Synthesis and characterization of colloidal nanocrystals of ternary chalcogenide compounds

Colloidal nanocrystals of CuInS₂ and CuInSe₂ were synthesized in an apolar noncoordinating medium using 1-dodecanethiol as a ligand. A semiconductor shell of ZnS was formed for CuInS₂ nanocrystals obtained by the injection method. The obtained samples were characterized by absorption spectroscopy and photoluminescence.

     

Optical transient bleaching/absorption of surface-oxidized CuInS2 nanocrystals

2 nanocrystals in a polymer film have been studied with the picosecond pump-probe technique. The oxidized CuInS₂ nanocrystals have an additional absorption band with a peak at 1.03 eV, which is bleached under picosecond excitation. Rapid (∼50 ps) trapping into midgap surface states results in long-lived (≫300 ps) bleaching and induced absorption features. A schematical energy-level diagram for oxidized CuInS₂ nanocrystals is given based on the experimental results. Received: 7 January 1997/Revised version: 16 April 1997     

直流三极溅射法制备CuInS2 薄膜

采用直流三极溅射装置制备获得了CuInS₂薄膜, 其中溅射靶采用一定面积比的[Cu]/[In]混合靶,反应气体采用CS₂气体. 本文中主要研究了0.02 Pa分压反应气体条件下不同面积比的[Cu]/[In]混合靶和沉积基板温度对CuInS₂薄膜结构和成分的影响, 其中CuInS₂薄膜制备所用时间为2 h生长的厚度为1—2 μm. 通过对CuInS₂薄膜的EPMA, X射线衍射测试分析表明, 最佳的CuInS₂薄膜可在面积比[Cu]/[In]混合靶为1.4:1和可控温度(150, 250和350 ℃)的条件下制备获得, 并且其结构被确认为黄铜矿结构. 通过实验结果计算出CuInS₂薄膜层有约为8.9%的C杂质含量.     

Investigations of solvents and various sulfur sources influence on the shape-controlled synthesis of CuInS2 nanocrystals

CuInS₂ (CIS) nanocrystals were successfully synthesized through a hot-injection technique employing a reaction of copper (I) acetate and indium (III) acetate with tert-dodecanethiol as a source of sulfur, and trioctylphosphine oxide and 1-dodecanethiol were used as ligands. The reaction medium was a mixture of two solvents: oleylamine and 1-octadecene. Varying the ratio between both solvents leads to the formation of wurtzite CuInS₂ particles with shapes ranging from triangular to rod-shaped with length up to 50 nm. Oleylamine turned out to influence the reaction condition in two opposite ways: by leading to monomer depletion before the injection of the sulfur precursor, and at the same time increasing the activity of the monomers remaining in solution. By changing the sulfur source from tert-dodecanethiol to sulfur dissolved in oleylamine, triangular particles with zinc blend structure and a smaller size (~5 nm) were synthesized. The final materials were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDX), and absorption spectroscopy (UV?CVis).     

Properties of CuIn(SxSe1−x)2 polycrystalline thin films prepared by chemical spray pyrolysis

CuIn(S_xSe_1−x)₂ thin polycrystalline films were grown by the chemical spray pyrolysis method on the glass substrate at 280-400°C. The alloy composition in the film was studied with relation to that in the splay solution. Films were characterized by X-ray diffraction, optical absorption, Raman spectroscopy, resistivity and surface morphology. The CuInSe₂-rich alloy films grown at high substrate temperature had chalcopyrite structure, while, the CuInS₂-rich films grown at low substrate temperature exhibited sphalerite structure. Optical-gap energies were smaller than that of the bulk crystal by 0.1-0.2 eV for CuInS₂-rich films. Raman spectra exhibited both CuInSe₂-like and CuInS₂-like A₁ modes, and their relative changed systematically with alloy composition.     

Optical properties of CuInS2 nanoparticles in the region of the fundamental absorption edge

Glasses are obtained that contain CuInS₂ nanoparticles dispersed in a silicate matrix. The absorption and luminescence spectra of the glasses containing CuInS₂ nanocrystals with particle dimensions of 10–70 nm are studied. The possible reasons for the longwave shift of the fundamental absorption edge and inconsistency of the crystal structure of the CuInS₂ nanoparticles with a chalcopyrite lattice are discussed. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 3, pp. 387–393, May–June, 1998.     

Fabrication of nanostructured CuInS2 thin films by ion layer gas reaction method

CuInS₂ thin films were prepared by a two-stage ion layer gas reaction (ILGAR) process in which the Cu and In precursors were deposited on glass substrate by using a simple and low-cost dip coating technique and annealed in H₂S atmosphere at different temperatures. The influence of the annealing temperature (250-450 °C) on the particle size, crystal structure and optical properties of the CuInS₂ thin films was studied. Transmission electron microscopy revealed that the particle radii varied in the range 6-21 nm with annealing. XRD and SAED patterns indicated polycrystalline nature of the nanoparticles. The optical band gap (E_g) varied from 1.48 to 1.56 eV with variation of particle size. The variation of Urbach tail with temperature indicated higher density of the defects for the films annealed at lower temperature. From the Raman study, it was observed that the FWHM of the A₁ mode at ∼292 cm⁻¹ corresponding to the chalcopyrite phase of CuInS₂ decreased with increasing annealing temperature.     

Real-time study of phase transformations in Cu-In chalcogenide thin films using in situ Raman spectroscopy and XRD

The growth of polycrystalline CuInSe₂ and CuInS₂ thin films from metallic precursor layers is investigated using two complementary in situ methods which give bulk sensitive (XRD) and surface sensitive (Raman) information. From the time evolution of the XRD and Raman peak intensities the phase transformation sequences and the reaction kinetics can be derived. In both cases the chalcogenization of the Cu-In precursors proceeds at the top surface. Thus, the process is at least limited by cation diffusion through the metallic precursor. However, the growth kinetics of CuInSe₂ and CuInS₂ films differ. While the CuInSe₂ growth is limited by the reaction of binary phases, CuInS₂ growth is controlled by fast diffusion which is solely restricted to the period of raising temperature during the process.     

Cooling dynamics of self‐assembled monolayer coating for integrated gold nanocrystals on a glass substrate

Picosecond time‐resolved X‐ray diffraction has been used to study the nanoscale thermal transportation dynamics of bare gold nanocrystals and thiol‐based self‐assembled monolayer (SAM)‐coated integrated gold nanocrystals on a SiO₂ glass substrate. A temporal lattice expansion of 0.30–0.33% was observed in the bare and SAM‐coated nanocrystals on the glass substrate; the thermal energy inside the gold nanocrystals was transported to the contacted substrate through the gold–SiO₂ interface. The interfacial thermal conductivity between the single‐layered gold nanocrystal film and the SiO₂ substrate is estimated to be 45 MW m^?2 K^?1 from the decay of the Au 111 peak shift, which was linearly dependent on the transient temperature. For the SAM‐coated gold nanocrystals, the thermal dissipation was faster than that of the bare gold nanocrystal film. The thermal flow from the nanocrystals to the SAM‐coated molecules promotes heat dissipation from the laser‐heated SAM‐coated gold nanocrystals. The thermal transportation of the laser‐heated SAM‐coated gold nanocrystal film was analyzed using the bidirectional thermal dissipation model.     

Effect of [Cu]/[In] ratio on properties of CuInS2 thin films prepared by successive ionic layer absorption and reaction method

CuInS₂ ternary films were prepared by a soft solution processing, i.e. successive ionic layer absorption and reaction (SILAR) method. The films were deposited on glass substrates at room temperature and heat-treated under Ar atmosphere at 500 °C for 1 h. CuCl₂ and InCl₃ mixed solutions with different ionic ratios ([Cu]/[In]) were used as cation precursor and Na₂S as the anion precursor. The effect of the [Cu]/[In] ratio in precursor solution on the structural, chemical stoichiometry, topographical, optical and electrical properties of CuInS₂ thin films was investigated. XPS results demonstrated that stoichiometric CuInS₂ film can be obtained by adjusting [Cu]/[In] ratios in solution. Chalcopyrite structure of the film was confirmed by XRD analysis. The near stoichiometric CuInS₂ film has the optical band gap E_g of 1.45 and resistivity decreased with increase of [Cu]/[In] ratios.     

Structural and optical characterization of Sb-doped CuInS2 thin films grown by vacuum evaporation method

Structural, electrical and optical properties of Sb-doped CuInS₂ thin films grown by single source thermal evaporation method were studied. The films were annealed from 100 to 500 °C in air after the evaporation. The X-ray diffraction spectra indicated that polycrystalline CuInS₂ films were successfully obtained by annealing above 200 °C. This temperature was lower than that of non-doped CuInS₂ films. Furthermore, We found that the Sb-doped CuInS₂ thin films became close to stoichiometry in comparison with non-doped CuInS₂ thin films. The Sb-doped samples annealed above 200 °C has bandgap energy of 1.43–1.50 eV.     

Controllable synthesis and shape-dependent photocatalytic activity of ZnO nanorods with a cone and different aspect ratios and of short-and-fat ZnO microrods by varying the reaction temperature and time

ZnO nanorods with a cone and different aspect ratios and short-and-fat ZnO microrods were synthesized via a hydrothermal reaction of Zn with Zn(CH₃COO)₂ and H₂O. The control over these ZnO nanocrystals with a wurtzite structure and different shapes was achieved by adjusting only the reaction temperature and time. A possible kinetic mechanism was proposed to account for the growth of these ZnO nanocrystals with different shapes. Photocatalytic activities of ZnO nanocrystals with distinctive shapes in the degradation of methyl orange were investigated. The results indicate that the photocatalytic ability of the ZnO nanorods with a cone and different aspect ratios is stronger than that of the short-and-fat microrods.     

使用硫化物纳米前驱物墨水法制备铜铟硫薄膜

提出了一种通过反应烧结来制备CuInS₂多晶薄膜的低成本旋涂工艺路线．通过将前驱物粉末在氢气中预还原的方法来优化旋涂时使用的墨水成分,氢气还原会使前驱物纳米粉末从硫化物混合粉末转变成CuInS₂和Cu-In合金的混合物．扫描电子显微镜、电子能谱、X射线衍射以及拉曼图谱的结果表明,这种优化能极大的提高CuInS₂多晶薄膜的性能,其中包括薄膜的排列密度更高,杂质相减少,薄膜质量变得更好等．吸收光谱测得优化后的铜铟硫薄膜的带隙约为1.45 eV．     

Annealing study of electrodeposited CuInSe<Subscript>2</Subscript> and CuInS<Subscript>2</Subscript> thin films

In this study CuInSe₂ and CuInS₂ thin films were prepared onto ITO glass substrate using the electrodeposition technique in aqueous solution. The electrodeposited films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray analysis. The annealing effects on electrodeposited precursors were investigated. The chalcopyrite structure of CuInSe₂/CuInS₂ showed an enhancement of crystallinity after subsequent selenization/sulfurization treatment in Se/S atmosphere, respectively. XRD and SEM studies revealed a dramatic improvement of the crystalline quality of CIS films after annealing treatments. Mott–Schottky measurements were used to assess the conductivity type of the films and their carrier concentration. The prepared samples underwent an etching process to remove the binary accumulated Cu_2?x(Se,S) phases shown in FESEM pictures. This etching process has shown a noticeable decrease in both, the flat band potential, V_fb (V), and the number of acceptors, N_A (cm^?3) in selenized CuInSe₂ and sulfurized CuInS₂ samples.     

Ethylene glycol-assisted solvothermal fabrication of ZnWO4 nanostructures with tunable size,optical properties,and photocatalytic activities

Large scale of uniform small ZnWO₄ nanocrystals and ZnWO₄ nanorods with tunable size have been fabricated in ethylene glycol (EG)-assisted solvothermal process, ZnWO₄ samples ranging in shape from tiny nanocrystals to nanorods were dependent on the volume ratio of EG and water (H₂O). The optical properties of ZnWO₄ nanocrystals and nanorods were investigated by photoluminescence (PL) spectroscopy, showing longer ZnWO₄ nanorods own the increased PL intensity in comparison with that of shorter ones and small ZnWO₄ nanocrystals. The photocatalytic performance of ZnWO₄ nanostructures was studied also, which indicated that the increased size of ZnWO₄ nanorods resulted the degradation of photocatalytic performance in aqueous solution.     

CuInS2 solar cell absorber plasmonically modified by gold nanoparticles

Thin CuInS₂ light-absorbing layer prospective for the solar cell applications is modified by gold nanoparticles. Theoretical and experimental possibilities of placement nanoparticles over or under the CuInS₂ coating were tested. It was revealed that placement of nanoparticles under the CuInS₂ layer is better in terms of spray pyrolysis technique. It results in more effective plasmon-enhanced light absorption in the CuInS₂ layer at the visible/near infrared 650–700 nm spectral range.     

Luminescence enhancement of Mn doped ZnS nanocrystals passivated with zinc hydroxide

Mn-doped ZnS nanocrystals prepared by solvothermal method have been successfully coated with different thicknesses of Zn(OH)₂ shells through precipitation reaction. The impact of Zn(OH)₂ shells on luminescent properties of the ZnS:Mn nanocrystals was investigated. X-ray diffraction (XRD) measurements showed that the ZnS:Mn nanocrystals have cubic zinc blende structure. The morphology of nanocrystals is spherical shape measured by transmission electron microscopy (TEM). ZnS:Mn/Zn(OH)₂ core/shell nanocrystals exhibited much improved luminescent properties than those of unpassivated ZnS:Mn nanocrystals. The luminescence enhancement was observed with the Zn(OH)₂ shell thickening by photoluminescence (PL) spectra at room temperature and the luminescence lifetime of transition from ⁴T₁ to ⁶A₁ of Mn²⁺ ions was also prolonged. This result was led by the effective, robust passivation of ZnS surface states by the Zn(OH)₂ shells, which consequently suppressed nonradiative recombination transitions.     

Hydrothermal synthesis of chalcopyrite CuInS2, CuInSe2 and CuInTe2 nanocubes and their characterization

CuInS₂, CuInSe₂ and CuInTe₂ nanocubes of chalcopyrite structure have been successfully synthesized by hydrothermal process using deionized water as solvent at 180 °C for 20 h. The crystallinity, compositional, morphological and optical properties of the synthesized samples were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray (EDX), Raman and photoluminescence (PL) spectra analyses. The Raman spectra of the synthesized CuInS₂, CuInSe₂ and CuInTe₂ samples show the dominant A₁ modes at 293, 172 and 121 cm⁻¹ respectively. The possible chemical reaction and mechanism of nanocubes formation were discussed. The emission wavelength of as synthesized CuInS₂, CuInSe₂ and CuInTe₂ samples were blue shifted at 746 nm (1.66 eV), 863 nm (1.43 eV) and 859 nm (1.44 eV) respectively.     

A theoretical analysis of epitaxial growth of CuInS2 by chemical vapour deposition

Summary A theoretical analysis has been carried out to investigate the kinetics involved in the CVD growth of CuInS₂. A stagnant-layer model is assumed for the numerical, simulation. Computational results for the growth rate as a function of the substrate temperature, mean, gas velocity and partial pressures in the reaction tube are obtained. This analysis indicates that the substrate temperature plays a dominant role in the growth rate, which is consistent with our experimental data. Paper presented at the ?V International Conference on Ternary and Multinary Compounds?, held in Cagliari, September 14–16, 1982.     

Temperature-dependent photoluminescence of CuInS2 quantum dots

Temperature-dependent photoluminescence (PL) spectroscopy of CuInS₂ core and CuInS₂/ZnS core–shell quantum dots (QDs) was studied for understanding the influence of a ZnS shell on the PL mechanism. The PL quantum yield and lifetime of CuInS₂ core QDs were significantly enhanced after the QD surface was coated with the ZnS shell. The temperature dependences of the PL energy, linewidth, and intensity for the core and core–shell QDs were studied in the temperature range from 92 to 287 K. The temperature-dependent shifts of 98 meV and 35 meV for the PL energies of the QDs were much larger than those of the excitons in their bulk semiconductors. It was surprisingly found that the core and core–shell QDs exhibited a similar temperature dependence of the PL intensity. The PL in the CuInS₂/ZnS core–shell QDs was suggested to originate from recombination of many kinds of defect-related emission centers in the interior of the cores.