CdS半导体纳米晶的生长及其光谱研究

用玻璃沉淀技术制备了含过饱和CdS的玻璃固溶体,在一定条件下晶化处理使其长出CdS量子点,并采用了X射线衍射、高分辨扫描电镜、光吸收谱和荧光发光光谱等测试手段分析其性能,结果表明经过晶化处理可以在玻璃中长出CdS量子点,尺寸大约为10～25nm,吸收谱中出现明显的红移现象,反映出量子点的量子限域效应,荧光发光图谱中可以看出量子点发光主要由带隙发光和表面缺陷态发光组成,提高热处理温度可以改善晶粒的完整性.     

CdS纳米粒子的LB膜自组装研究

采用杯[8]衍生物的LB膜成功制备了尺寸可控的CdS纳米微粒.并用AFM、吸收谱、PL谱对其表面形貌和光学性能进行了研究.吸收谱表明循环1次时CdS纳米粒子的吸收边为425nm,这个值同体材料的520nm相比发生了明显的蓝移.随着循环次数的增加,CdS纳米粒子的吸收边逐渐红移,当循环3次时,其吸收边已经移到475nm,这表明纳米粒子的粒径在逐渐长大.CdS纳米粒子的PL谱表明,随着循环次数的增加,其发射峰值逐渐红移,这可能是由于量子尺寸效应造成的.     

SBS-OH模板制备CdS纳米粒子及表征

以SBS为基本原料,通过大分子化学反应制备得到羟基化SBS(SBS-OH).以N,N-二甲基甲酰胺为溶剂,SBS-OH为模板,乙酸镉及硫化钠为前驱物,在常温条件下"原位反应"制备得到CdS纳米粒子.通过UV-Vis、PL系统考察了SBS-OH浓度、前驱物浓度及配比等因素对CdS纳米粒子光学性质的影响.通过TEM对CdS纳米粒子的尺寸及形貌进行了表征.研究表明,利用SBS-OH的两亲性质,可以在极性溶剂DMF中得到具有冠状复合结构的CdS纳米粒子.随着前驱物浓度的增加,CdS纳米粒子的吸收强度增加,吸收带边红移,表现出较明显的量子尺寸效应.PL光谱表明CdS纳米粒子可以产生表面缺陷态的荧光发光特性,通过对实验结果的总结分析,探讨了复合结构CdS纳米粒子可能的形成机制.     

尺寸分布和界面混合对InAs/GaAs量子点光学性质的影响

研究了自组织生长模式(S-K modes)下量子点尺寸的不均匀分布对量子点发光性质的影响,对其光致发光峰进行了拟合计算.研究发现,量子点尺寸的不均匀分布导致了量子点发光峰的展宽以及发光峰位的红移.另一方面,后处理工艺中的退火及质子注入引起的界面混合导致了量子点PL谱发光峰的蓝移及半高宽的减小.     

核壳结构CdS/ZnS荧光量子点的制备与荧光性能研究

以氧化镉为镉源、硫单质为硫源、油酸为配体、在十八烯体系中合成单分散的CdS纳米颗粒,研究了配体浓度对纳米微粒的生长动力学、颗粒尺寸分布的影响.采用乙基黄原酸锌作为Zn、S源的反应前体,采用逐滴滴加的方法制备了具有核壳结构的CdS/ZnS量子点,吸收光谱和荧光光谱表明CdS/ZnS纳米粒子比单一的CdS纳米粒子具有更优异的发光特性.透射电子显微镜、X射线粉末衍射、X射线光电子能谱、选区电子衍射证明ZnS在CdS表面进行了有效包覆.所制备核壳结构纳米粒子具有较好的尺寸分布,荧光发射峰半高峰宽为18～20nm,荧光量子产率达40%.     

CdSe与CdSe/ZnS量子点合成及稀土掺杂

在LSS(liquid-solid-solution)多相体系中制得了CdSe、CdSe/ZnS量子点和Eu掺杂的量子点。利用TEM、XRD、PL、EDS对产物进行了表征。TEM结果显示所得的量子点形貌规则、尺寸均匀。XRD结果显示CdSe/ZnS量子点呈六方晶系。PL结果对比表明,合适厚度壳层ZnS包覆后的CdSe量子点发光效率明显提高,发光峰的半高宽有大幅度提高,并分析了所得的结果。掺杂稀土元素Eu后,CdSe(Eu)量子点在红光区域产生了新的发光峰;而CdSe(Eu)/ZnS量子点在红光区域内没有出现发光峰,并阐明了这种现象的原因。     

纳米CdS／聚（苯胺-邻氨基苯甲酸）复合薄膜的制备及表征

以苯胺和邻氨基苯甲酸为单体共聚而成的聚（苯胺-邻氨基苯甲酸）（PAOAA）为基体，制备了纳米CdS／PAOAA复合薄膜。纳米CdS粒子大小均匀，粒径分布窄，较稳定地存在于基体中，且随着硫化时间的延长粒径尺寸有所增加。荧光光谱表明纳米CdS／PAOAA复合薄膜的发光由CdS纳米粒子和PAOAA共同作用产生，在430nm和520nm附近出现了两大发光峰；CdS粒径的增加导致电子-空穴对在CdS内复合增大，表现为纳米CdS的荧光特征峰增强而PAOAA的荧光特征峰减弱。     

CdS纳米线阵列光致发光的研究

用直流电沉积法在多孔氧化铝模板中制备了高度有序的CdS纳米线阵列,SEM和XRD的观察和测量表明,CdS纳米线尺寸均匀、排列规整,具有六方纤锌矿结构,Cd和S的化学计量比为11.CdS纳米线阵列的光致发光测量显示,激发波长为325nm时,CdS纳米线阵列在450nm处有一强的PL峰,在484nm处还有一肩峰.对其光致发光机理进行了分析.     

圆偏振光诱导CdTe量子点再生长及其对光致发光的影响

实验研究了以3-巯基丙酸为配体合成的水溶性CdTe量子点经过非偏振光与圆偏振光照射处理后, 量子点的再生长变化规律。采用光致发光谱、紫外-可见吸收光谱、透射电子显微镜与X射线衍射等表征手段分析表明: 非偏振光会促进CdTe量子点的光氧化, 导致量子点尺寸缩小, 荧光发光峰位蓝移, 且发光效率降低; 而圆偏振光增强了配体的光氧化, 在量子点表面形成CdS层, 导致量子点尺寸进一步增大, 荧光发光峰红移, 且发光效率提升。进一步讨论了CdTe量子点与配体之间的键合作用, 相关光化学反应机制及其对量子点光致发光性质的影响。     

CdS及其稀土掺杂纳米带的制备与发光性质的研究

采用热蒸发法制备CdS及其稀土掺杂的纳米带(CdS∶Ce3+、CdS∶Er3+)。利用扫描电子显微镜(SEM)、X射线衍射仪(XRD)和荧光光谱仪(PL)对纳米带的形貌、晶体结构和发光性质进行了表征和分析。结果表明,所制备的纳米带的外形规则,表面光滑、平整,纳米带的厚度大约在20～60nm范围内;纳米带具有六方结构,晶格常数a=0.414nm、c=0.671nm;CdS纳米带的光致发光谱的谱峰位于405nm左右;CdS∶Ce3+纳米带的光致发光谱的谱峰位于523和535nm处;CdS∶Er3+纳米带的光致发光谱中观察到3个强的发光峰,分别位于525、556和582nm处。     

Preparation and characterization of overcoated II-VI quantum dots

A convenient route for the synthesis of high-quality overcoated II-VI quantum dots (QDs) is reported in this paper. Simple salts, such as Cd(Ac)2 and Zn(Ac)2 were used to replace organometallics, whose disadvantage is obvious. Size-tunable core/shell structured QDs (CdSe/ZnS, CdSe/CdS, etc.) were synthesized. They were of narrow size distribution and had good monodispersivity and photoluminescence (PL) properties. The spectrum was symmetrical and sharp-pointed (with the full width at half-maximum (fwhm) of about 20-30 nm). The quantum yield (QY) was improved to 60-80% from 20-30% for bare QDs and remained stable at least for 6 months. The primary overcoated QDs were modified with biomacromolecules by a direct mechanical rubbing strategy, which is very simple and fast. The results obtained by UV-vis, PL, atomic force microscopy (AFM), and fluorescence microscopy imaging showed that the modified QDs were of good fluorescent and monodisperse characteristics. They are likely to be used further for biological labels.     

Preparation of lanthanide doped CdS, ZnS quantum dots in natural polysaccharide template and their optical properties

Employing a biomimic method using polysaccharide as template, luminescent lanthanide ions doped CdS and ZnS quantum dots (QDs) were prepared. According to the results of TEM and absorbance, nanocrystals with an average size of 6 nm were formed under mild condition without any toxic and expensive agent applied. Differentiating from the un-doped CdS and ZnS QDs prepared in polysaccharide template, the lanthanide doped QDs exhibited obvious dopant emission in their photoluminescence spectrum. It was also found that the dopant PL became more prominent with increasing lanthanide doping concentration, while the highest PL intensity was obtained at a doping level of 1% for both of CdS and ZnS QDs. When different lanthanide ions were introduced into the CdS QDs in polysaccharide template, varied emission wavelength were able to be obtained. This study provides an easy, mild and environmental friendly alternative method to prepare doped quantum dots. In addition, the bioactivity and processabilities endowed by the polysaccharide template may expand the applications potential of this type of optical materials.     

Preparation, optical properties and solar cell applications of CdS quantum dots synthesized by chemical bath deposition

We reported on temperature-dependent photoluminescence (PL) studies of CdS quantum dots (QDs, ~5 nm in diameter) grown onto TiO₂ nanorod arrays by chemical bath deposition. By constructing a liquid-junction solar cell, a power conversion efficiency of 0.88 % was demonstrated. In addition, we observed anomalous emission behavior, specifically a ‘Λ’-shaped (blueshift–redshift) temperature dependence of the peak energy for CdS related PL with increasing temperature. From a study of the integrated PL intensity as a function of temperature, it was revealed that thermionic dissociation of excitons (carriers) out of local potential minima into higher energy states was the dominant mechanism leading to the quenching behavior of the QDs related PL. At 110 K, the localized excitons were totally dissociated and converted to the free excitons. Our results shed light on the exciton-dissociation process in CdS QDs and can be used for the proposed solar cell application.     

Radiative interface state study in CdSe/ZnS quantum dots covered by polymer

The paper presents the transformation of photoluminescence (PL) spectra of nonconjugated and bioconjugated core/shell CdSe/ZnS QDs covered by PEG polymer at the aging in ambient air. Studied QDs are characterized by the sizes: (i) 3.6-4.0 nm and color emission with the maxima at 560-565 nm (2.19-2.25 eV) and (ii) 5.2-5.3 nm and with emission at 605-610 nm (2.02-2.08 eV). The part of 565 nm CdSe/ZnS QDs has been bioconjugated to the mouse anti PSA (Prostate-Specific Antigen) antibodies and the part of 605 nm QDs has been bioconjugated to the antihuman IL10 (Interleukin 10) antibodies using the commercially available 565 nm and 605 nm QD conjugation kits. It is revealed that the aging process in ambient air has the very strong impact on PL spectra of nonconjugated core/shell CdSe/ZnS QDs covered with PEG polymer. The aging process relates to the polymer modification in ambient air that is accompanied by the three effects: (i) polymer transparency increasing for the emission of CdSe cores (2.03 or 2.20 eV), (ii) the intensity stimulation of high energy PL bands (2.37, 2.73 and 3.06 eV) related to the interface states at the ZnS/PEG polymer interface and (iii) the elastic strain modification in QD systems. The concentration of interface states at the ZnS/polymer interface increases at the aging of PEG polymer in ambient air.     

Metal ion (silver, cadmium and zinc ions) modified CdS quantum dots for ultrasensitive copper ion sensing

Metal ion (Ag(+), Cd(2+), Zn(2+)) modified CdS quantum dots (QDs) were synthesized and used for Cu(2+) sensing. Modification by these metal ions could enhance the PL intensity of CdS QDs with the extent of the PL enhancement being related to the concentration of the metal ions. Different metal ion (Ag(+), Cd(2+), Zn(2+)) modified CdS QDs also showed different analytical characteristics for Cu(2+) sensing. In particular, Ag( + ) modified CdS QDs showed greatly enhanced sensitivity for Cu(2+) determination than did the unmodified CdS QDs. A limit of detection (LOD) of 2.0 × 10(-10) M was obtained for Ag(+) modified CdS QDs, which is the lowest LOD obtained using QDs as fluorescence probes for Cu(2+) sensing. This study demonstrates the important role of surface state of QDs in fluorescence sensing.     

Effect of cadmium sulphide quantum dot processing and post thermal annealing on P3HT/PCBM photovoltaic device

The present study demonstrates the effect on photovoltaic performance of poly(3-hexylthiophene) (P3HT) on doping of cadmium sulphide (CdS) quantum dots (QDs). The P3HT/CdS nanocomposite shows a 10 nm blue shift in the UV-vis absorption relative to the pristine P3HT. The blue shift in the absorption of the P3HT/CdS nanocomposite can be assigned to the quantum confinement effect from the CdS nanoparticles. Significant PL quenching was observed for the nanocomposite films, attributed to additional decaying paths of the excited electrons through the CdS. Solar cell performance of pure P3HT and dispersed with CdS QDs have been studied in the device configuration viz indium tin oxide (ITO)/poly(3,4-ethylendioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS)/P3HT:PCBM/Al and ITO/PEDOT:PSS/ P3HT:CdS:PCBM/Al, respectively. Incorporation of CdS QDs in the P3HT matrix results in the enhancement in the device efficiency (?) of the solar cell from 0.45 to 0.87%. Postproduction thermal annealing at 150 °C for 30 min improves device performance due to enhancement in the device parameters like FF, V_OC and improvement in contact between active layer and Al.     

Temperature dependent luminescence of azobenzene capped CdS quantum dots

Cadmium sulfide (CdS) quantum dots (QDs) are prepared at room temperature by "form-fill-seal" method, while the azobenzene is used as surfactant to control the particle size and to prevent agglomeration. The typical size of CdS nanoparticles is estimated as 2 nm by X-ray diffraction. The absorption spectra of CdS QDs are measured at room temperature and a new absorption peak associated with the surface excited state is found. The luminescence property of the CdS QDs is studied at room temperature and low temperature. Two photoluminescence peaks exist in the temperature range of 8-300 K. One peak at 460 nm is attributed to CdS QDs, while the other one at 667 nm comes from the transition of surface excited state and its intensity decreases with temperature increasing.     

Fast-grown CdS quantum dots: Single-source precursor approach vs microwave route

A cross-disciplinary protocol of characterization by joint techniques enables one to closely compare chemical and physical properties of CdS quantum dots (QDs) grown by single source precursor methodology (SSPM) or by microwave synthetic route (MWSR). The results are discussed in relation with the synthesis protocols. The QD average sizes, reproducible as a function of the temperatures involved in the growth processes, range complementarily in 2.8–4.5 nm and 4.5–5.2 nm for SSPM and MWSR, respectively. Hexagonal and cubic structures after X-ray diffraction on SSPM and MWSR grown CdS QDs, respectively, are tentatively correlated to a better crystalline quality of the latter with respect to the further ones, suggested by (i) a remarkable stability of the MWSR grown QDs after exposure to air during several days and (ii) no evidence of their fragmentation during mass spectrometry (MS) analyses, after a fair agreement between size dispersities obtained by transmission electron microscopy (TEM) and MS, in contrast with the discrepancy found for the SSPM grown QDs. Correlatively, a better optical quality is suggested for the MWSR grown QDs by the resolution of n > 1 excitonic transitions in their absorption spectra. The QD average sizes obtained by TEM and deduced from MS are in overall agreement. This agreement is improved for the MWSR grown QDs, taking into account a prolate shape of the QDs also observed in the TEM images. For both series of samples, the excitonic responses vs the average sizes are consistent with the commonly admitted empirical energy-size correspondence. A low energy PL band is observed in the case of the SSPM grown QDs. Its decrease in intensity with QD size increase suggests a surface origin tentatively attributed to S vacancies. In the case of the MWSR grown QDs, the absence of this PL is tentatively correlated to an absence of S vacancies and therefore to the stable behavior observed when the QDs are exposed to air.     

CdS/TiO2纳米棒阵列复合材料的制备及其光电化学特性

以水热法在氟掺杂的氧化锡透明导电玻璃(FTO)上制备的TiO₂纳米棒阵列为衬底, 通过连续化学水浴沉积(S-CBD)法将CdS量子点 (QDs)沉积在TiO₂纳米棒上, 形成CdS/TiO₂阵列复合材料。分别利用高分辨透射电子显微镜(HRTEM)、 场发射扫描电子显微镜(FESEM)、 X射线衍射(XRD)和紫外可见光谱(UV-vis)等对样品的形貌、 晶型以及光吸收性能进行了表征。结果表明, TiO₂纳米棒阵列长度约为2.9 μm, CdS QDs的尺寸大约在5~9 nm。随着沉积层数的增加, CdS QDs的厚度增加, 同时伴随着光吸收边的红移。通过电流-电压特性曲线对其光电流-电压特性进行了分析, 发现光电流和光电转换效率均呈现出先增大后减小的规律。100 mW/cm²的光照下, 在S-CBD为7层时, 光电流和开路电压最大值分别达到2.49 mA·cm^-2和1.10 V, 而电池的效率达到最大值1.91%。     

CdSe/Cd1−x Zn x S core/shell quantum dots with tunable emission: growth and morphology evolution

We demonstrate an organic synthesis to fabricate hydrophobic core/shell CdSe/Cd_1?x Zn _x S quantum dots (QDs) with tunable photoluminescence (PL) between green and red at relatively low temperature using trioctylphosphine S reacted directly with cadmium and zinc acetate. A seeded growth strategy was used for preparing large CdSe cores. Large CdSe cores revealed a rod-like morphology while small one exhibited a spherical shape. Being coated with a Cd_1?x Zn _x S shell on spherical CdSe cores with an average size of 3.9 nm in diameter, core/shell QDs exhibited a cubic morphology (a length of 5 nm). In contrast, the core/shell QDs created using a small core (3.3 nm in diameter) show a spherical morphology. Namely, the anisotropic aggregation behavior of CdS monomers on CdSe cores occurs when the rod-like core is coated with a Cd_1?x Zn _x S shell. CdS interlayer plays an important role for such morphology evolution because all CdSe cores with a pure ZnS shell exhibited a spherical morphology. The PL properties of CdSe/Cd_1?x Zn _x S core/shell QDs depended strongly on the size and morphology of the cores. The QDs revealed a narrow and tunable PL spectrum. It is believed that this facile strategy can be extended to synthesize other core–shell QDs at low temperature.