金纳米粒子的最新研究进展

金纳米粒子是最稳定的金属纳米粒子之一，由于其具有优良的稳定性和光学性质，使其在许多领域有着广阔的应用前景。本文主要对金纳米粒子和表面修饰金纳米粒子的制备方法进行分析总结，指出各种方法的制备原理及特点。同时，阐述了金纳米粒子的一些特殊性能，如：表面吸收带效应、荧光效应、量子尺寸效应、单电子跃迁等。并对金纳米粒子的应用进行了展望。     

微乳法制备纳米金及其生物电催化性能研究

纳米金具有特殊的电催化性能。采用水/AOT(2-乙基己基琥珀酸酯磺酸钠)/环己烷微乳体系制备纳米金颗粒,通过改变水与AOT的物质的量比(ω)制备不同尺寸的纳米金,并通过透射电镜、紫外分光光度计、电化学工作站对纳米金颗粒的形貌尺寸、紫外吸收光谱、电化学性能进行分析与研究。结果表明,纳米金呈球形,尺寸均一,单分散性较好。通过对纳米金颗粒电催化析氢性能的测试发现,纳米金粒子分散性较好,形成的是均相溶液,纳米金粒子与Pt/C相比电催化性能稍弱,但是与纳米银、金铁合金和纳米硒化钨相比都显现出较好的电催化活性,说明纳米金粒子具有比较优良的电催化性能,为纳米金颗粒在生物电催化领域的应用奠定理论基础。     

二氧化硅纳米颗粒的反应离子刻蚀及其在硅纳米针尖制备中的应用

系统地研究了硅衬底上二氧化硅纳米颗粒的反应离子刻蚀（R IE）过程,并在此基础上制备了可用于场发射的硅纳米针尖阵列.首先,采用改进的蒸发法在硅衬底上实现二氧化硅纳米颗粒的单层密排结构,再采用典型的刻蚀二氧化硅的RIE技术同时刻蚀硅衬底和二氧化硅纳米颗粒,在对纳米颗粒尺寸随刻蚀进行而改变的电镜照片分析的基础上,获得了相应的二氧化硅纳米颗粒刻蚀模型,计算得到横向和纵向的刻蚀速率;当刻蚀后的二氧化硅纳米颗粒从衬底上脱落后,进一步对硅衬底的刻蚀可以得到锐利的硅纳米针尖阵列,初步的实验结果表明,所制备的硅纳米针尖具有较好的场发射特性.     

利用湿化学法对不同粒径硅粉进行表面改性研究

通过湿化学方法,利用硅氢化反应,通过对刻蚀体系、脱氧方式、刻蚀后硅粒子的分离方法等工艺的优化,成功地实现了微米硅、纳米硅及硅量子点的表面烃基改性。傅里叶变换红外光谱及扫描电子显微镜测试结果表明,硅粒子的表面是通过Si—C键的连接方式实现了烃基改性。与改性前相比,改性后的硅粒子具有显著提升的抗氧化性和抗团簇能力,能够在有机溶剂中形成稳定的分散体系。值得一提的是,与未经改性的硅量子点相比,经烃基改性后的硅量子点的荧光发射性能有了大幅提高,有望应用于光电领域。     

磁性/荧光双功能纳米颗粒的制备及性能研究

通过对Fe3O4纳米颗粒的SiO2包覆和表面胺基化修饰,成功地将CdSe量子点（QDs）均匀地包覆在Fe3O4纳米粒子表面,制备了稳定的、具有磁性/荧光双功能的纳米颗粒,结果表明,所制备的纳米颗粒具有良好的分散性、优异的磁响应特性和荧光发射性能,为制备该类双功能纳米材料,拓宽其应用领域提供了新的途径。     

金属辅助化学刻蚀法制备硅纳米线的研究进展

硅纳米线(Si NWs)由于具有独特的一维结构、热电导率、光电性质、电化学性能等特点,被广泛应用于热电与传感器件、光电子元器件、太阳能电池、锂离子电池等领域。金属辅助化学刻蚀法(MACE)是制备Si NWs的常用方法之一,具有操作简便、设备简单、成本低廉和高效等优点,可大规模商业化应用,因而近年来被广泛研究。金属辅助化学刻蚀制备硅纳米线的过程可以分为两步:首先在洁净的硅衬底表面沉积一层金属(Ag、Au、Pt等)纳米颗粒,以催化、氧化它附近的硅原子;然后利用HF溶解氧化层,从而对硅晶片进行刻蚀,形成纳米线阵列。然而,这种简单高效的制备硅纳米线的方法存在一些难以控制的缺点:(1)金属纳米颗粒聚集、相连后造成Si NWs之间的缝隙比较大,从而导致Si NWs密度较低;(2)由于金属纳米颗粒沉积的随机性,在硅晶片表面分布不均匀,不仅导致刻蚀出的纳米线直径范围(50～200 nm)较宽,而且使制得的纳米线阵列排列无序且间距不易调控;(3)当刻蚀出的硅纳米线太长时,范德华力等作用会造成纳米线顶端出现严重的团簇现象。针对常规法存在的一些问题以及不同的器件对硅纳米线的形貌、类型和直径等的要求,近年来的研究主要集中在如何减少纳米线顶端团簇、调控纳米表面粗糙度和直径、低成本制备有序硅纳米线等方面。目前一些改进常规金属辅助化学刻蚀的方法取得了进展,比如:(1)用酸溶液或UV/Ozone对硅晶片预处理,在表面形成氧化层,可以使纳米线的均匀性得到改善并增大其密度(从18%提高到38%);(2)使用物理气相沉积法在硅晶片表面沉积一层金属纳米薄膜,然后再刻蚀,这种方法能够减少纳米线顶端团簇和有效调控纳米线直径;(3)利用模板法(聚苯乙烯小球模板、氧化铝模板、二氧化硅模板和光刻胶模板等)可以制备出有序的硅纳米线阵列。本课题组用离子束刻蚀的方法制备了直径范围可以控制在30～90 nm的聚苯乙烯小球模板,为小尺寸有序硅纳米线的制备打下了坚实的基础。本文简要介绍了常规MACE的原理和制备流程,总结了硅晶片的类型、刻蚀溶液的浓度、温度和刻蚀时间等因素对Si NWs形貌、尺度、表面粗糙度、刻蚀方向以及刻蚀速率的影响,用相关的机制解释了H2O2过量时刻蚀路径偏离垂直方向的机理以及刻蚀速率随溶液浓度变化的原因,重点综述了氧化层预处理、物理法沉积贵金属纳米薄膜、退火处理和模板法等改进方法在减少纳米线顶部团簇、改善均匀性、制备有序且直径和间距可控纳米线中的研究进展。     

Fe3O4/CdTe磁性荧光纳米复合物的逐步杂凝聚法合成及其表征

采用逐步杂凝聚法合成了Fe3O4/CdTe磁性荧光纳米复合物.以化学共沉淀法制备Fe3O4纳米颗粒,经油酸修饰后分散在表面活性剂中形成磁流体.CdTe量子点以巯基乙酸为稳定剂制得.最后以聚乙烯亚胺(PEI)为联接剂,成功制备了Fe3 O4 /CdTe磁性荧光双功能纳米复合物颗粒.该复合物颗粒平均尺寸为(30±5)nm,荧光产率为0.186,饱和磁化强度为15.745emu/g,该纳米粒子既具有优异的荧光特性,也具有较强的超顺磁性.     

一种在硅材料表面组装金纳米颗粒的新方法

以氯金酸、L-半胱氨酸为反应试剂,利用内电流和金硫自组装效应,在硅材料表面组装了较为均一的金纳米颗粒,并利用荧光分析与硅纳米线场效应晶体管对该方法进行了相关验证。结果表明:经氢氟酸处理后的硅材料,在氯金酸和L-半胱氨酸混合溶液中反应3min可在硅表面得到较为均匀、稳定的金纳米颗粒层,其中,氯金酸浓度为0.5mmol/L,氯金酸和L-半胱氨酸浓度比为3∶1。荧光分析表明该方法组装的金颗粒表面已氨基功能化,使得金纳米颗粒修饰的硅材料在应用于生物检测时可直接醛基化修饰蛋白,简化了实验操作。同时,该方法可以在硅纳米线场效应晶体管中特异性组装金纳米颗粒,有力地支持了相关器件在疾病检测方面的应用。     

单分散Fe3O4@SiO2/Au复合纳米颗粒的制备

制备了尺寸为30nm,具有磁响应的单分散Fe3O4@SiO2/Au核壳纳米颗粒,并研究其光学性质。首先利用热分解法制备油酸修饰的Fe3O4纳米粒子,再用反相微乳法制备Fe3O4@SiO2纳米粒子,最后利用表面修饰的氨基还原性,获得Fe3O4@SiO2/Au核壳复合纳米颗粒。分别用TEM、XRD、Zeta电位与粒度分析仪对产物形貌、结构、表面电位和粒径分布进行表征,用紫外-可见分光光度计对光学性质进行了测试。     

硅基体表面无钯活化化学镀镍工艺

硅材化学镀镍的活化是为了获取金属原子沉积中心,但现有的活化工艺存在种种不足。金纳米粒子具有小尺寸效应、表面与界面效应,呈现出良好的催化活性。采用金纳米粒子对硅基体进行活化后化学镀镍,并采用浸泡腐蚀试验,SEM及EDS测试将其与传统的钯活化法对比,研究了活化后的沉积速度及镀层形貌、结构、耐腐蚀性能,结果表明：金纳米粒子活...     

硅基含能材料爆炸性能研究

采用电化学双槽腐蚀法在P型单晶硅片表面生长多孔硅膜。通过扫描电镜（SEM）、能量色谱（EDS）对多孔硅结构参数以及多孔硅含能材料性能进行了分析,同时进行了爆炸性能测试。结果表明：采用电化学腐蚀法可以制备出20nm左右孔径的多孔硅膜;通过原位装药技术形成的多孔硅含能材料在开放空间以及热能、机械撞击、电能、激光能量刺激下发生猛烈爆炸作用。     

一种在硅材料表面组装金纳米颗粒的新方法

以氯金酸、L-半胱氨酸为反应试剂,利用内电流和金硫自组装效应,在硅材料表面组装了较为均一的金纳米颗粒,并利用荧光分析与硅纳米线场效应晶体管对该方法进行了相关验证.结果表明:经氢氟酸处理后的硅材料,在氯金酸和L_半胱氨酸混合溶液中反应3 min可在硅表面得到较为均匀、稳定的金纳米颗粒层,其中,氯金酸浓度为0.5mmol/L,氯金酸和L-半耽氨酸浓度比为3∶1.荧光分析表明该方法组装的金颗粒表面已氨基功能化,使得金纳米颗粒修饰的硅材料在应用于生物检测时可直接醛基化修饰蛋白,简化了实验操作,同时,该方法可以在硅纳米线场效应晶体管中特异性组装金纳米颗粒,有力地支持了相关器件在疾病检测方面的应用.     

Multi-band silicon quantum dots embedded in an amorphous matrix of silicon carbide

Silicon quantum dots embedded in an amorphous matrix of silicon carbide were realized by a magnetron co-sputtering process and post-annealing. X-ray photoelectron spectroscopy, glancing x-ray diffraction, Raman spectroscopy and high-resolution transmission electron microscopy were used to characterize the chemical composition and the microstructural properties. The results show that the sizes and size distribution of silicon quantum dots can be tuned by changing the annealing atmosphere and the atom ratio of silicon and carbon in the matrix. A physicochemical mechanism is proposed to demonstrate this formation process. Photoluminescence measurements indicate a multi-band configuration due to the quantum confinement effect of silicon quantum dots with different sizes. The PL spectra are further widened as a result of the existence of amorphous silicon quantum dots. This multi-band configuration would be extremely advantageous in improving the photoelectric conversion efficiency of photovoltaic solar cells.     

电催化金属辅助化学刻蚀法制备硅纳米线/多孔硅复合结构

量子限制效应使硅纳米线具有良好的场致发射特性,结合多孔硅的准弹道电子漂移模型可提高场发射器件的性能。传统的金属辅助化学刻蚀法制备硅纳米线的效率较低,本研究在传统方法的基础上引入恒流源,提出电催化金属辅助化学刻蚀法,高效制备了硅纳米线/多孔硅复合结构。在外加30mA恒定电流的条件下,硅纳米线的平均制备速率可达308nm/min,较传统方法提升了173%。研究了AgNO₃浓度、刻蚀时间和刻蚀电流对复合结构形貌的影响规律;测试了采用电催化金属辅助化学刻蚀法制备样品的场发射特性。结果显示样品的阈值场强为10.83 V/μm,当场强为14.16 V/μm时,电流密度为64μA/cm²。     

纳米多孔硅的电化学制备及性能研究

纳米多孔硅是一种潜在的化学和生物传感材料,本文采用电化学腐蚀法制备纳米多孔硅。采用SEM技术分析多孔硅的表面形貌,研究了腐蚀条件对多孔硅的孔隙率、厚度、I-V特性的影响。结果表明,多孔硅的孔隙率随着腐蚀电流密度和腐蚀时间的增加而呈线性增大趋势;其厚度随着腐蚀电流密度的增加而近似呈线性增大趋势,随腐蚀时间的成倍增加而显著增大;其I-V特性表现出非整流的欧姆接触。     

原位聚合法制备聚丙烯酸修饰的ZnS量子点

采用原位聚合法对ZnS量子点表面进行聚丙烯酸(PAA)的修饰。利用XRD、FTIR、TEM、TGA、荧光测试等对ZnS@PAA复合纳米粒子进行系列表征。XRD分析表明,修饰后的ZnS仍为立方晶相。FTIR和TGA结果证明,ZnS纳米粒子表面存在PAA。TEM结果表明,修饰后ZnS@PAA复合纳米粒子在去离子水中分散良好,其直径有所增加,约为28 nm,且呈较明显的核-壳结构。荧光测试发现,修饰PAA前后ZnS@PAA复合纳米粒子的发光特性没有发生明显改变。实验表明,经PAA修饰后,ZnS@PAA复合纳米粒子在水溶液中的分散性和稳定性得到提高,抗氧化性和荧光稳定性也得到了一定的增强。      

Designed synthesis of chlorine and nitrogen co-doped Ti3C2 MXene quantum dots and their outstanding hydroxyl radical scavenging properties

As a novel zero-dimensional(0D)material,metal carbides and/or carbonitrides(MXenes)quantum dots(MQDs)show unique photoluminescence properties and excellent biocompatibility.However,due to the limited synthesis methods and research to date,many new features have yet to be uncovered.Here,to explore their new properties and expand biological applications,chlorine and nitrogen co-doped Ti3C2 MXene quantum dots(Cl,N-Ti3C2 MQDs)were designed and synthesized,and their hydroxyl radical scavenging properties were investigated for the first time,revealing outstanding performance.Cl,N-Ti3C2 MQDs was directly stripped from bulk Ti3 AlC2 by electrochemical etching,while N and Cl are successfully introduced to carbon skeleton and Ti boundaries in the etching process by electrochemical reactions between selected electrolytes and Ti3C2 skeleton,respectively.The obtained Cl,N-Ti3C2 MQDs exhibit large surface-to-volume ratio due to small particle size(ca.3.45 nm)and excellent higher scavenging activity(93.3％)and lower usage(12.5 μg/mL)towards hydroxyl radicals than the previous reported graphene-based nanoparticles.The underlying mechanism of scavenging activity was also studied based on the reduction experiment with potassium permanganate(KMnO4).The reducing ability of the intrinsic Ti3C2 structure and electron donation of double dopants are the main contributors to the outstanding scavenging activity.     

Study of silicon nanoparticles in dielectric oxides obtained by sol–gel route

Silicon nanoparticles (Si-NPs) obtained by electrochemical etching of silicon wafer were incorporated into various dielectric matrices using sol–gel method. To attain a wide range of dielectric constant and band gap energy, three matrices are selected (SiO₂, ZrO₂ and TiO₂) and the Si-NPs were incorporated in these matrices at different concentrations. Structural studies by transmission electron microscopy and Raman spectroscopy confirm the presence of Si-NPs in the matrices. Moreover, the significant compressive stress induced by the matrix is observed. Photoluminescence (PL) studies show that Si-NPs preserve their luminescent properties in SiO₂ matrix and ZrO₂ matrix but not in TiO₂ matrix. The PL peak position depends not only on the dimension of Si-NPs but also depends on their concentrations. This is due to the coupling effect between the nanoparticles which increases with concentration.     

Properties of electrospun CdS and CdSe filled poly(methyl methacrylate) (PMMA) nanofibres

Electrospinning technique was used to fabricate poly(methyl methacrylate) (PMMA) fibres incorporating CdS and CdSe quantum dots (nanoparticles). Different nanoparticle loadings (2, 5 and 10 wt% with respect to PMMA) were used and the effect of the quantum dots on the properties of the fibres was studied. The optical properties of the hybrid composite fibres were investigated by photoluminescence and UV-vis spectrophotometry. Scanning electron microscopy (SEM), X-ray diffraction and FTIR spectrophotometry were also used to investigate the morphology and structure of the fibres. The optical studies showed that the size-tunable optical properties can be achieved in the polymer fibres by addition of quantum dots. SEM images showed that the morphologies of the fibres were dependent on the added amounts of quantum dots. A spiral type of morphology was observed with an increase in the concentration of CdS and CdSe nanoparticles. Less beaded structures and bigger diameter fibres were obtained at higher quantum dot concentrations. X-ray diffractometry detected the amorphous peaks of the polymer and even after the quantum dots were added and the FTIR analysis shows that there was no considerable interaction between the quantum dots and the polymer fibres at low concentration of quantum dots however at higher concentrations some interactions were observed which shows that QDs were present on the surfaces of the fibres.     

InGaAs quantum dots grown by molecular beam epitaxy for light emission on Si substrates

The aim of this study is to achieve homogeneous, high density and dislocation free InGaAs quantum dots grown by molecular beam epitaxy for light emission on silicon substrates. This work is part of a project which aims at overcoming the severe limitation suffered by silicon regarding its optoelectronic applications, especially efficient light emission device. For this study, one of the key points is to overcome the expected type II InGaAs/Si interface by inserting the InGaAs quantum dots inside a thin silicon quantum well in SiO2 fabricated on a SOI substrate. Confinement effects of the Si/SiO2 quantum well are expected to heighten the indirect silicon bandgap and then give rise to a type I interface with the InGaAs quantum dots. Band structure and optical properties are modeled within the tight binding approximation: direct energy bandgap is demonstrated in SiO2/Si/InAs/Si/SiO2 heterostructures for very thin Si layers and absorption coefficient is calculated. Thinned SOI substrates are successfully prepared using successive etching process resulting in a 2 nm-thick Si layer on top of silica. Another key point to get light emission from InGaAs quantum dots is to avoid any dislocations or defects in the quantum dots. We investigate the quantum dot size distribution, density and structural quality at different V/III beam equivalent pressure ratios, different growth temperatures and as a function of the amount of deposited material. This study was performed for InGaAs quantum dots grown on Si(001) substrates. The capping of InGaAs quantum dots by a silicon epilayer is performed in order to get efficient photoluminescence emission from quantum dots. Scanning transmission electronic microscopy images are used to study the structural quality of the quantum dots. Dislocation free In50Ga50As QDs are successfully obtained on a (001) silicon substrate. The analysis of QDs capped with silicon by Rutherford Backscattering Spectrometry in a channeling geometry is also presented.