基于石墨烯-钙钛矿量子点场效应晶体管的光电探测器

以等离子增强化学气相沉积法制备的石墨烯作为导电沟道材料,将其与无机CsPbI_3钙钛矿量子点结合,设计并制备了石墨烯-钙钛矿量子点场效应晶体管光电探测器.研究和分析了石墨烯作为场效应晶体管的电学特性及其与钙钛矿量子点结合作为光电探测器的光电特性.结果表明,石墨烯在场效应晶体管中表现出良好的电学性质,其与钙钛矿量子点的结合对波长为400 nm的光辐射具有明显的光响应,在光强为12μW时器件光生电流最大为64μA,响应率达6.4 A·W~(-1),对应的光电导增益和探测率分别为3.7×10~4,6×10~7Jones(1 Jones=1 cm·Hz~(1/2)·W~(-1)).     

边界对石墨烯量子点非线性光学性质的影响

石墨烯作为一种新型非线性光学材料,在光子学领域具有重要的应用前景,引起研究人员的极大兴趣.本文运用量子化学计算方法研究了边界引入碳碳双键(C=C)和掺杂环硼氮烷(B₃N₃)环对石墨烯量子点非线性光学性质和紫外-可见吸收光谱的影响.研究发现,扶手椅边界上引入C=C双键后,六角形石墨烯量子点分子结构对称性降低,电荷分布对称性发生破缺,导致分子二阶非线性光学活性增强.石墨烯量子点在从扶手椅型边界向锯齿型边界过渡的过程中,随着边界C=C双键数目的增加,六角形石墨烯量子点和B3N3掺杂六角形石墨烯量子点的极化率和第二超极化率分别呈线性增加.此外,边界对石墨烯量子点的吸收光谱也有重要影响.无论是石墨烯量子点还是B₃N₃掺杂石墨烯量子点,扶手椅型边界上引入C=C双键导致最高占据分子轨道能级升高,最低未占分子轨道能级的降低,前线分子轨道能级差减小,因而最大吸收波长发生了红移.中心掺杂B₃N₃环后会增大石墨烯量子点的分子前线轨道能级差,导致B3N3掺杂后的石墨烯量子点紫外-可见吸收光谱发生蓝移.本文研究为边界修饰调控石墨烯量子点非线性光学响应提供了一定的理论指导.     

Synthesis and Adsorption Study of BSA Surface Imprinted Polymer on CdS Quantum Dots

开发了CdS量子点用于牛血清白蛋白(BSA)表面压印的方法,将CdS量子点掺杂进BSA的分子压印聚合物中. 实验过程中对制备条件和吸附条件进行了优化. 量子点(QDs)和量子点分子压印聚合物(QDs-MIP)的形貌用扫描电子显微镜进行了表征. 当该QDs-MIP重新结合模板分子BSA时,CdS量子点的荧光被淬灭. 荧光淬灭的原因可能是量子点与模板蛋白质分子之间的荧光共振能量转移. 该聚合物对压印分子的吸附为单分子层吸附,符合Langmuir等温吸附模型. 化学吸附为速率控制步骤. 该新型聚合物的最大吸附容量可达226.0 mg/g,比未掺杂量子点的BSA压印聚合物提高142.4 mg/g.     

CdSe/ZnSe量子点在油水两相体系下的聚合物包覆相转移及其光谱表征

采用油水两相溶液体系,借助于双亲聚合物包覆实现了CdSe/ZnSe核壳结构量子点自油相到水相的相转移。油水两相中的聚合物包覆与已经报道的均相溶液中聚合物包覆量子点的方法不同,包覆过程在油水两相界面处完成,有效地减少了聚合物缠绕引起的量子点团聚,实现了聚合物对量子点的无团聚单分散包覆。透射电镜和激光粒度分析仪对聚合物包覆量子点的表征结果表明获得的水溶性量子点具有良好的分散性,均一的水力尺寸。吸收和发射光谱表明聚合物包覆过程对量子点的发射峰位和峰型没有引起明显的改变,维持了较高的量子产率。通过荧光微区成像技术成功实现了对人IgG蛋白的特异性检测,证实这种方法获得的聚合物包覆量子点具有较好的与生物分子偶联的功能化基团,适合于生物学标记应用。     

PbSe量子点调控的聚合物太阳能电池性能

为提升聚合物太阳能电池的光电转换效率,在有源层中掺杂PbSe量子点,研究对电池性能的影响。首先采用热化学法制备PbSe量子点,通过改变油酸的添加量及反应时间,调控PbSe量子点的尺寸及结晶性。通过透射电子显微镜和X射线衍射,对量子点进行表征,确定最佳反应条件。然后将不同质量分数的PbSe量子点掺杂至结构为ITO/ZnO/PTB7∶PC_(71)BM/MoO_3/Ag的聚合物太阳能电池中,通过J-V性能测试和紫外吸收光谱测试,分析了PbSe量子点对电池的影响机理。实验结果表明,当PbO与OA的量比为1∶2、反应时间为3 min时,可得到尺寸均匀分布在3～7 nm之间、结晶性较好的量子点,掺杂量子点质量分数为3%时,短路电流密度提升了8.37%,光电转换效率提升了37.41%,有效提升了聚合物太阳能电池的性能。     

PbS量子点掺杂聚合物宽带光纤放大器

随着人工智能、大数据、云计算、物联网、移动电子等的发展，传统的稀土离子掺杂单芯单模光纤放大器承载的光纤通信系统的传输容量已经逐渐接近香农极限，需要发展新型材料体系，以拓宽光纤通信系统的传输容量。相比于稀土离子，量子点具有较宽的发光带宽、可调波长的发光特性，且量子点的发光性质可以通过多种化学手段调控，在量子点光放大器上显示出了宽带光放大特性，受到学术界和产业界的广泛关注。在该背景下，本文提出将化学合成的PbS/CdS核壳量子点与低损耗聚合物集成，获得量子点掺杂光纤放大器，实现近红外通信波段可调波长、宽带光放大特性。文章研究并揭示了影响固化后的聚合物纤芯连续性的因素和影响机制，提出了降低固化胶前驱体液面附加压力、固化收缩力、聚合物前驱体与光纤内壁的摩擦力，并提高抽真空产生的牵引力以获得连续光纤，在此基础上获得了基于热固化聚二甲基硅氧烷（PDMS）和光固化NOA61、NOA85固化胶的纤芯连续光纤，量子点光纤在1 530～1 630 nm获得了增益带宽达到100 nm以上的开关增益，最高增益达到6.5 dB。本文的研究结果将促进量子点光纤器件和宽带光通信技术的发展。     

尺寸调控SnO_2量子点的阻变性能及调控机理

零维SnO_2量子点因具有优异的物理化学稳定性、高电子迁移率和能带结构可调等特性,是阻变存储器中阻变功能材料的良好选择,受到了研究者的广泛关注.本文采用溶剂热法制备了尺寸为2.51 nm,2.96 nm和3.53 nm的SnO_2量子点,在较小尺寸范围内证明了SnO_2量子点能带结构随尺寸离散化的量子尺寸效应;并基于其量子尺寸效应,实现了对SnO_2量子点阻变存储器开关电压的有效调控.研究表明,尺寸为3.53 nm的SnO_2量子点具有较低的开关电压(-2.02 V/3.08 V)与较大的阻变开关比( 10~4),器件在经过2 × 10~4次的耐久性测试后,阻变性能变化率小于5%,具有较好的稳定性与保持性.基于库仑阻塞效应,SnO_2量子点内部缺陷势阱作为俘获中心对电子的自俘获/脱俘作用,是其实现阻变效应的原因;此外,SnO_2量子点与ITO,Au界面肖特基势垒高度的有效控制则是精准调控其阻变开关电压的关键.以上工作揭示了SnO_2量子点在阻变存储领域的巨大应用潜力和商业化应用价值,为阻变存储器的发展提供了一项新的选择.     

ZnO@GQDs核壳结构量子点的制备及性能研究

采用原位聚合法制备了以ZnO量子点为核、石墨烯量子点（GQDs）为壳的ZnO@ GQDs核壳结构量子点。通过TEM和HR-TEM对量子点进行形貌和结构的分析表征。结果表明,合成的ZnO@ GQDs核壳结构量子点为球形,粒径为～7 nm,且尺寸均匀。PL光谱研究表明,新型量子点的发射峰位于369 nm,发光峰窄、强度高;相对于ZnO的本征发射峰,GQDs的引入使得ZnO@GQDs核壳量子点的荧光发射峰出现蓝移、强度变高,从而使复合量子点的荧光具有较纯的色度和较高的强度,说明GQDs的引入具有协同优化效应。该量子点有望应用于LED显示器件。     

水热法快速制备荧光氧化石墨烯量子点及其在细胞成像中的应用

作为一种新型荧光纳米材料,氧化石墨烯量子点(GO QDs)凭借其良好的水溶性和生物相容性得到广泛的关注。以氧化石墨烯为原料,过氧化氢为氧化剂,一步水热法在90 min内快速制备氧化石墨烯量子点,实现了快速、高效及绿色制备氧化石墨烯量子点。所制备得到的氧化石墨烯量子点分布均匀,透射电镜(TEM)图片表明氧化石墨烯量子点粒径分布在2.25～5.25 nm,傅里叶红外光谱(FTIR)和X射线电子能谱(XPS)显示氧化石墨烯量子点表面含有大量的羟基、羧基、羰基等含氧功能团,表明氧化石墨烯量子点具有很好的水溶性。荧光发射光谱(PL)表明氧化石墨烯量子点具有激发波长依赖性。基于其独特的纳米结构,良好的光学性能和生物相容性,氧化石墨烯量子点可替代传统荧光纳米材料应用于细胞成像。     

ZnO@GQDs核壳结构量子点的制备及性能研究

采用原位聚合法制备了以ZnO量子点为核、石墨烯量子点(GQDs)为壳的ZnO@GQDs核壳结构量子点。通过TEM和HR-TEM对量子点进行形貌和结构的分析表征。结果表明,合成的ZnO@GQDs核壳结构量子点为球形,粒径为~7 nm,且尺寸均匀。PL光谱研究表明,新型量子点的发射峰位于369 nm,发光峰窄、强度高;相对于ZnO的本征发射峰,GQDs的引入使得ZnO@GQDs核壳量子点的荧光发射峰出现蓝移、强度变高,从而使复合量子点的荧光具有较纯的色度和较高的强度,说明GQDs的引入具有协同优化效应。该量子点有望应用于LED显示器件。     

Hydrothermal synthesis of graphene oxide/multiwalled carbon nanotube/Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> ternary nanocomposite for removal of Cu (II) and methylene blue

In this work, highly activated graphene oxide/multiwalled carbon nanotube/Fe₃O₄ ternary nanocomposite adsorbent was prepared from a simple hydrothermal route by using ferrous sulfate as precursor. For this purpose, the graphene oxide/multiwalled carbon nanotube architectures were formed through the π-π attractions between them, followed by attaching Fe₃O₄ nanoparticles onto their surface. The structure and composition of as-prepared ternary nanocomposite were characterized by XRD, FTIR, XPS, SEM, TEM, Raman, TGA, and BET. It was found that the resultant porous graphene oxide/multiwalled carbon nanotube/Fe₃O₄ ternary nanocomposite with large surface area could effectively prevent the π-π stacking interactions between graphene oxide nanosheets and greatly improve sorption sites on the surfaces. Thus, owing to the unique ternary nanocomposite architecture and synergistic effect among various components, as-prepared ternary nanocomposite exhibited high separation efficiency when they were used to remove the Cu (II) and methylene blue from aqueous solutions. Furthermore, the adsorption isotherms of ternary nanocomposite structures for Cu (II) and methylene blue removal fitted the Langmuir isotherm model. This work demonstrated that the graphene oxide/multiwalled carbon nanotube/Fe₃O₄ ternary nanocomposite was promising as an efficient adsorbent for heavy metal ions and organic dye removal from wastewater in low concentration.     

Specific features of low-frequency vibrational dynamics and low-temperature heat capacity of double-walled carbon nanotubes

A continuous model has been constructed for low-frequency dynamics of a double-walled carbon nanotube. The formation of the low-frequency part of the phonon spectrum of a double-walled nanotube from phonon spectra of its constituent single-walled nanotubes has been considered in the framework of the proposed approach. The influence of the environment on the phonon spectrum of a single double-walled carbon nanotube has been analyzed. A combined method has been proposed for estimating the coefficients of the van der Waals interaction between the walls of the nanotube from the spectroscopic data and the known values of the elastic moduli of graphite. The low-temperature specific heat has been calculated for doublewalled carbon nanotubes, which in the field of applicability of the model (T < 35 K) is substantially less than the sum of specific heats of two individual single-walled nanotubes forming it.     

Effect of temperature and geometrical nonlinearity on wave propagation characteristics of carbon nanotubes

Considering the effect of temperature and geometrical nonlinearity in the constitutive relation, the equation of motion for a carbon nanotube is obtained based on the Euler–Bernouli beam model. Also, the effect of van der Waals forces is taken into account in the formulation. The carbon nanotube is assumed to be under the application of a constant distributed external load. At any temperature, the equilibrium solutions of the governing equations for a single-walled carbon nanotube (SWCNT) and a double-walled carbon nanotube (DWCNT) are obtained. A small perturbation is assumed around the equilibrium solution. Using this perturbation, the nonlinear equations of motion are linearized. Using the linearized form of the equations of motion, the characteristic equations and dispersion relations are obtained. It is shown that in the linear case and for the case of high temperature there exists a temperature beyond which the phase velocity does not exist. It is shown that in the case of room or low temperature there is no critical value for temperature. Based on the dispersion equation, a relation for the critical value of temperature is obtained. It is found that when the large deformation effect is taken into account, the critical value for temperature does not exist. Also, the effect of large deformations on phase velocities and lateral deformations of single-walled and double-walled carbon nanotube beams are studied. It is found that unlike the linear theory, the nonlinear theory predicts a non-zero phase velocity at the temperature corresponding to linear critical temperature.     

Preparation of few-layer nitrogen-doped graphene nanosheets by DC arc discharge under nitrogen atmosphere of high temperature

Few-layer N-doped graphene nanosheets (GNSs) were prepared by a DC arc discharge under a nitrogen atmosphere of high temperature. HRTEM characterization shows the typical morphology of the several layer GNSs and some GNSs stacking together in the form of terrace. The typically rotational stacking faults can be observed in the GNSs. The Raman spectrum shows the characteristic peak of the graphene. It is confirmed by XRD, EELS, and EDX characterizations that the GNSs are doped with nitrogen. The content of few-layer N-doped GNSs in the column-shaped deposits formed on the top of the cathode is larger than 50 weight %. The formation mechanism of N-doped GNSs is discussed on the foundation of our results and other related published work.     

Hydrothermal Preparation of Photoluminescent Graphene Quantum Dots Characterized Excitation‐Independent Emission and its Application as a Bioimaging Reagent

Zero‐dimensional photoluminescent (PL) graphene quantum dots (GQDs) that can be used as the cell‐imaging reagent are prepared by a hydrothermal route using the graphene oxide (GO) as the carbon source. Under the optimized hydrothermal conditions, an initial hydrogen peroxide concentration of 0.5 mg mL^?1 at 180 °C for 120 min, the GO sheets can be cut into nanocrystals with lateral dimensions in the range of 1.5–5.5 nm and an average thickness of around 1.1 nm. The as‐prepared GQDs exhibit an abundance of hydrophilic hydroxy and carboxyl groups and emit bright blue luminescence with up‐conversion properties in a water solution at neutral pH. Most interestingly, they indicate excitation‐independent emission characteristics, and the surface state is demonstrated to have a key role in the PL properties. The fluorescence quantum yield of the GQDs is tested to be around 6.99% using quinine sulfate as a standard. In addition, the as‐prepared GQDs can enter into HeLa cells easily as a fluorescent imaging reagent without any further functionalization, indicating they are aqueous stability, biocompatibility, and promising for potential applications in biolabeling and solution state optoelectronics.     

Frequency change by inter-walled length difference of double-wall carbon nanotube resonator

Ultrahigh frequency nanomechanical resonators based on double-walled carbon nanotubes with different wall lengths were investigated via classical molecular dynamics simulations. For a double-walled carbon nanotube resonator with a short outer wall, the free edge of the short outer wall plays an important role in the vibration of the long inner wall. For a double-walled carbon nanotube resonator with a short inner wall, the short inner wall can be considered as a flexible core, thus, the fundamental frequency is influenced by its length. By controlling the length of the inner or outer wall, various frequency devices can be realized by a single type of double-walled carbon nanotube with walls of equal length.     

Nonlinear dynamics of bi-layered graphene sheet,double-walled carbon nanotube and nanotube bundle

Due to strong van der Waals (vdW) interactions, the graphene sheets and nanotubes stick to each other and form clusters of these corresponding nanostructures, viz. bi-layered graphene sheet (BLGS), double-walled carbon nanotube (DWCNT) and nanotube bundle (NB) or ropes. This research work is concerned with the study of nonlinear dynamics of BLGS, DWCNT and NB due to nonlinear interlayer vdW forces using multiscale atomistic finite element method. The energy between two adjacent carbon atoms is represented by the multibody interatomic Tersoff–Brenner potential, whereas the nonlinear interlayer vdW forces are represented by Lennard-Jones 6–12 potential function. The equivalent nonlinear material model of carbon–carbon bond is used to model it based on its force–deflection relation. Newmark’s algorithm is used to solve the nonlinear matrix equation governing the motion of the BLGS, DWCNT and NB. An impulse and harmonic excitations are used to excite these nanostructures under cantilevered, bridged and clamped boundary conditions. The frequency responses of these nanostructures are computed, and the dominant resonant frequencies are identified. Along with the forced vibration of these structures, the eigenvalue extraction problem of armchair and zigzag NB is also considered. The natural frequencies and corresponding mode shapes are extracted for the different length and boundary conditions of the nanotube bundle.     

基于石墨烯量子点的荧光探针应用于抗坏血酸检测的研究

基于石墨烯量子点(GQDs)的荧光性能建立了一种非标记荧光方法,用于灵敏和选择性测定抗坏血酸(AA)。GQDs溶液在紫外光激发下发出很强的蓝色荧光,当向溶液中加入AA后,GQDs溶液的荧光被猝灭。猝灭机理可能为在弱酸性介质中,AA与GQDs发生氧化还原反应,AA转移电子给GQDs。荧光猝灭强度与AA浓度在5.0×10~(-6)~7.5×10~(-5)mol/L范围内呈良好的线性关系,检出限低至1.0×10~(-6)mol/L。该体系成本低、操作简单,并且在多种可能干扰的物质存在下对AA表现出很高的选择性。本方法应用于生物样品中AA的检测,回收率在95.2%~115.3%之间。     

Effect of doping on electronic properties of double-walled carbon and boron nitride hetero-nanotubes

The effect of boron nitride (BN) doping on electronic properties of armchair double-walled carbon and hetero-nanotubes is studied using ab initio molecular dynamics method. The armchair double-walled hetero-nanotubes are predicted to be semiconductor and their electronic structures depend strongly on the electronic properties of the single-walled carbon nanotube. It is found that electronic structures of BN-doped double-walled hetero-nanotubes are intermediate between those of double-walled boron nitride nanotubes and double-walled carbon and boron nitride hetero-nanotubes. Increasing the amount of doping leads to a stronger intertube interaction and also increases the energy gap.     

热力耦合作用下双层碳纳米管的扭转屈曲

考虑碳纳米管周边弹性介质和层间范德瓦耳斯力的作用,利用连续介质力学的壳体理论,建立了热力耦合作用下碳纳米管屈曲问题的控制方程,给出了相应的临界屈曲扭矩的解析解.数值模拟结果表明,在低温和室温环境下,碳纳米管的临界屈曲载荷随着温度变化量的增加而提高;在高温环境下,碳纳米管的临界屈曲载荷随着温度变化量的增加而降低. 关键词： 碳纳米管 屈曲 热力耦合