Diagrams of the formation of In2S3 and In2Se3 films on vitroceramic upon precipitation, according to potentiometric titration

Boundary conditions and ranges of the formation of indium(III) sulfide and selenide upon precipitation by thiocarbamide and selenocarbamide are determined. Potentiometric titration of indium chloride (InCl₃) in the concentration range of 0.0001 to 0.100 mol/L by a solution of sodium hydroxide is performed. It is found that the following pH ranges are optimal for In₂S₃ and In₂Se₃ film precipitation: from 3.0 to 4.5 and from 9.0 to 14.0. Indium selenide layers 100 to 300 nm thick are prepared on vitroceramic by hydrochemcial precipitation.     

Thermal decomposition of butylindium thiolates and preparation of indium sulfide powders

Thermal properties of organoindium thiolates were investigated by means of thermogravimetric (TG) and differential thermal (DT) analysis. Dibutyl-indium propylthiolates (Buⁿ₂InSPrⁿ, Buⁿ₂InSPrⁱ, Buⁱ₂InSPrⁿ and Buⁱ₂InSPrⁱ) decomposed up to 280°C along with an exothermic DT peak and gave indium(I) sulfide (InS) powders. Although the arylthiolate Buⁿ₂InSPh also afforded InS powders, it decomposed at a slightly higher temperature. In contrast, the dithiolate and the dithiocarbamate complexes [BuⁿIn(SPrⁱ)₂ and In (S₂CNBu₂)₃] gave indium(III) sulfide (In₂S₃) powders.     

Anodic behavior of tin, indium, and tin–indium alloys in oxalic acid solution

The anodic behavior of tin, indium, and tin–indium alloys was studied in oxalic acid solution using potentiodynamic technique and characterized by X-ray diffraction and scanning electron microscopy. The E/I curves showed that the anodic behavior of all investigated electrodes exhibits active/passive transition. In the case of tin, the active dissolution region involves two anodic peaks (I and II) prior to permanent passive region. On the other hand, the active dissolution of indium involves four peaks (I–IV) prior to permanent passive region. The first (I) can be associated with the active dissolution of indium to InOOH, the second peak (II) to the formation of In(OH)₃, the third peak (III) to partially dehydration of In(OH)₃, and the peak (IV) to complete dehydration of In(OH)₃ to In₂O₃. When the surface is entirely covered with In₂O₃ film, the anodic current falls to a small value (I _pass) indicating the onset of passivation. The active dissolution potential region of the first three tin–indium alloys involves a net anodic contribution peak, and this is followed by a passive region. It is expected that the investigated peak is related to the formation of In₂O₃ and SnO (mixed oxides). When the formation of oxides (the oxides of In and Sn) exceeds its dissolution rate, the current drops, indicating the onset of passivation precipitation of In₂O₃/SnO and SnO₂ on the surface which blocks the dissolution of active sites. The alloys IV and V showed small second peak at about −620 mV which may be related to oxidation of In to In₂O₃ due to high In content in the two examined alloys. The active dissolution and passive current are increase with increasing temperature for all investigated metals and their alloys.     

Interaction of indium antimonide with saturated sulfur vapor

The chemical reaction of single-crystal indium antimonide with saturated elemental sulfur vapor is diffusion-limited and leads to the formation of the triple layer In₂S₃–(xIn₂S₃ + (1–x)Sb₂S₃)–Sb on the surface of the samples. A model explaining the experimental facts is proposed.     

Preparation,surface morphology,and optical properties of indium(III) oxide nanoparticles by thermolysis of indium–poly(vinyl alcohol) coordination polymer

First report on the preparation of well-dispersed, indium(III) oxide (In₂O₃) nanoparticles with 22–35?nm size by polymer thermolysis is presented. Indium–poly(vinyl alcohol) (PVA) coordination polymer films were prepared by ‘solution casting technique’ from the homogeneous aqueous solution of coordination polymer prepared using PVA and indium(III) nitrate as starting materials; subsequently the films were calcined at 550?°C to yield In₂O₃ nanoparticles. Both indium–PVA coordination polymer that served as the precursor and the titled nanoparticles were characterized by Fourier transform-infrared spectroscopy, photoluminescence (PL), powder X-ray diffraction (XRD), transmission electron microscopy, and thermal analysis. Room temperature PL spectra of the prepared indium oxide nanoparticles showed intense blue emissions around 360, 410 and 430?nm, characteristic of indium oxide nanoparticles due to oxygen vacancies. The lower energy PL emission decreases with an increase of indium(III) content in the precursor. The size of the nanoparticles calculated from line broadening of XRD pattern (cubic; JCPDS: 06-0416) was found to be around 24?nm. The average particle size of the synthesized nanoparticles increased with metal ion content in the precursor coordination polymer.     

Selecting indium-containing systems as solid electrolytes

Quasi-binary salt systems InCl₃-MeCl₂, where Me²⁺ stands for Mg²⁺, Cd²⁺, Zn²⁺, Sn²⁺, Co²⁺, or Mn²⁺, in the region of solid solutions on the basis of InCl₃ are considered. A comparative characteristic of some transport properties of these systems is given and optimum compositions for all systems under consideration are determined. The conduction mechanism that presumably takes place in systems InCl₃-MgCl₂ and InCl₃-CdCl₂ is confirmed by data that are obtained with the aid of the Tubandt method. In order to raise the reversibility with respect to the indium ion, also considered is the In₂S₃-InCl₃ system, in which the basis compound is In₂S₃. Methods of electroconduction and XRD are used to establish the existence of a region of limited solid solutions on the basis of indium sulfide. The current efficiency in a system with solid electrolyte In₂S₃-InCl₃ is determined (CE > 50%) and the dependence of the current efficiency on the electrolysis regime is considered. Thermodynamic investigation of some indium-containing compounds and the doping with indium are conducted with use made of indium-containing solid electrolytes of optimum compositions. Data concerning the magnitude of the alteration occurring in the Gibbs energy during the formation of indium-containing semiconducting compounds, which are close to reference data, are obtained.     

A convenient synthesis of methylindium(III) dithiolate complexes—precursors for indium sulfides

Methylindium(III) dithiolate complexes of the general formulae [Me₂In(S^∩S)] ( 1 ) and [MeIn(S^∩S)₂] ( 2 ) [S^∩S = (EtO)₂PS₂^?, (PrⁱO)₂PS₂^?, Et₂NCS₂^?, , O(CH₂CH₂)₂NCS₂^?, EtOCS₂^? and PrⁱOCS₂^?] have been isolated conveniently by the reaction of Me₃In·OEt₂ with In(S^∩S)₃ ( 3 ) in an appropriate stoichiometry. Both 1 and 2 have been characterized by indium analysis, IR, NMR (¹H, ¹³C{¹H} and ³¹P{H}) and mass spectral data. NMR data of 3 are also included for comparison. The Me–In and S^∩S resonances are sensitive to the number of methyl groups attached to indium metal. The mass spectral data indicate that these complexes are monomeric in nature. The thermal behavior of a few complexes has been investigated. The xanthate and dithiocarbamate complexes on pyrolysis under dynamic vacuum or flowing nitrogen atmosphere gave either In₂S₃ or a mixture of InS, In₂S₃ and In₆S₇, which were characterized using EDAX and powder XRD. Copyright © 2005 John Wiley & Sons, Ltd.     

Band‐Edge Electronic Structure of β‐In2S3: The Role of s or p Orbitals of Atoms at Different Lattice Positions

As a promising solar‐energy material, the electronic structure and optical properties of Beta phase indium sulfide (β‐In₂S₃) are still not thoroughly understood. This paper devotes to solve these issues using density functional theory calculations. β‐In₂S₃ is found to be an indirect band gap semiconductor. The roles of its atoms at different lattice positions are not exactly identical because of the unique crystal structure. Additonally, a significant phenomenon of optical anisotropy was observed near the absorption edge. Owing to the low coordination numbers of the In3 and S2 atoms, the corresponding In3‐5s states and S2‐3p states are crucial for the composition of the band‐edge electronic structure, leading to special optical properties and excellent optoelectronic performances.     

IR-Spektroskopische und Röntgenographische Untersuchungen an Thiospinellmischkristallen

The effect of the tetrahedral and octahedral coordinated metal and nonmetal atoms on the vibrational spectra of spinels is studied by investigation of mixed crystals and defect spinels like In₂S₃. The following solid solutions of chromium thiospinels and indium sulfides have been prepared and investigated by X-rays and FIR-spectroscopy: Hg_xZn_{1 ? x}Cr₂S₄ (I), ZnIn_xCr_{2 ? x}S₄ (II), CdIn_xCr_{2 ? x}S₄ (III), ZnCr₂Se_xS_{4 ? x} (IV), α-In₂S₃ (V), β-In₂S₃ (VI) and Cr_xIn_{2 ? x}S₃ (VII). The lattice constants of (I), (III), (IV) and (VII) obey Vegard's rule. (III) has a miscibility gap between x = 0.3 and x = 1.8. The spectroscopic behavior of the solid solutions (all the four peaks of the spinel spectra split or shift) can not be interpreted on the basis of internal vibrations of different coordination polyhedra. An explanation of the additional peaks in the spectra of the mixed crystals is given according to order of the atoms or distortion of the spinel structure.     

Theoretical DFT study of the structure and chemical activity of small indium(III) oxide clusters

The B3LYP/Lanl2dz and B3LYP/SDD levels of DFT have been used to describe the structural properties of small stoichiometric indium(III) oxide clusters. It was shown that the most stable structures for the monomer and dimer are linear and cubic, respectively, in origin. The most stable trimer is due to the formation of three eight-membered and two six-membered rings with alternation of In and O atoms. Among neutral and monocation tetrameric structures, formation of an ??arrowhead?? isomer is energetically less favorable than the global minimum structure that has eight six-membered and six four-membered rings. In the pentamer and octamer, a few centers of higher coordination number and a variety of In?CO bond lengths are observed. The other centers cannot be fitted to the characteristic bixbyite structure, however, so the larger octamer cannot be a good model for mimicking the properties of the In₂O₃ crystal structure. An H-terminated cluster model consisting of In₁₃O₂₇H₁₅ is proposed that well describes basic features of indium oxide and tin-doped indium oxide (ITO) structures.     

Kationenverteilung und Überstrukturordnung in ternären und quaternären Sulfidspinellen MIIMS4 – Einkristallstrukturuntersuchungen

Cation Distribution and Superstructure Ordering in Ternary and Quaternary Sulfide Spinels M^IIM₂^III S₄ – Single Crystal Structure Determinations The crystal structures of spinel type MIn₂S₄ (M ? Mn, Co, Ni), MCr_2?2xIn_2xS₄ (M ? Mn, Ni), and Cd_0.52Co_0,48Cr₂S₄ were reinvestigated by X-ray methods using single crystals grown by vapour phase transport technique. The indium sulfides possess a partially inverse distribution of the metal ions on the tetrahedral (8a) and octahedral sites (16d) of the structure. The degrees of inversion λ are 0.34 (MnIn₂S₄, a = 1072.0(1) pm, structural parameter u = 0.25726(2)), 0.84 (CoIn₂S₄, a = 1058.1(1) pm, u = 0.26921(5)) und 0.93 (NiIn₂S₄ a = 1050.5(1), u = 0.26040(3)). In the case of the chromium indium sulfide solid solutions, the degrees of inversion (and the structural parameters) increase (and decrease) linearly with increase in indium content x. ψ-scans of reflections not allowed in the space group Fd3 m do not prove simultaneous diffraction. Refinement of the structure of MnIn₂S₄ in space group F4 3m results in a partial superstructure ordering of Mn and In on the tetrahedral sites, 4a Mn_0.83In_0.17, 4c Mn_0.49In_0.51. In the case of Cd_0.52Co_0.48Cr₂S₄, superstructure ordering is like Cd_0.41Co_0.59 and Cd_0.62Co_0.38, respectively.     

化学浴沉积方法制备硫化铟敏化太阳电池及其性能研究

硫化铟是一种稳定、低毒性的半导体材料. 本文采用低成本的化学浴沉积方法制备了硫化铟敏化太阳电池, X射线衍射(XRD)、光电子能谱(XPS)和扫描电镜(SEM)结果表明形成了硫化铟敏化的二氧化钛薄膜. 化学浴沉积温度对所得硫化铟敏化薄膜的形貌有显著的影响, 进而影响电池性能. 温度太低时, 化学浴沉积反应速率太低, 只发生少量沉积; 温度太高时, 化学浴沉积反应速率较快, 硫化铟来不及沉积到二氧化钛多孔薄膜内部. 当温度在40℃时, 硫化铟沉积均匀性最好, 薄膜的光吸收性能最佳, 电池的短路电流最大, 另外, 填充因子达到最佳, 为65%, 电池总体光电转换效率为0.32%.     

Tailored indium sulfide-based materials for solar-energy conversion and utilization

To relieve the growing pressure originated from the energy shortage and environmental issues, solar-energy conversion into chemical or electrical energy has undergone an unprecedented development as a promising strategy in recent years. Indium sulfide (In₂S₃), an efficient visible-light harvester, has been extensively investigated in the field of photoconversion, owing to the fascinating merits including superior photo-absorption coefficient, photoelectric sensitivity, favorable carrier mobility, moderate band gap, excellent stability, and low toxicity. To take full advantage of these properties and further expand beyond the existing short board like low quantum efficiency, various In₂S₃-based functional nanostructures like nanoparticles, nanotubes, atomic two-dimensional sheets, and nanosheets-assembled complexes have been developed. Meanwhile, pleasurable characters of In₂S₃ have been modulated via defective engineering, doping, and hybridization (with inorganic materials or bio-molecules). Gratifyingly, In₂S₃-based photocatalytic, photoelectrocatalytic and photovoltaic systems have made significant impact on the field of energy and environmental issues. Therefore, this review provides an overview of crystal and morphologic structures of pristine In₂S₃ as well as many outstanding properties. Moreover, the pristine In₂S₃ and its derivatives with diverse synthesis routes are systematically summarized. Further, the advancement of In₂S₃-based photocatalytic, photoelectrocatalytic and photovoltaic systems, especially in environmental decontamination, artificial photosynthesis for renewable fuels and solar cells, are highlighted in detail. Ultimately, we conclude with a summary and propose some invigorating perspectives on the challenges from atomic (or macroscopical) structure modulation in material nature, photochemical behavior understanding to solar photovoltaic applications at the forefront of this research platform.     

Preparation and characterization of In<Subscript>2</Subscript>S<Subscript>3</Subscript> semiconductor thin films using the sol–gel method

This study describes the In₂S₃ semiconductor thin film coating on glass substrate by sol–gel method. The In₂S₃ thin film samples were prepared and examined by the X-ray diffraction (XRD), the UV–visible optical absorption and transmission study, and the Scanning Electron Microscope (SEM) image analyses. The XRD analysis results show that the In₂S₃ semiconductor thin films prepared by sol–gel method is formed at T~360–520 °C temperature interval. Band gap energy and optical absorption spectrum analysis of the In₂S₃ thin films reveal that Eg~2.51 eV for the In₂S₃ thin films. According to the EDX result the film was In-rich with the In/S = 1.42 ratio. The thickness of prepared In₂S₃ layer is about 400 nm.     

Useful and accessible organometallic precursors for preparation of zinc sulfide and indium sulfide thin films via solution pyrolysis (printing) method

Polycrystalline β-zinc sulfide thin films were prepared by solution pyrolysis of an ethylzinc isopropylthiolate–zinc bis(dibutyldithiocarbamate) combined precursor (EtZnSiPr–Zn(S₂CNnBu₂)₂) in chloroform solution on glass or silicon(111) substrates at 300°C. Homogeneous but amorphous indium sulfide thin films were obtained from butylindium bis(isopropylthiolate) (nBuInSiPr₂) in P-xylene on these substrates at 300°C similarly. The sulfide thin films obtained were characterized by means of X-ray photoelectron spectroscopy (XPS), X-ray fluorescence Microanalysis, scanning electron microscopy (SEM) and optical band gap measurements.     

Effect of sintering temperature on the structural, optical and electrical properties of sol–gel derived indium oxide thin films

Sol gel derived indium oxide, In₂O₃; films were prepared by spin coating technique. The films were dried and sintered at different sintering temperatures (300, 400, 450 and 500 °C) in air. The effect of sintering temperature on the structural, optical and electrical properties of In₂O₃ thin films was studied. The morphology and structure of the films were analyzed by scanning electron microscope and X-ray diffraction. The films showed a bcc structure that changes its 400-preferential orientation to 222 orientation as the sintering temperature increases from 300 to 500 °C. The optical behavior of the films was studied by measuring the transmission spectra in the wavelength range 200–2,500 nm. Different optical models have been proposed for fitting the transmittance data and simulate the optical constants as well as the film thickness of In₂O₃ films. The best fitting of the data was obtained by combining the classical Drude and OJL models coupled with the Bruggeman effective medium approximation. The optical parameters of Drude model (plasma frequency and damping constant) are used calculate the electrical properties of the films. The calculated values of the electrical sheet resistance were compared with those measured experimentally by four probes. The correlation between the film orientation change and its optical and electrical properties was discussed.     

Chemical‐Bath‐Deposited Indium Oxide Microcubes for Solar Water Splitting

We fabricated films of cubic indium oxide (In₂O₃) by chemical bath deposition (CBD) for solar water splitting. The fabricated films were characterized by X‐ray diffraction analysis, Raman scattering, X‐ray photoelectron spectroscopy, and scanning electron microscopy, and the three‐dimensional microstructure of the In₂O₃ cubes was elucidated. The CBD deposition time was varied, to study its effect on the growth of the In₂O₃ microcubes. The optimal deposition time was determined to be 24 h, and the corresponding film exhibited a photocurrent density of 0.55 mA cm^?2. Finally, the film stability was tested by illuminating the films with light from an AM 1.5 filter with an intensity of 100 mW cm^?2.     

Effects of annealing on the structural,electrical and optical properties of reactively evaporated thin fdlms of indium oxide

Thin films of indium oxide were prepared by thermal reactive evaporation of a mixture of indium oxide and metallic indium. This work is an experimental study of the modifications induced by an annealing treatment, on the structural, electrical and optical properties of indium oxide (In₂O₃). The results show important changes of different parameters determined after annealing. The films obtained after annealing at 350 °C for 3 hours under oxygen atmosphere have a good cristallinity. These films showed a transmittance of more than 80% in the visible region and a conductivity >10³ (Ω.cm)⁻¹.     

Anodic formation of semiconductive sulfide films at cadmium and bismuth: Rotating ring-disk electrode studies

CdS and Bi₂S₃ films from anodization of the metals in alkaline sulfide solution wereearlier shown to possess the photoelectrochemical and spectral properties of the corresponding n-type crystals, but with lower efficiency in semiconductor-liquid junction solar cells. The formation and removal of these films have been followed by rotating ring-disk electrode (RRDE) voltammetry, under dark and illuminated conditions, to define the regions of sulfide uptake and release, photovoltaic activity, hydroxide participation and mechanism of sulfur generation.