substrate was further studied. The peak shift and line shape of Raman spectroscopy indicated a nonuniform strain distribution in the Ag/Si supported graphene film.     

Effect of strain on geometric and electronic structures of graphene on Ru(0001) surface

The atomic and electronic structures of a graphene monolayer on a Ru(0001) surface under compressive strain are investigated by using first-principles calculations. Three models of graphene monolayers with different carbon periodicities due to the lattice mismatch are proposed in the presence and the absence of the Ru(0001) substrate separately. Considering the strain induced by the lattice mismatch, we optimize the atomic structures and investigate the electronic properties of the graphene. Our calculation results show that the graphene layers turn into periodic corrugations and there exist strong chemical bonds in the interface between the graphene N×N superlattice and the substrate. The strain does not induce significant changes in electronic structure. Furthermore, the results calculated in the local density approximation (LDA) are compared with those obtained in the generalized gradient approximation (GGA), showing that the LDA results are more reasonable than the GGA results when only two substrate layers are used in calculation.     

The improvement of InAs/GaAs quantum dot properties capped by Graphene

InAs self‐assembled quantum dots (QDs) were grown by molecular beam epitaxy on (001) GaAs substrate. Uncapped and capped QDs with GaAs and graphene layers were studied using atomic force microscopy and Raman spectroscopy. Graphene multi‐layer was grown by chemical vapor deposition and transferred on InAs/GaAs QDs. It is well known that the presence of a cap layer modifies the size, shape, and density of the QDs. According to the atomic force microscopy study, in contrast to the GaAs capped sample, which induce a dramatic decrease of the density and height of dots, graphene cap layer sample presents a slight influence on the surface morphology and the density of the islands compared with the uncapped one. The difference shown in the Raman spectra of the samples is due to change of strain and alloy disorder effects on the QDs. Residuals strain and the relaxation coefficients have been investigated. All results confirm the best crystalline quality of the graphene cap layer dots sample relative to the GaAs capped one. So graphene can be used to replace GaAs in capping InAs/GaAs dots. To our knowledge, such study has not been carried out until now. Copyright © 2013 John Wiley & Sons, Ltd.     

pH‐dependent surface‐enhanced Raman scattering of aromatic molecules on graphene oxide

Graphene has become an ideal substrate for surface‐enhanced Raman scattering (SERS) to study the chemical enhancement mechanism. In comparison with mechanically exfoliated graphene, graphene oxide (GO) has been found to be a better substrate due to its highly negatively charged oxygen functional groups. In this work, the pH‐dependent SERS effect of aromatic molecules on GO are investigated. The results demonstrate that the Raman enhancement of dyes deposited on GO performs differently over a wide range of pH values (2 to 10). Adsorption experiments show that the pH‐dependent SERS effect is closely related to the adsorption of aromatic molecules on GO, which is dominated by the electrostatic interaction. Thus, the influence of pH in GO‐mediated SERS should be carefully considered, especially in its biomedical application. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis,mechanical, and barrier properties of LDPE/graphene nanocomposites using vinyl triethoxysilane as a coupling agent

Precise interface control and dispersal of graphene nanosheets in polymer hosts are challenging to develop high performance graphene-based nanocomposites due to their strong interlayer cohesive energy and surface inertia. Here, we firstly report an efficient and novel method to functionalize graphene nanosheets with vinyl triethoxysilane (VTES) and successfully blend them with low density polyethylene (LDPE) to prepare nanocomposites. Fourier transforms infrared spectra (FTIR), Raman spectra, and thermogravimetric analysis (TGA) proved that the graphene sheets were covalently bonded with VTES. The resulting nanocomposites obtained the increases of up to 27.0 and 92.8% in the tensile strength and Young’s modulus, respectively, compared to neat LDPE. The VTES–graphene not only remarkably improved the tensile strength of the composites, but also enhanced its toughness by 17.7%. Oil permeability measurements showed that the absorption ratio of toluene by the LDPE/graphene composites decreased from 56 to 39%, and its barrier properties have obviously been improved. This study opens a new route to optimize interface structures and improve the comprehensive performances of graphene–polymer nanocomposites.     

Raman analysis of epitaxial graphene grown on 4Hben SiC (0001) substrate under low pressure condition

In this paper, we report a feasible route of growing epitaxial graphene on 4H-SiC (0001) substrate in a low pressure of 4 mbar (1 bar=10⁵ Pa) with an argon flux of 2 standard liters per minute at 1200, 1300, 1400, and 1500 ℃ in a commercial chemical vapour deposition SiC reactor. Using Raman spectroscopy and scanning electron microscopy, we confirm that epitaxial graphene evidently forms on SiC surface above 1300 ℃ with a size of several microns. By fitting the 2D band of Raman data with two-Lorentzian function, and comparing with the published reports, we conclude that epitaxial graphene grown at 1300 ℃ is four-layer graphene.     

纳米结构表面形貌成型机理及其对石墨烯拉曼光谱的影响

通过真空热蒸镀和高温退火法制备的金属纳米复结构SERS基底因其具有良好的灵敏度,稳定性和均匀性而广泛应用于各种检测领域。石墨烯具有优良的光学特性,化学惰性以及荧光猝灭效应,自被发现以后一直是光学微纳器件中的一大热门材料。石墨烯还可以有效分离探针分子与基底,优化拉曼光谱质量,因此广泛应用于SERS研究领域。同时石墨烯可以有效隔绝金属纳米结构与空气的直接接触防止金属纳米结构被氧化而失效,也可以催化氧化银的脱氧反应提升SERS基底的稳定性。在石墨烯/金属纳米复合结构SERS基底在制备过程中,受到金属膜的种类、厚度参数、气体种类、退火时间、温度和气压等因素的影响,制备的金属纳米结构形貌存在很大差异。石墨烯的拉曼光谱会因为应力和掺杂导致其拉曼特征峰出现不同程度的增强,移动以及展宽。（1）采用真空热蒸镀法和高温退火法制备石墨烯/银纳米复合结构SERS基底,建立了金属纳米颗粒成型机理的模型,从孔洞形成、孔洞生长、金属纳米岛形成三个阶段分析了金属纳米粒子的成型过程,实验沉积5,10,15以及20 nm的银薄膜,退火后银纳米结构的覆盖率分别为~35.1%,~24.4%,~30%以及~96.0%,在沉积银薄膜样品上使用湿法转移石墨烯,退火处理后发现石墨烯阻止了银纳米岛的形成过程;（2）理论分析了银薄膜厚度、石墨烯覆盖对复合结构的几何形貌、拉曼增强特性的影响,石墨烯由于其具有较高的杨氏模量和表面张力,可以有效抑制退火过程中银薄膜向纳米粒子转变的过程,从而实现对复合结构表面形貌的调控;（3）实验研究了银纳米粒结构形貌对石墨烯拉曼光谱的影响,并理论分析了蒸镀不同银薄膜厚度的样品对石墨烯的拉曼光谱增强,移动以及展宽影响的具体原因。     

The influence of AlN/GaN superlattice intermediate layer on the properties of GaN grown on Si（111） substrates

AlN/GaN superlattice buffer is inserted between GaN epitaxial layer and Si substrate before epitaxial growth of GaN layer. High-quality and crack-free GaN epitaxial layers can be obtained by inserting AlN/GaN superlattice buffer layer. The influence of AlN/GaN superlattice buffer layer on the properties of GaN films are investigated in this paper. One of the important roles of the superlattice is to release tensile strain between Si substrate and epilayer. Raman spectra show a substantial decrease of in-plane tensile strain in GaN layers by using AlN/GaN superlattice buffer layer. Moreover, TEM cross-sectional images show that the densities of both screw and edge dislocations are significantly reduced. The GaN films grown on Si with the superlattice buffer also have better surface morphology and optical properties.     

Mechanical Properties of Ni-Coated Single Graphene Sheet and Their Embedded Aluminum Matrix Composites

The effects of Ni coating on the mechanical behaviors of single graphene sheet and their embedded Al matrix composites under axial tensionare investigated using molecular dynamics (MD) simulation method. Theresults show that the Young's moduli and tensile strength of grapheneobviously decrease after Ni coating. The results also show that the mechanical properties of Al matrix can be obviously increased by embedding asingle graphene sheet. From the simulation, we also find that the Young'smodulus and tensile strength of the Ni-coated graphene/Al composite isobviously larger than those of the uncoated graphene/Al composite. Theincreased magnitude of the Young's modulus and tensile strength ofgraphene/Al composite are 52.27 and 32.32 at 0.01 K, respectively,due to Ni coating. By exploring the effects of temperature on the mechanicalproperties of single graphene sheet and their embedded Al matrix composites, it is found that the higher temperature leads to the lower critical strain and tensile strength.     

纳米银/石墨烯复合SERS基底的制备及对铀(Ⅵ)的拉曼光谱研究

铀是核工业中一种重要的核燃料,研究其在水溶液中的浓度和种态信息具有重要意义。铀(Ⅵ)在水溶液中最稳定的存在形式UO2+₂,其标准Raman散射峰为871 cm-1。然而利用表面增强拉曼散射(SERS)技术检测铀(Ⅵ)时,铀(Ⅵ)与SERS基底的直接相互作用,使得铀(Ⅵ)的Raman峰存在很大程度的偏移,甚至偏移到710 cm-1。使用不同的SERS基底,其偏移程度也不同,无法反映溶液中铀(Ⅵ)的真实Raman信息,为解析溶液中铀(Ⅵ)的种态带来了很大困难。通过抗坏血酸活化银纳米粒子(AgNPs),在硅衬底上自组装AgNPs阵列,得到SERS基底。利用石墨烯介质隔层的化学惰性和完整性,通过悬空自助转移法在该自组装AgNPs SERS基底表面转移单层石墨烯,制备了纳米银/石墨烯复合SERS基底。并表征了该复合SERS基底的形貌,AgNPs粒子紧密连接在一起,形成纳米链结构,纳米链均匀地分布于衬底表面,单层石墨烯紧密覆盖于AgNPs表面,且石墨烯的亚纳米级厚度没有改变AgNPs的形貌。将这两类SERS基底用于检测硝酸铀酰,对于未覆盖石墨烯的AgNPs基底,UO2+₂的对称伸缩振动峰为719 cm-1,基底与UO2+₂的相互作用导致谱峰宽化,并向低波数移动。而在覆盖了石墨烯的G-AgNPs复合SERS基底表面,UO2+₂的对称伸缩振动峰为771 cm-1,回移了52 cm-1,这种大幅度的回移表明石墨烯隔层在一定程度上隔绝了UO2+₂与AgNPs的相互作用。     

Raman study of InAs quantum dots on GaAs/InP grown by low pressure metal-organic chemical vapor deposition

Raman spectra of InAs quantum dots (QDs) on InP substrate were investigated. Both longitudinal-optic (LO) and transverse-optic (TO) frequency of InAs QDs showed a large blue-shift comparing to its bulk due to the compressive strain in InAs QDs. Raman scattering of InAs QDs with a thin GaAs interlayer was studied. We obtained that the peak position of LO and TO mode of InAs QDs became larger blue-shifted when we inserted the GaAs layer. At the same time, we found a red-shift of the frequency of GaAs LO mode because of tensile strain. Theoretical calculation was performed and its prediction coincided with our experiment results well. They both showed that strain played an important role in formation of InAs QDs.     

Strain status of epitaxial Ge film on a Si (001) substrate

An epitaxial Ge film was grown on a Si (001) substrate via a two-step process through the molecular beam epitaxy technique. The strain status of non-annealed and annealed epitaxial Ge films was determined by X-ray diffraction, Raman spectroscopy, and a combination of high-resolution transmission electron microscopy and geometric phase analysis. Results showed that the strain in non-annealed and annealed epitaxial Ge films is nonhomogeneous from the Ge/Si interface to the Ge film surface. The strain parallel to the interface in the non-annealed epitaxial Ge film is compressive; this strain reaches a minimum near the surface and a maximum at the interface. By contrast, the strain parallel to the interface in the annealed epitaxial Ge film is tensile; this strain reaches a minimum at the interface and a maximum near the surface.     

石墨烯对ZnO微米棒光学特性的影响

采用化学气相沉积(CVD)方法制备了具有良好结晶质量和(002)择优取向的ZnO微米棒。在此基础上,选取单根ZnO微米棒,将其部分搁置于单层石墨烯表面。光致发光(PL)谱结果表明,石墨烯不仅增强了ZnO微米棒的紫外发光强度,同时也对光场在ZnO微米棒中的分布有很大的限域作用。分析认为这是由于石墨烯的表面等离子效应引起了ZnO微米棒与石墨烯之间的光-物质相互作用导致的。在拉曼(Raman)光谱中,石墨烯对ZnO微米棒的E2(L)声子振动模和E2(H)声子振动模的强度具有明显的减弱效应,这进一步证明二者之间存在光子的传输和电荷的转移,从而导致其晶格振动受到抑制。     

Energy of substitution of atoms in the epitaxial graphene-buffer layer-SiC substrate system

The binding energy of atom X (X = B, Al, Ga, In, N, P, As, Sb) substituting for carbon atoms in single-layer graphene, a buffer layer, and on the ( 000[`1] )\left( {000\bar 1} \right) surface of SiC substrate or for a silicon atom on the (0001) surface of SiC substrate has been studied by the Harrison bond-orbital method. In terms of a simple model based on atomic radii, the contribution of the strain energy due to relaxation of an impurity bond has been considered. The expressions have been obtained for the difference between the energies of substitution for a carbon atom in the buffer layer and in single-layer graphene and in the case of substitution for silicon and carbon atoms on the SiC-substrate surface.     

Field emissions of graphene films deposited on different substrates by CVD system

<正>Graphene films are deposited on copper(Cu) and aluminum(Al) substrates,respectively,by using a microwave plasma chemical vapour deposition technique.Furthermore,these graphene films are characterized by a field emission type scanning electron microscope(FE-SEM),Raman spectra,and field emission(FE) I-V measurements.It is found that the surface morphologies of the films deposited on Cu and Al substrates are different:the field emission property of graphene film deposited on the Cu substrate is better than that on the Al substrate,and the lowest turn-on field of 2.4 V/μm is obtained for graphene film deposited on the Cu substrate.The macroscopic areas of the graphene samples are all above 400 mm~2.     

Signatures of epitaxial graphene grown on Si-terminated 6H-SiC (0 0 0 1)

Epitaxial graphene layers thermally grown on Si-terminated 6H-SiC (0 0 0 1) have been probed using Auger electron spectroscopy, Raman microspectroscopy, and scanning tunneling microscopy (STM). The average multilayer graphene thickness is determined by attenuation of the Si (L₂₃VV) and C (KVV) Auger electron signals. Systematic changes in the Raman spectra are observed as the film thickness increases from one to three layers. The most striking observation is a large increase in the intensity of the Raman 2D-band (overtone of the D-band and also known as the G′-band) for samples with a mean thickness of more than ∼1.5 graphene layers. Correlating this information with STM images, we show that the first graphene layer imaged by STM produces very little 2D intensity, but the second imaged layer shows a single-Lorentzian 2D peak near 2750 cm⁻¹, similar to spectra acquired from single-layer micromechanically cleaved graphene (CG). The 4-10 cm⁻¹ higher frequency shift of the G peak relative to CG can be associated with charge exchange with the underlying SiC substrate and the formation of finite size domains of graphene. The much greater (41-50 cm⁻¹) blue shift observed for the 2D-band may be correlated with these domains and compressive strain.