Zn_xCd_(1-x)S∶Ag纳米晶的合成及其光学性质研究

以巯基丙酸(MPA)为稳定剂,利用共沉淀法制备了水溶性的Ag掺杂的ZnxCd1-xS合金型纳米晶.Ag掺杂后ZnxCd1-xS纳米晶产生新的发射峰,并且发光效率得到了有效提高.通过改变纳米粒子中Zn/Cd比例可有效地调控ZnxCd1-xS∶Ag纳米晶的吸收带隙宽度,同时可以在425~603 nm之间实现对ZnxCd1-xS∶Ag纳米晶发射峰位的连续调控.     

近红外光驱动的UCNPs/ZnxCd1-xS纳米复合结构的化学合成并用于光化学还原六价铬

近红外光约占入射太阳能的 44% 以上, 为实现太阳能量的最大化利用, 近红外光 (NIR) 驱动的光催化技术成为科学研究的热点. 由于上转换荧光纳米材料 (UCNPs) 是优良的红外能量转换器, 合金半导体 ZnxCd1-xS 具有较好的化学稳定性以及生物相容性, 本文发展了一种简易的水热法, 将 UCNPs 和 ZnxCd1-xS 合金结合, 成功构建了 NIR 与可见光响应的核壳纳米结构. 由于这两种材料的晶格失配度较高, 很难直接外延生长, 我们通过引入非晶 TiO2将形成的催化剂纳米颗粒ZnxCd1-xS 紧紧束缚在 UCNPs 外面形成蛋黄-蛋壳结构, 在 NIR 光照下获得了较高的能量转换效率.首先, 在 UCNPs 外面外延生长一层 AA-Zn[(OH)4]2–复合物, 形成 UCNPs@AA-Zn[(OH)4]2–复合纳米结构, 然后在其核壳结构外面外延生长薄层的非晶 TiO2, 以稳定后续要制备的合金半导体 ZnxCd1-xS; 在水热条件下, UCNPs@AA-Zn[(OH)4]2–/TiO2与醋酸镉和硫脲反应, 形成 UCNPs@ZnxCd1-xS/TiO2复合材料. 在此, 我们选择β-NaYF4:Yb(30%),Tm(0.5%)@NaYF4:Yb(20%),Er(2%) 作为 NIR 的能量转换器. 样品的形貌、物相及化学组成分别采用场发射扫描电子显微镜、透射电子显微镜、X 射线衍射和原子吸收光谱法进行表征.研究表明, 我们成功制备了具有蛋黄-蛋壳结构的 UCNPs@ZnxCd1-xS/TiO2纳米颗粒. 此外, 非晶态 TiO2将 UCNPs 与ZnxCd1-xS 紧密结合, 对最终样品 UCNPs@ZnxCd1-xS 核壳纳米粒子的形成起到重要作用. 而且, 合金 ZnxCd1-xS 的化学组成可通过调整镉源和锌源的用量进行调节. 所制备的 UCNPs@ZnxCd1-xS 核壳纳米粒子在 NIR 光线或模拟太阳光照射下显示出高效的光化学还原 Cr(VI) 性能. 溶液中 70% 以上的 Cr(VI) 在 NIR 光照射 30 min 后被还原为 Cr(III). 本研究将为环境污水处理和太阳能利用提供一种可供选择的策略, 且所制的复合纳米结构在肿瘤治疗、药物释放和能量转换等领域也有着潜在的应用价值.     

Ag∶InP/ZnSe纳米晶的合成与生物成像

采用高温热注入法,以P[N(CH_3)_2]_3为磷源合成了具有近红外荧光的Ag∶InP/ZnSe纳米晶.采用紫外-可见-近红外吸收光谱(UV-Vis-NIR)、荧光光谱、透射电子显微镜(TEM)、X射线衍射(XRD)等对产物的结构和光学性质进行了表征,并分析了Ag掺杂浓度和温度对InP纳米晶荧光性能的影响.通过调节Ag掺杂浓度和反应温度,发现当Ag掺杂量为6%,反应温度为200℃时,Ag∶InP纳米晶的发光效率最高.将制备的Ag∶InP的表面包覆ZnSe,粒子的荧光效率从原来的20%提高到45%.将具有近红外荧光的Ag∶InP/ZnSe纳米晶应用于细胞成像,结果表明制备的荧光纳米晶在细胞成像中清晰可见且毒性较低.     

微波辅助合成发光可调ZnS∶Cu纳米晶

以巯基丙酸(MPA)为稳定剂, 利用微波辐射加热方法制备了水溶性的Cu掺杂的ZnS纳米晶. 通过改变微波条件, 可以在460～572 nm之间实现对ZnS∶Cu纳米晶发射峰位的连续调控. 通过XRD、 UV-Vis、荧光及荧光衰减对ZnS∶Cu纳米晶的结构和发光性质进行了详细探索, 并利用时间分辨荧光光谱对其发光机理进行了初步研究.     

微波辅助合成发光可调ZnS∶Cu纳米晶

以巯基丙酸(MPA)为稳定剂,利用微波辐射加热方法制备了水溶性的Cu掺杂的ZnS纳米晶.通过改变微波条件,可以在460~572nm之间实现对ZnS∶Cu纳米晶发射峰位的连续调控.通过XRD、UV-Vis、荧光及荧光衰减对ZnS∶Cu纳米晶的结构和发光性质进行了详细探索,并利用时间分辨荧光光谱对其发光机理进行了初步研究,     

纳米晶ZnO∶Er3+的制备及其室温上转换发射

采用化学沉淀法成功地将Er3+掺杂到纳米晶ZnO基质晶格中, 所制备的纳米晶ZnO∶Er3+粉体具有强室温发射现象, 并观测到其室温上转换发射现象. 纳米晶ZnO∶Er具有较高的上转换效率, 用978 nm激光激发, 肉眼可观察到绿色发光. 本文制备的纳米晶ZnO∶Er3+粉体发光材料不同于Er掺杂的体材料ZnO粉体.     

TiO2/Ag2O纳米材料的制备及其对甲醛的气敏性能

采用溶胶-凝胶法制备了掺杂Ag的TiO2纳米晶粉体. 用XRD、TEM和BET方法对纳米晶的晶型﹑晶粒大小和表面性能进行了表征. 分析结果显示, 相同条件下掺杂Ag的TiO2比纯TiO2纳米材料具有更大的比表面积. 气敏性能测试结果表明, 掺杂Ag的TiO2传感器对甲醛有较好的灵敏度和更高的选择性.当焙烧温度为500 ℃, 掺杂Ag的摩尔比为5%(n(AgNO3)/n(Ti(OC4H9)4)=5%)时, TiO2对甲醛气体敏感性能最好. 在最佳工作电流124 mA下, 该元件对10 μL·L-1 HCHO的灵敏度S 接近4, 它的响应时间不超过1 s, 恢复时间为9 s.     

Ag∶InP/ZnSe纳米晶的合成与生物成像

采用高温热注入法, 以P[N(CH3)2]3为磷源合成了具有近红外荧光的Ag∶InP/ZnSe纳米晶. 采用紫外|可见|近红外吸收光谱(UV|Vis|NIR)、 荧光光谱、 透射电子显微镜(TEM)、 X 射线衍射(XRD)等对产物的结构和光学性质进行了表征, 并分析了Ag掺杂浓度和温度对InP纳米晶荧光性能的影响. 通过调节Ag掺杂浓度和反应温度, 发现当Ag掺杂量为6%, 反应温度为200 ℃时, Ag∶InP纳米晶的发光效率最高. 将制备的Ag∶InP的表面包覆ZnSe, 粒子的荧光效率从原来的20%提高到45%. 将具有近红外荧光的Ag∶InP/ZnSe纳米晶应用于细胞成像, 结果表明制备的荧光纳米晶在细胞成像中清晰可见且毒性较低.     

Ag掺杂对n-ZnO纳米棒/p-GaN异质结结构和发光性能的影响

利用简单的水热合成法在p-GaN薄膜上制备了Ag掺杂的一维ZnO纳米棒(ZnO NRs),并且研究了Ag掺杂对于ZnO NRs结构和形貌以及n-ZnO NRs/p-GaN异质结发光特性的影响。结果表明,不同Ag掺杂浓度的ZnO纳米棒截面均呈六边形的棒状结构,且纳米棒的取向垂直于衬底;XRD分析结果表明,随着Ag掺杂浓度的增加,ZnO纳米棒(0002)晶面的峰位向衍射角减小的方向移动,表明Ag+置换了ZnO晶格中的部分Zn2+后使其晶格常数略增加;随着Ag掺杂浓度的增加,ZnO纳米棒近带边发光峰发生一定的红移并且强度逐渐减弱,黄带发光峰逐渐增强,n-ZnO NRs/p-GaN异质结具有更好的传输效率。     

Ag掺杂对n-ZnO纳米棒/p-GaN异质结结构和发光性能的影响

利用简单的水热合成法在p-GaN薄膜上制备了Ag掺杂的一维ZnO纳米棒（ZnO NRs）,并且研究了Ag掺杂对于ZnO NRs结构和形貌以及n-ZnO NRs/p-GaN异质结发光特性的影响。结果表明,不同Ag掺杂浓度的ZnO纳米棒截面均呈六边形的棒状结构,且纳米棒的取向垂直于衬底;XRD分析结果表明,随着Ag掺杂浓度的增加,ZnO纳米棒（0002）晶面的峰位向衍射角减小的方向移动,表明Ag⁺置换了ZnO晶格中的部分Zn²⁺后使其晶格常数略增加;随着Ag掺杂浓度的增加,ZnO纳米棒近带边发光峰发生一定的红移并且强度逐渐减弱,黄带发光峰逐渐增强,n-ZnO NRs/p-GaN异质结具有更好的传输效率。     

Alloyed (ZnSe)(x)(CuInSe2)(1-x) and CuInSe(x)S(2-x) nanocrystals with a monophase zinc blende structure over the entire composition range

Metastable zinc blende CuInSe(2) nanocrystals were synthesized by a hot-injection approach. It was found that the lattice mismatches between zinc blende CuInSe(2) and ZnSe as well as CuInSe(2) and CuInS(2) are only 2.0% and 4.6%, respectively. Thus, alloyed (ZnSe)(x)(CuInSe(2))(1-x) and CuInSe(x)S(2-x) nanocrystals with a zinc blende structure have been successfully synthesized over the entire composition range, and the band gaps of alloys can be tuned in the range from 2.82 to 0.96 eV and 1.43 to 0.98 eV, respectively. These alloyed (ZnSe)(x)(CuInSe(2))(1-x) and CuInSe(x)S(2-x) nanocrystals with a broad tunable band gap have a high potential for photovoltaic and photocatalytic applications.     

Fast scintillation processes in CsCl crystals comprising semiconductor nanocrystals

We analyzed the scintillation mechanism in CsCl single crystals comprising CsPbCl₃-like semiconductor nanocrystals. A decay component with a subnanosecond lifetime was observed and ascribed to the exciton luminescence in the nanocrystals. This is the first observation of scintillation from semiconductor nanocrystals. In addition, slower components were observed and ascribed to the intraionic transition at isolated Pb²⁺ ions and the Auger-free luminescence in the CsCl matrix. Furthermore, it was shown that the nanocrystals absorbed and re-emitted the scintillation photons from the isolated Pb²⁺ ions. The results in this report clearly indicates that the semiconductor nanocrystals function as ultrafast “luminescent centers,” and complicated scintillation dynamics are observed due to the luminescence from different components in the crystal and the radiative energy transfer between them.     

Synthesis of highly luminescent Cd(Se,S) nanocrystals

Highly luminescent semiconductor nanocrystals with graded band gap were synthesized using a hot injection method. The band gap of nanocrystals were controlled by gradual incorporation of sulfur to CdSe nanocrystals by applying severely asymmetric composition of reactants [(Cd)/(Se,S) ? 1]. The maximum emission wavelength of the grown nanocrystals was varied by controlling the concentration ratio of VI group element, i.e. Se and S. A green light was emitted from Cd(Se,S) nanocrystals with [Se]:[S] = 1:3 in the reactant mixture and the maximum quantum yield measured by comparing with Rhodamine 6G was larger than 80%.

     

On the Origin of the Large Stokes-Shift of the Emission of CdS Nanoparticles Embedded in a Phosphate Glass Matrix

XRD and TEM characterisation evidenced the formation of well-dispersed CdS nanoparticles inside a phosphate glass matrix. Optical absorption and time-resolved photoluminescence study were carried out on the prepared glass samples. Optical absorption revealed the fast character of the growth of CdS nanoparticles in this medium. Photoluminescence spectra showed only one large band with a maximum at almost 740 nm, which was associated to transitions between energy levels within the bandgap of the CdS nanoparticles. From the steady state and time-resolved measurements, it was suggested that the emission comes mainly from sulfur vacancies inside the nanocrystals and on its surface, which act as deep traps for the photogenerated electrons. The creation of such vacancies was attributed to the loss of sulfur during the glass preparation as evidenced from a chemical analysis using energy dispersive X-ray spectrometry. These traps may be also induced by the fast growth of CdS nanocrystals in this matrix or laser exposure during PL measurements. These CdS-doped glasses with an intense absorption in the UV–Vis region and a large emission band with long lifetime and a large Stokes-shift are adequate for luminescent solar concentrators, photocatalytic applications and solid-state lasers.     

CdS:Mn nanocrystals passivated by ZnS: synthesis and luminescent properties

Synthesis and characterization of highly luminescent ZnS-passivated CdS:Mn (CdS:Mn/ZnS) core/shell structured nanocrystals are reported. Mn-doped CdS core nanocrystals are produced ranging from 1.5 to 2.3 nm in diameter with epitaxial ZnS shell of wider band gap via a reverse micelle process. UV irradiation-stimulated photo-oxidation of the ZnS shell results in formation of sulfate (ZnSO(4)) as determined by x-ray photoelectron spectroscopy, which increases the photoluminescence emission intensity and subsequent photostability. Luminescent relaxation lifetime data present two different decay components, consisting of slow decay emission from the Mn center and a fast decay emission from a defect-related center. The impact of the density of surface defect states upon the emission spectra is discussed.     

Chirality of silver nanoparticles synthesized on DNA

Silver nanocrystals grown on a poly(dG)-poly(dC) double stranded DNA scaffold displayed circular dichroism at their surface plasmon excitation band. This chiral plasmon signature was not observed in a control experiment where silver nanocrystals of similar size were produced without the DNA template and adsorbed to the DNA. It is concluded that the DNA templated Ag nanocrystals had a preferred structural handedness.     

胶体半导体纳米晶的能带宽调控新方法

由于量子限域效应,半导体纳米晶的能带宽随粒子大小而改变。单纯依靠改变纳米晶大小来调控能带宽将引起许多技术和应用上的不便。本文对胶体半导体纳米晶的能带宽调控新概念和新的合成途径,包括近年来发展起来的通过采用合金纳米晶、反转Type－I及Type－II核/壳结构等进行了综述,并对各种途径的优缺点进行了描述。     

High quality CdSeS nanocrystals synthesized by facile single injection process and their electroluminescence

Highly luminescent CdSeS nanocrystals (quantum efficiency up to 85%), showing tunable luminescence properties from red to blue region with narrow band edge (FWHM = 34 nm), were synthesized by one-step addition of Se and S source mixture into the Cd precursor solution at elevated temperature, and the resulting nanocrystals were successfully embedded in a traditional OLED structure to give spectrally clean and narrow electroluminescence emission at identical positions of the photoluminescence spectrum.     

Magneto‐Optical Studies of HgTe/HgxCd1−xTe(S) Core–Shell Nanocrystals

The synthesis and magneto‐optical properties of HgTe nanocrystals capped with Hg_xCd_1?xTe(S) alloyed shells have been investigated. The magneto‐optical measurements included the use of optically detected magnetic resonance (ODMR) and circular polarized photoluminescence (CP‐PL) spectroscopy. The PL spectra suggest the existence of luminescence events from both the core HgTe and the Hg_xCd_1?xTe(S) shells. The continuous‐wave (cw) and time‐resolved ODMR measurements revealed that the luminescence at the shell regime is associated with a trap‐to‐band recombination emission. The electron trap is comprised of a Cd–Hg mixed site, confirming the existence of an alloyed Hg_xCd_1?xTe(S) composition. The ODMR data and the CP‐PL measurements together revealed the g‐values of the trapped electron and the valence band hole.