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。     

TiO_2/石墨烯/Ag复合结构SERS实验

基于氧化物半导体的光催化特性,能够降解有机物分子,使表面增强拉曼散射基底得以重复使用。提出了银纳米颗粒有效修饰覆盖有石墨烯的二氧化钛纳米棒阵列(TiO_2/石墨烯/Ag)复合结构作为表面增强拉曼散射基底,并对其进行了实验研究。利用水热法制备了二氧化钛纳米棒阵列;采用湿法转移石墨烯和光照还原方法制备了TiO_2/石墨烯/Ag复合结构。用罗丹明6G(R6G)分子作为探测分子,结果表明:随着紫外光照沉积时间增加,探针分子的拉曼信号先增强后减弱;计算得到最大增强因子值约为2.6×106。此外,还对TiO_2/石墨烯/Ag复合结构的紫外自清洁特性进行了初步实验,结果表明,紫外光照射20min后,其拉曼强度下降到42.3%,具有一定的紫外清洁效果。     

Preparation and photoelectrochemical performance of Ag/graphene/TiO2 composite film

By dipping-lifting in sol-gel solution and reducing process, the graphene/TiO₂ composite film on the glass plate was first prepared. Then, the Ag/graphene/TiO₂ composite film was fabricated by interface reaction with AgNO₃ and N₂H₄·H₂O on the surface of graphene/TiO₂ composite film. The characterization results show that the uniform porous TiO₂ film is made up of the anatase crystal, and the Ag/graphene/TiO₂ composite film is constructed by doping or depositing graphene sheets and Ag nanoparticles on the surface of TiO₂ film. The photoelectrochemical measurement results indicate that the Ag/graphene/TiO₂ composite film has an excellent photoelectrochemical conversion property.     

Formation of graphene on amorphous SiC film by surface-confined heating with electron beam irradiation

It is demonstrated experimentally that graphene can form on the surface of an amorphous SiC film by irradiating electron beam (e-beam) at low acceleration voltage. As the electron irradiation fluency increases, the crystallinity and uniformity of graphene improve, which is confirmed by the changes of the measured Raman spectra and secondary electron microscopy images. Due to the shallow penetration depth of e-beam with low acceleration voltage, only the region near the surface of SiC film will be heated by the thermalization of irradiated electrons with multiple scattering processes. The thermalized electrons are expected to weaken the bond strength between Si and C atoms so that the thermal agitation required for triggering the sublimation of Si atoms decreases. With these assistances of irradiated electrons, it is considered that graphene can grow on the surface of SiC film at temperature reduced substantially in comparison with the conventional vacuum annealing process.     

Structural evolution of single-layer films during deposition of silicon on silver: a first-principles study

In the quest for the construction of silicene, the silicon analogue of graphene, recent experimental studies have identified a number of distinct ultrathin Si over-layer structures on a Ag(111) surface. Here we use first-principles calculations to probe associated atomic-scale mechanisms that can give rise to this rich behavior of Si wetting layers. We find that the interaction between the Si film and the Ag substrate, neither too strong nor too weak, combined with the possibility of buckling, allows for the incorporation of a number of excess Si adatoms in continuous overlayers with a honeycomb network topology. Depending on the Si coverage, we thus obtain a hierarchy of Si mono-atomic films, in agreement with experiments.     

Raman analysis of bilayer graphene film prepared on commercial Cu(0.5 at% Ni) foil

This study reports the Raman analysis of bilayer graphene films prepared on commercial dilute Cu(0.5 at% Ni) foils using atmospheric pressure chemical vapor deposition. A bilayer graphene film obtained on Cu foil is known to have small areas of bilayer (islands) with a significant fraction of non‐Bernal stacking, while that obtained on Cu/Ni is known to grow over a large area with Bernal stacking. In the Raman optical microscope images, a wafer‐scale monolayer and large‐area bilayer graphene films were distinguished and confirmed with Raman spectra intensities ratios of 2D to G peaks. The large‐area part of bilayer graphene film obtained was assisted by Ni surface segregation because Ni has higher methane decomposition rate and carbon solubility compared with Cu. The Raman data suggest a Bernal stacking order in the prepared bilayer graphene film. A four‐point probe sheet resistance of graphene films confirmed a bilayer graphene film sheet resistance distinguished from that of monolayer graphene. A relatively higher Ni surface concentration in Cu(0.5 at% Ni) foil was confirmed with time‐of‐flight secondary ion mass spectrometry. The inhomogeneous distribution of Ni in a foil and the diverse crystallographic surface of a foil (confirmed with proton‐induced X‐ray emission and electron backscatter diffraction, respectively) could be a reason for incomplete wafer‐scale bilayer graphene film. The Ni surface segregation in dilute Cu(0.5 at% Ni) foil has a potential to impact on atmospheric pressure chemical vapor deposition growth of large‐area bilayer graphene film. Copyright © 2015 John Wiley & Sons, Ltd.     

New surface structure analysis of Ag-Si phase by quantitative auger electron spectroscopy method

Ag or Au was deposited on a clean Si substrate at room temperature. These systems, Ag/Si and Au/Si, were annealed at various temperatures or various heating times. Due to the annealing, Ag or Au diffused into Si and/or Si diffused into the metal. The changes of the surface composition are analyzed by a quantitative Auger Electron Spectroscopy (AES) method which is newly developed as a non-destructive method. In the case of Ag/Si, Ag migrated into the Si substrate and/or Si diffused into Ag. Then, Ag-Si solid solution was produced. After the annealing, the Ag/Si system is changed into Ag/(Ag-Si)/Si of the three-phase structure. In the case of Au/Si (Au film thickness < 15 Å), the Au film thickness became thinner by annealing. The Au/Si system always keeps the Au/Si phase after annealing, while there was no Au-Si solution area. The difference between the Ag/(Ag-Si)/Si and the Au/Si structure is attributed to the reason that Au diffuses more quickly than Ag into the Si substrate. AES results after annealing cannot be explained by the model of the formation of the three-dimensional island structure which is commonly referenced.     

Green synthesis of silver-graphene nanocomposite-based transparent conducting film

In the present work, silver nanoparticles (Ag NPs)/graphene nanocomposite has been synthesized successfully by simple solvothermal method via green route. Citric acid is used as green reducing agent for the reduction of graphene oxide (GO) and Ag ions. Silver nitrate is used as a precursor material for Ag NPs. As synthesized Ag NPs/graphene nanocomposite has been characterized by X-ray diffraction, Raman spectroscopy, Fourier transform infra-red spectroscopy, UV–vis spectroscopy, thermal gravimetric analysis, field emission scanning electron microscopy, and X-ray photoelectron spectroscopy. Experimental results confirm the reduction of GO and the successful formation of Ag NPs decorated graphene nanosheets. In addition, spray coating technique is employed for the fabrication of transparent conducting films. Enhancement in the optoelectrical signatures has been achieved using thermal graphitization of fabricated films. Thermal graphitization at 800 °C for 1 h marks the best performance of fabricated film with sheet resistance of ~3.4 kΩ/□ and transmittance (550 nm) of ~66.40%, respectively.     

Synthesis of graphene oxide sheets decorated by silver nanoparticles in organic phase and their catalytic activity

The graphene oxide(GO) sheets decorated by Ag nanoparticles were prepared using a liquid–liquid two-phase method at the room temperature. The synthesized samples existed in the organic phase and were characterized by X-ray diffraction, transmission electron microscopy, UV–vis spectroscopy and Raman spectra. The results demonstrate that these silver-nanoparticles with diameter of about 10 nm assembled on graphene oxide sheets are flexible and can form stable suspensions in organic phase. Raman signals of graphene oxide sheets are increased by the attached silver nanoparticles, displaying higher surface-enhanced Raman scattering activity. Furthermore, Ag/GO are found to serve as effective catalysts to activate the reduction of 4-nitrophenol (4NP) in the presence of NaBH₄.     

Dependence of the solar cell performance on nanocarbon/Si heterojunctions

Solar cells that combine single-crystalline silicon(Si) with graphene(G) have been widely researched in order to develop next-generation photovoltaic devices. However, the power conversion efficiency(PCE) of G/Si solar cell without chemical doping is commonly low due to the relatively high resistance of graphene. In this work, through combining graphene with carbon nanotube(CNT) networks, we fabricated three kinds of hybrid nanocarbon film/Si heterojunction solar cells in order to increase the PCE of the graphene based Si solar cell. We investigated the characteristics of different nanocarbon film/Si solar cells and found that their performance depends on the heterojunctions. Specifically, a doping-free G-CNT/Si solar cell demonstrated a high PCE of 7.9%, which is nearly equal to the combined value of two individuals(G/Si and CNT/Si). This high efficiency is attributed to the synergistic effect of graphene and CNTs, and can be further increased to 9.1% after applying a PMMA antireflection coating. This study provides a potential way to further improve the Si based heterojunction solar cells.     

Raman光谱研究厚度对La0.9Sr0.1MnO3/Si薄膜结构的影响

通过溶胶-凝胶旋涂方法结合后退火工艺在Si（100）上制备了不同厚度的La_0.9Sr_0.1MnO₃（LSMO）薄膜,利用X射线衍射（XRD）和共焦显微拉曼散射（Raman）研究了LSMO/Si（100）薄膜的微结构．研究结果表明90 nm厚的LSMO薄膜具有正交相结构,当厚度大于150 nm时,薄膜具有菱方相结构. 150 nm厚的薄膜的Raman图谱中,490 cm^-1和602 cm^-1正交结构 关键词： 薄膜 1-xSr_xMnO₃')" href="#">La_1-xSr_xMnO₃ 共焦显微拉曼 微结构     

Reduction of silver nanoparticles onto graphene oxide nanosheets with <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-dimethylformamide and SERS activities of GO/Ag composites

Silver nanoparticles (Ag NPs) have been homogeneously deposited onto graphene oxide (GO) nanosheets by an optimal method, in which N,N-dimethylformamide (DMF) as a co-dispersant of GO and reductant of sliver ions is added to an aqueous suspension of GO and AgNO₃. GO nanosheets are uniformly covered by Ag NPs with a narrow size distribution and inter-particle gap. Raman signals of GO are greatly enhanced after deposition owing to the charge transfer interaction of GO with Ag NPs. The GO/Ag composite can be further utilized as an effective surface-enhanced Raman scattering (SERS) active substrate. Several new Raman bands and frequency shifts are clearly observed in using 4-aminothiophenol (4-ATP) as a Raman probe on GO/Ag compared to the normal Raman spectrum of solid 4-ATP. The Raman enhancement arises from a major electromagnetic effect and a minor chemical effect.     

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.

     

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。     

金属衬底上高质量大面积石墨烯的插层及其机制

石墨烯作为一种新型二维材料,因其优异的性质,在科学和应用领域具有非常重要的意义.而其超高的载流子迁移率、室温量子霍尔效应等,使其在信息器件领域备受关注.如何获得高质量并且与当代硅基工艺兼容的石墨烯功能器件,是未来将石墨烯应用于电子学领域的关键.近年来,研究人员发展了一种在外延石墨烯和金属衬底之间实现硅插层的技术,将金属表面外延石墨烯高质量、大面积的特点与当代硅基工艺结合起来,实现了无需转移且无损地将高质量石墨烯置于半导体之上.通过系统的实验研究并结合理论计算,揭示了插层过程包含四个主要阶段:诱导产生缺陷、异质原子插层、石墨烯自我修复和异质原子扩散成膜,并证实了这一插层机制的普适性.拉曼和角分辨光电子能谱实验结果表明,插层后的石墨烯恢复了本征特性,接近自由状态.此外,还实现了多种单质元素的插层.不同种类的原子形成不同的插层结构,从而构成了多种石墨烯/插层异质结.这为调控石墨烯的性质提供了实验基础,也展现了该插层技术的普适性.     

Graphene/Ag2ZnSnSe4诱导p-n结薄膜太阳电池数值模拟

银锌锡硒(Ag2ZnSnSe4)是一种禁带宽度为1.4 eV的n型半导体材料.本文提出一种由n型Ag2ZnSnSe4与石墨烯(Graphene)组成的Graphene/Ag2ZnSnSe4诱导p-n结薄膜太阳电池,并借助wxAMPS软件对电池的物理机理和性能影响因素进行模拟研究.模拟结果表明,高功函数的石墨烯与n型Ag2ZnSnSe4半导体接触时,Ag2ZnSnSe4吸收层的前端能带向上弯曲,在n型Ag2ZnSnSe4吸收层表面诱导形成p型Ag2ZnSnSe4反型层,p型Ag2ZnSnSe4和n型Ag2ZnSnSe4组成p-n同质结.模拟发现石墨烯和背接触的功函数会影响载流子的分离、输运和收集,严重影响器件性能,石墨烯功函数达到5.5 eV,背接触功函数不高于4.4 eV,都有利于提高器件性能.Ag2ZnSnSe4吸收层的掺杂浓度主要影响器件的短路电流,而Ag2ZnSnSe4吸收层的体内缺陷对器件整体性能产生影响.在石墨烯和背接触功函数分别为5.5和3.8 eV,Ag2ZnSnSe4吸收层的掺杂浓度和缺陷密度分别为1016和1014 cm–3时,Graphene/Ag2ZnSnSe4诱导p-n结薄膜太阳电池能够取得高达23.42%的效率.这些模拟结果为设计新型高效低成本太阳电池提供了思路和物理阐释.     

单晶硅表面有机硅烷/Ag2O纳米微粒复合自组装膜的制备和表征

利用分子自组装成膜技术 ,在单晶硅表面制备了有机硅烷 /Ag2 O纳米微粒复合膜 .应用接触角测定仪、原子力显微镜和X射线光电子能谱仪分析表征了薄膜的组成和结构 .结果表明 ,通过硅烷偶联剂 3 氨丙基 三乙氧基硅烷在单晶硅基底表面的成功组装 ,获得了较为均匀的硅烷化表面 ,而Ag2 O纳米微粒可在硅烷化表面成功地进行组装 ,并呈亚单层排布     

基于气相沉积等离激元纳米粒子/三维石墨烯-镍泡沫复合结构的高灵敏度表面增强拉曼检测

本文提出一种基于气相沉积银纳米粒子和三维石墨烯-镍泡沫的复合等离激元结构.该结构是利用气相纳米团簇束流技术将高密度的银纳米粒子直接沉积于三维石墨烯-镍泡沫的表面制备而成.与传统银纳米结构相比,复合三维等离激元纳米结构具有"热点"数量多,局域场更强的特点,可作为基于表面增强拉曼技术的高灵敏度化学传感器.拉曼测试实验结果表明,该三维纳米结构在表面增强拉曼检测中可获得灵敏度高,重复性好的探针拉曼信号.通过进一步的理论模拟,发现该三维等离激元结构中增强的拉曼信号主要归因于纳米粒子与纳米粒子之间以及纳米粒子与石墨烯-镍泡沫衬底之间的多重近场耦合效应.     

Localized insulator-conductor transformation of graphene oxide thin films via focused laser beam irradiation

By scanning a focused laser beam over graphene oxide (GO) film deposited on SiO₂/Si substrates, conductive strips as small as 1 μm can be patterned directly either as a channel in the insulating matrix, or as a stand-alone micro belt. The conductivity was increased by at least two orders of magnitude with the mobility estimated in the range of 1–10 cm²/V s. Raman mapping and X-ray photoelectron spectroscopy studies demonstrated the reduction of GO in the laser-irradiated area. The conductance of the patterned channel was independent of the change in oxide-electrode contact resistance of the graphene, and increased linearly with increasing channel width. Increasing irradiation power by repeated scanning initially increased the conductivity of the irradiated area and saturated at a conductivity of ∼36 S/cm. Partial oxidative burning combined with photothermal reduction was identified as the underlying mechanism for the enhancement of the conductivity after laser irradiation on the GO film. Oxidative burning can be controlled by varying the film thickness and laser power.     

Evidence of structural strain in epitaxial graphene layers on 6H-SiC(0001)

The early stages of epitaxial graphene layer growth on the Si-terminated 6H-SiC (0001) are investigated by Auger electron spectroscopy (AES) and depolarized Raman spectroscopy. The selection of the depolarized component of the scattered light results in a significant increase in the C-C bond signal over the second order SiC Raman signal, which allows us to resolve submonolayer growth, including individual, localized C=C dimers in a diamondlike carbon matrix for AES C/Si ratio of approximately 3, and a strained graphene layer with delocalized electrons and Dirac single-band dispersion for AES C/Si ratio >6. The linear strain, measured at room temperature, is found to be compressive, which can be attributed to the large difference between the coefficients of thermal expansion of graphene and SiC. The magnitude of the compressive strain can be varied by adjusting the growth time at fixed annealing temperature.