Asymmetric effect of (000$\bar{1}$) and (0001) facets on surface and interface properties of CdS single crystal

A different effect of (0001) and (000[`1]\bar{1}) crystal facets of the cadmium sulfide (CdS) wurtzite structure terminated with Cd and S atoms, respectively, was observed in respect to the properties of the crystal surface and interface with metal or organic semiconductor contacts. In addition to the different surface morphology, a bare CdS single crystal showed different features in photoluminescence from the Cd- and S-terminated surfaces. Different adhesive behavior of poly(3,4-ethylenedioxythiophene): poly(styrene sulfonic acid) (PEDOT:PSS) films in respect to the Cd- and S-terminated facets of the crystal has also been found. Photovoltaic properties of hybrid CdS/PEDOT:PSS heterojunctions have been shown to be sensitive in respect to the crystal facet used. Thin films of aluminum (Al) equally deposited onto the opposite crystal facets revealed much smaller sheet resistance on the sulfur facet than on the cadmium one, which has been assigned to the difference in both chemical interaction with the surface atoms and surface morphology. Current–voltage characteristics of an apparently symmetric Al/CdS/Al structure with Al electrodes deposited onto the opposite crystal facets showed asymmetric behavior depending on the bias direction applied to the Cd or S-terminated facet, with the barrier for electrons at the Al/S-terminated interface, respectively.     

采用紫外光照法在磷酸盐玻璃中合成CdS/Ag复合微粒

掺杂有Ⅱ-Ⅵ族半导体纳米颗粒(如CdS)或者过渡金属(如Ag)的玻璃由于其较大的非线性光学效应而引起人们的极大兴趣,而同时掺杂有半导体/金属的复合微粒则可以进一步增强玻璃的三阶非线性效应,因此成为目前的研究热点。我们利用玻璃沉淀技术及随后的热处理和紫外光还原技术制备了含高浓度(1%)Ag微粒的玻璃,并采用X射线衍射分析了其物相,用高分辨扫描电镜分析了其形貌,以及测试了其吸收和发光性能。从CdS/Ag复合微粒的扫描照片可以发现晶粒均匀分布在玻璃中,尺寸约为1μm。X射线衍射发现经过热处理和紫外光照的样品衍射峰中含有CdS和Ag,而只进行热处理的样品则只含有CdS,未处理的样品则显非晶态。CdS/Ag复合微粒的吸收峰呈现典型的表面等离子共振峰(420nm)以及CdS的峰(600nm),只含有CdS微粒的样品的吸收峰则在480nm附近,未处理的样品在320nm附近有一个吸收峰,这可能是由于样品在快速冷却过程中的微小晶化造成的。只含有CdS微粒的样品有三个明显的发光峰,然而CdS/Ag复合微粒的发过峰则消失。我们提出了共振能量转移机制来解释该现象。讨论了紫外光照还原Ag微粒的机制。可以认为通过紫外光照,CdS表面的电子被激发出来还原Ag+,从而形成银颗粒,伴随着空穴则被表面缺陷所捕获。     

反应前驱物中n(S)∶n(Cd)对CdS薄膜结构及发光特性的影响

采用化学水浴以CdCl2·H2O、CS( NH2)2、NH4Cl、NH3·H2O和去离子水作为反应前驱物制备CdS纳米晶薄膜.采用扫描电镜( SEM)、X射线衍射(XRD)、透射光谱和稳态荧光光谱,研究了反应前驱物中不同的n(S)∶n(Cd)对所制备的CdS薄膜的形貌、结构和光学性能的影响.结果表明:反应前驱物中n(S...     

Performance improvement in CdTe solar cells by modifying the CdS/CdTe interface with a Cd treatment

The performance of n-CdS/p-CdTe solar cells is often degraded under light soaking or thermal stress, even though the technology of CdTe solar cells is close to a commercial level. The Cu diffusion from a Cu back contact to a CdS window layer might degrade the cell's performance. To prevent the Cu diffusion, a very-thin intrinsic CdTe layer was introduced at the n-CdS/p-CdTe interface by depositing a very-thin Cd metal layer on the CdS film and converting the Cd metal into intrinsic CdTe during p-CdTe deposition at high temperature. By the Cd treatment on CdS surface, pinholes or voids were eliminated at the CdS/CdTe and the intermixing of Te and S at the interface was much suppressed. The depletion width was much increased and the intensity of LTPL peak was increased. The analysis suggested that an intrinsic CdTe interlayer was formed and the surface recombination rate was suppressed by the intrinsic interlayer. As a result, the short circuit current of the CdTe solar cell was significantly increased due the increased current gain in the blue wavelength region. The thermal stability of the CdTe solar cell was also greatly improved and the Cu diffusion was retarded by the intrinsic CdTe interlayer at the n-CdS/p-CdTe.     

Cadmium (II) pyrrolidine dithiocarbamate complex as single source precursor for the preparation of CdS nanocrystals by microwave irradiation and conventional heating process

The complex of cadmium with pyrrolidine dithiocarbamate Cd(pdtc)₂ has been used as single source precursor for the synthesis of CdS nanoparticles. The formation of CdS nanostructures was achieved by thermal decomposition of the complex under microwave irradiation and conventional heating in presence of hexadecylamine. The CdS nanoparticles with disordered close-packed structure were obtained under microwave irradiation, whereas wurtzite hexagonal phase CdS nanorods were obtained by conventional heating method (up to 150 °C). Scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and high resolution transmission electron microscopy (HRTEM) studies also were carried out to study the structure and morphology of nanoparticles. The optical property of the CdS nanoparticles was studied by UV-visible and fluorescence emission spectral studies. Fluorescence measurements on the CdS nanoparticles show a strong emission spectrum with two sub bands that are attributed to band-edge and surface-defect emissions. The reduction of a suitable cadmium metal complex is considered to be one of the single pot methods to generate CdS semiconductor nanoparticles with different shapes and high yield.     

Intercalative route to heterostructured nanohybrids

We have successfully synthesized inorganic–inorganic, organic–inorganic and bio-inorganic nanohybrids by applying an intercalation technique systematically to layered titanate, molybdenum disulfide (MoS₂), Bi-based cuprate superconductors (Bi₂Sr₂Ca_m−1Cu_mO_y (m=1, 2, and 3; BSCCO)), and to layered double hydroxides (LDHs), those which are of high importance in terms of basic understanding of intercalation reactions and of their practical applications. The inorganic–inorganic systems such as TiO₂-pillared titanate, TiO₂-pillared MoS₂, and CdS–MoS₂ hybrids were synthesized by exfoliation–restacking method. A novel pillaring process using an osmotic swelling was developed to prepare TiO₂-pillared layered titanate with a large surface area, high thermal stability, and enhanced photocatalytic activity. And the intercalation of TiO₂ and/or CdS nanocluster into the two dimensional MoS₂ lattice could be also realized by exfoliating and reassembling the lithiated molybdenum disulfide (LiMoS₂) in the presence of cationic TiO₂ and/or CdS nanocluster in an aqueous solution, respectively, to obtain the semiconductor–semiconductor hybrids. On the other hands, the organic–inorganic hybrids were achieved via intercalative complexation of iodine intercalated BSCOO with organic salt of Py–C_nH_2n+1I (Py=pyridine). The high-T_c superconducting intercalate with its remarkable lattice expansion can be applied as a precursor for superconducting colloids when dispersed in an appropriate solvent. This superconducting hybrid material had an unique structural feature of a superconducting-insulating-superconducting multilayer with atomically clean interfaces. Especially, this organic–inorganic nanohybrid is expected to be a promising precursor for preparing the superconducting colloidal suspension, which could be applied to the fabrication of superconducting films or wires. Recently, we were very successful in demonstrating in which the formation of bio-inorganic hybrids stabilized in the interlayer space of LDH retain their chemical and biological integrity. If necessary, LDH, as a reservoir, can be intentionally removed by dissolving it in an acidic media in such a way the interlayer biomolecules can be recovered or the intercalated biomolecules can be released from the LDH via ion-exchange reaction in electrolyte. It is, therefore, concluded that the inorganic LDH can play a role as a gene reservoir or carrier for various unstable organic or bio-molecules such as drugs and genes.     

Hybrid polymer-inorganic materials: multiscale hierarchy

The paper describes a new approach to producing hybrid composite materials with multiscale morphologies. We doped polymer submicrometer spheres with semiconductor or metal (CdS or Ag, respectively) nanoparticles and used these doped microspheres as the functional building blocks in production of hybrid periodically structured materials. The preparation of hybrid polymer particles included the following stages: (i) synthesis of monodisperse polymer microspheres, (ii) in situ synthesis of the inorganic nanoparticles either on the surface, or in the bulk of the polymer beads, and (iii) encapsulation of hybrid microspheres with a hydrophobic shell. We demonstrated that by changing the composition of the polymer beads good control could be achieved over the size of the nanoparticles.     

合成聚丙酰胺-硫属半导体复合纳米材料的新技术

在水溶液体系中采用同步聚合－水解技术制备聚丙烯酰胺－半导体纳米复合材料，该ＳＰＨ技术是基于丙烯胺单体的聚合和ＭＳ纳米粒子的形成同步发生，使生成的半导体纳米粒子可均匀分散在聚丙烯酰胺基质中，该技术还为制备其它有机聚合物－金属硫化物纳米复合物提供了一种新途径。     

Investigation of polymer/inorganic hybrid photovoltaic device using quantum dots as the interface modifier

CdS quantum dots (QDs) were introduced as an interface modifier in the poly(3-hexylthiophene) (P3HT)/TiO₂ nanorod arrays hybrid photovoltaic device. The presence of CdS QDs interlayer was found to provide enhanced light absorption, increased interfacial recombination resistance at the P3HT/TiO₂ interfaces, thus leading to a lower recombination rate of the electrons due to the stepwise structure of band edge in P3HT/CdS/TiO₂, which accounts for the observed enhanced photocurrent and photovoltage of the hybrid solar cells. The optimized performance was achieved in P3HT/CdS/TiO₂ hybrid solar cells after deposition of CdS QDs for 10 cycles, with a power conversion efficiency of 0.57 %, which is nearly ten times higher than that of P3HT/TiO₂. The findings indicate that inorganic semiconductor quantum dots provide effective means to improve the performance of polymer/TiO₂ hybrid solar cells.     

Photovoltaic characteristics of hybrid MEH-PPV-nanoparticles compound

Organic solar cell research has vastly developed in recent years. These organic solar cells however are still limited to low power conversion efficiencies. This has led to the generation of photovoltaic cells based on hybrid nanoparticle-organic polymer materials. The hybrid solar cell has the potential of bridging the efficiency gap which is present in organic and inorganic semiconductor materials. This paper focuses on characterization of fabricated hybrid active layer consisting of organic polymer infused with semiconductor nanoparticles. The active layer was deposited on the substrate using the spin coating technique. Materials used in the active layer are poly (2-methoxy, 5-(2-ethyl hexyloxy) p-phenyl vinylene) MEH-PPV, cadmium telluride (CdTe) and cadmium sulphide (CdS). The fabricated solar cells with active layer of MEH-PPV only were found to have a power conversion efficiency of 0.1% for 1 W, hybrid cell with active layer of MEH-PPV/CdTe has power conversion efficiency of 0.15% for 1 W and hybrid cell with active layer of MEH-PPV/CdTe/CdS has power conversion efficiency of 0.18% for 1 W.     

Role of surface modification of CdS nanoparticles on the performance of hybrid photovoltaic devices based on p-phenylenevinylene derivate

The role of organic capping ligand of semiconductor nanoparticles in dictating the interfacial charge transfer processes in hybrid semiconductor nanoparticles/polymer-based photovoltaic devices is investigated. Morphology, optical and structural study of the CdS nanoparticles and the hybrid material were accomplished using X-ray diffraction (XRD), absorption (UV–vis), atomic force microscopy (AFM), transmission electron microscopy (TEM), photoluminescence (PL) and time resolved photoluminescence spectroscopy (PLRT). A broad band absorption in UV–visible region and considerable fluorescence quenching of MEH-PPV in the composites are noted indicating a photo-induced charge transfer and dissociation of excitons. Time-resolved photoluminescence measurements indicating decreased lifetime further confirm this process. The solar cells open-circuit voltage and short-circuit current were improved using thiophenol modified CdS nanoparticles as electron acceptor in comparison to MEH-PPV only device demonstrating a promising approach to enhance charge transport in the hybrid nanoparticles–polymer composite photovoltaic cells (PV).     

CdS半导体超微粒样品光谱性质的研究

纳米尺度的半导体超微粒在线性和非线性光学方面表现出来的奇特性质使其成为研究和开发新的功能材料的热点。成键为 S、P轨道的 - 族金属硫化物半导体 ,电子结构和晶体结构均较为简单 ,结晶性能好 -界面无序结构少 ,在纳米尺度上其结构仍与体相材料近似 ,因此 ,成为研究量子尺寸效应的理想材料。本文对采用化学微乳液法合成的 Cd S半导体超微粒的光谱性质进行了研究 ,实验结果显示 ,Cd S超微粒样品的吸收光谱的带边与体相相比发生了蓝移 ;从吸收光谱中可以看到 ,Cd S超微粒样品的吸收边随粒径减少而向短波方向移动。拉曼光谱的电子—— L O声子耦合在粒子尺寸 2 .4- 2 .9nm范围内与粒子尺寸无关     

Colloidal semiconductor quantum dots: Potential tools for new diagnostic methods

We present and discuss the application of colloidal semiconductor quantum dots for diagnostic purposes, with special emphasis for cancer. We prepared and applied core-shell cadmium sulfide-cadmium hydroxide (CdS/Cd(OH)₂) semiconductor quantum dots in aqueous medium. Tissue and cells labeling was evaluated by laser scanning confocal microscopy as well as by conventional fluorescence microscopy. The procedure presented in this work, shown to be a promising tool for fast, low-cost and precise cancer diagnostic protocols.     

The origin of ferromagnetism in Pd-doped CdS

The electronic structures and magnetic properties of Pd-doped CdS have been studied by a first principles study. We find that the material becomes 100% spin-polarized when Pd substitutes for Cd atom in a 3×3×2 CdS supercell, and forms a diluted magnetic semiconductor (DMS). A long-range ferromagnetic (FM) coupling is obtained between two Pd dopants. We concluded that the hybridized Pd(4d)–S(3p)–Cd(4d)–S(3p)–Pd(4d) chain through p–d coupling is responsible for the long-range FM coupling.     

Surface-defect-states photoluminescence in CdS nanocrystals prepared by one-step aqueous synthesis method

CdS nanocrystals were prepared by a simple one-step aqueous synthesis method using thioglycolic acid (TGA) as the capping molecule, and characterized by X-ray powder diffraction (XRD), UV-vis absorption spectra and photoluminescence (PL) emission spectroscopy. The effects of both TGA/Cd and Cd/S molar ratio on the surface-defect-state PL intensity of CdS nanocrystals have been investigated. It was found that all of the as-prepared CdS nanocrystals showed a strong broad emission in the range of 450-700 nm centered at 560 nm, which was attributed to the recombination of an electron trapped in a sulfur vacancy with a hole in the valance band of CdS. The surface-defect-states emission intensity of CdS nanocrystals significantly increased with the increase of Cd/S molar ratio, and showed a maximum when Cd/S molar ratio was 2.0. If Cd/S molar ratio continued to increase, namely more than 2.0, the surface-defect-states emission intensity would decrease. It was found that the surface-defect-states emission intensity increased with the increase the TGA/Cd molar ratio, and showed a maximum when the TGA/Cd molar ratio was equal to 1.8, and a further increase of the TGA/Cd molar ratio would lead to the decrease of the surface-defect-states emission intensity.     

CdS纳米粒子的自组装单分子膜制备研究

利用疏基乙酸与草酸的混合自组装单分子膜成功制备了粒径分布均匀的CdS纳米粒子，并用SEM，XRD，XPS，PL对样品进行了表征。SEM表明形成在自组装单分子膜表面上的CdS纳米粒子的平均粒径约为45nm。XPS表明在自组装单分子膜表面形成了CdS纳米粒子。PL谱表明CdS纳米粒子在675nm有一峰值波长，我们认为这一发光是由表面缺陷造成的。     

Strong enhancement of band-edge photoluminescence in CdS nanocrystals prepared by one-step aqueous synthesis method

CdS nanocrystals were prepared by a simple one-step aqueous synthesis method using thioglycolic acid (TGA) as the capping molecule. The effects of Cd precursor concentration and the TGA/Cd molar ratio on the photoluminescence properties of the CdS nanocrystals were investigated. It was found that both the remained free cadmium monomers and Cd-(SR)_x complexes played an important role in the nanocrystal nucleation growth and surface reconstruction. CdS nanocrystals with desired surface state could be obtained at high Cd precursor concentration and low TGA/Cd molar ratio.     

利用Cd(OH)_2选择性包覆与光分解腐蚀缩小CdS纳米微粒的尺寸分布的研究

提出结合Ｃｄ（ＯＨ）２ 选择性包覆与光分解腐蚀法缩小ＣｄＳ纳米微粒的尺寸分布, 并通过对ＣｄＳ纳米微粒发射光谱的研究证实了这一设计思想． 以多聚磷酸钠（ＨＭＰ）为稳定剂合成ＣｄＳ纳米微粒, 再通过Ｃｄ２＋ 与ＯＨ－ 的选择性包覆在大粒径的ＣｄＳ纳米微粒表面形成一层Ｃｄ（ＯＨ）２, 然后溶液置于日光下辐照处理, 数天后, 未经包覆的小粒径ＣｄＳ纳米微粒被日光腐蚀分解, 溶液中只剩下被Ｃｄ（ＯＨ）２ 包覆的大粒径ＣｄＳ纳米微粒, 这样即可达到缩小ＣｄＳ纳米微粒尺寸分布的目的．     

Growth kinetics and long-term stability of CdS nanoparticles in aqueous solution under ambient conditions

The ubiquity of naturally occurring nanoparticles in the aquatic environment is now widely accepted, but a better understanding of the conditions that promote their formation and persistence is needed. Using cadmium sulfide (CdS) as a model metal sulfide species, thiolate-capped CdS nanoparticles were prepared in the laboratory to evaluate how aquatic conditions influence metal sulfide nanoparticle growth and stability. This work examines CdS nanoparticle growth directly in aqueous solution at room temperature by utilizing the size-dependent spectroscopic properties of semiconductors detectable by UV/vis. CdS nanoparticle growth was governed by oriented attachment, a non-classical mechanism of crystallization in which small precursor nanoparticles coalesce to form larger nanoparticle products. Nanoparticle growth was slowed with increasing capping agent and decreasing ionic strength. In addition to examining the short-term (hours) growth of the nanoparticles, a long-term study was conducted in which cysteine-capped CdS nanoparticles were monitored over 3 weeks in solutions of various ionic strengths. The long-term study revealed an apparent shift from small nanoparticles to nanoparticles twice their original size, suggesting nanoparticle growth may continue through oriented attachment over longer time scales. High-ionic strength solutions resulted in salt-induced aggregation and eventual settling of nanoparticles within days, whereas low-ionic strength solutions were stable against settling over the course of the experiment. Sulfide recovery from cysteine-capped CdS nanoparticles as acid volatile sulfide was nearly quantitative after 2 weeks in fully oxygenated water, demonstrating significantly slowed oxidation of sulfide when complexed to Cd(II) within CdS nanoparticles. The nanoparticles were also shown to be resistant to oxidation by Fe(III) (hydr)oxide. This study illustrates that aggregation, rather than chemical oxidation, is likely more important to the lifetime of many metal sulfide nanoparticles in the aquatic environment.     

Graphene nanocomposites of CdS and ZnS in effective water purification

The present work deals with syntheses of CdS/graphene and ZnS/graphene nanocomposites by hydrothermal reaction of graphene oxide and morpholine-4-carbodithioate complex of Cd and Zn, respectively. The corresponding nanocomposites has been investigated separately as photocatalyst in the decomposition of methylene blue in the presence of UV light and also as adsorbents in the removal of Cd(II) and Pb(II) ions in contaminated water. These studies have established that CdS/graphene and ZnS/graphene are effective photocatalyst as well as effective adsorbents in the removal of Cd(II) and Pb(II) ions to an extent of 97 and 99 % by ZnS/graphene and CdS/graphene nanocomposite, respectively, under 1 g L^?1 of adsorption dose and at pH ~7. Further studies also established Langmuir model befitting for the adsorption of Pb(II) and Cd(II) ions on CdS/graphene and ZnS/graphene, respectively. The presence of interfering ions on extent of Cd(II) and Pb(II) removal has also been reported.