Investigation of Cu2ZnSnS4 solar cell buffer layer fabricated via spray pyrolysis

Copper zinc tin sulfide solar cells were fabricated by using spray pyrolysis from a window layer to an absorber layer. ZnS and In₂S₃ buffer layers were deposited on the TiO₂ layer, and the photovoltaic characteristics were investigated. The ZnS buffer demonstrated a poor photovoltaic performance because of its poor surface coverage and micro-cracks at fluorine-doped tin oxide/TiO₂ layers. The In₂S₃ buffer layer sprayed at low temperature (<360 °C) showed a large difference between photo and dark currents beyond the open-circuit voltage (V_OC). When the spraying temperature exceeded 390 °C, the devices showed high dark leakage currents at reverse biases because of the high conductivity of the buffer layer, resulting in decreased V_OC and short-circuit current density (J_SC). The optimum temperature for spraying In₂S₃ is 360 °C, and the best performing device showed 410 mV, 30.4 mA/cm², 35.3%, and 4.4% of V_OC, J_SC, fill factor, and efficiency, respectively.     

The annealing effect on structural,optical and photoelectrical properties of CuInS2/In2S3 films

Successive Ionic Layer Adsorption and Reaction (SILAR) technique was used to deposit the CuInS₂/In₂S₃ multilayer thin film structure at room temperature. The as-deposited film was annealed at 100, 200, 300, 400 and 500 °C for 30 min in nitrogen atmosphere and the annealing effect on structural, optical and photoelectrical properties of the film was investigated. X-ray diffraction (XRD) and optical absorption spectroscopy were used for structural and optical studies. Current–Voltage (I–V) measurements were performed in dark environment and under 15, 30 and 50 mW/cm² light intensity to investigate the photosensitivity of the structure. Also, the electrical resistivity of the film was determined in the temperature range of 300–470 K. It was found that annealing temperature drastically affects the structural, optical and photoelectrical properties of the CuInS₂/In₂S₃ films.     

Electron trapping center and SnO2-doping mechanism of indium tin oxide

Indium tin oxide (ITO) and Er³⁺-doped ITO powders were prepared by a conventional ceramic method. The density of ITO powders and optical absorption spectra of Er³⁺ ions in Er³⁺-doped ITO were measured as a function of the SnO₂ doping level. The results obtained were discussed in terms of the trapping center for immobile electrons in ITO. Observed densities of ITO powders were in good agreement with those calculated from their lattice parameters, assuming that the immobile electrons were trapped at the excess interstitial oxygen. The optical absorption spectra of Er³⁺-doped ITO indicated that some In³⁺ ions in ITO were surrounded by 7 and/or 8 oxygen ions; the increase in the coordination number of In³⁺ from 6 in In₂O₃ to 7 and/or 8 in ITO must be caused by the introduction of excess interstitial oxygen into the quasi-anion site in the C-typerare-earth lattice upon SnO₂ doping. It was concluded that the immobile electrons in ITO are trapped at the excess interstitial oxygen, and that the mechanism of conduction carrier generation and compensation upon SnO₂ doping into In₂O₃ can be expressed by the defect equation, 2SnO₂?2Sn_In·+2(1-z)e^′+zO_i ^′′+3O_O ^×+(1-z)/2O₂. Received: 26 November 1999 / Accepted: 20 April 2000 / Published online: 13 September 2000     

CuInS2 thin films obtained through the annealing of chemically deposited In2S3-CuS thin films

In this work, we report the formation of CuInS₂ thin films on glass substrates by heating chemically deposited multilayers of copper sulfide (CuS) and indium sulfide (In₂S₃) at 300 and 350 °C in nitrogen atmosphere at 10 Torr. CIS thin films were prepared by varying the CuS layer thickness in the multilayers with indium sulfide. The XRD analysis showed that the crystallographic structure of the CuInS₂ (JCPDS 27-0159) is present on the deposited films. From the optical analysis it was estimated the band gap value for the CIS film (1.49 eV). The electrical conductivity varies from 3 × 10⁻⁸ to 3 Ω⁻¹ cm⁻¹ depending on the thickness of the CuS film. CIS films showed p-type conductivity.     

Application of MEH-PPV/SnO<Subscript>2</Subscript> bilayer as hybrid solar cell

The effects of oxygen content in the sputtering gas on the crystallographic and optoelectronic properties of 210 nm-thick Zr–doped In₂O₃ (Zr–In₂O₃) films by rf magnetron sputtering were initially studied. The results of X-ray diffraction show that the Zr–In₂O₃ films grown on glass substrates exhibit mixed crystallographic orientations. Moreover, the Zr–In₂O₃ film grown in an Ar atmosphere promotes the appearance of crystallographic orientation of (222). The surface of the Zr–In₂O₃ film becomes rougher as the oxygen content in the sputtering gas decreases; the current images obtained by conductive atomic force microscopy reveal that the surfaces of the Zr–In₂O₃ films exhibit a distribution of coexisting conducting and nonconducting regions, and that the area of the nonconducting surface increases with the oxygen content in the sputtering gas. The resistivity is minimized to 3.51×10⁻⁴ Ω cm when the Zr–In₂O₃ film is grown in an Ar atmosphere and the average transmittance in the visible light region is ∼85%. The optical band gap decreases as the oxygen content in the sputtering gas increases.     

Magnetic properties of LiNi<Subscript>0.5</Subscript>Mn<Subscript>0.47</Subscript>Al<Subscript>0.03</Subscript>O<Subscript>2</Subscript> as positive electrode for Li-ion batteries

The layered LiNi_0.5Mn_0.47Al_0.03O₂ was synthesized by wet chemical method and characterized by X-ray diffraction and analysis of magnetic measurements. The powders adopted the α-NaFeO₂ structure. This substitution of Al for Mn promotes the formation of Li(Ni_0.47²⁺Ni_0.03³⁺Mn_0.47⁴⁺Al_0.03³⁺)O₂ structures and induces an increase in the average oxidation state of Ni, thereby leading to the shrinkage of the lattice unit cell. The concentration of antisite defects in which Ni²⁺ occupies the (3a) Li lattice sites in the Wyckoff notation has been estimated from the ferromagnetic Ni²⁺(3a)–Mn⁴⁺(3b) pairing observed below 140 K. The substitution of 3% Al for Mn reduces the amount of antisite defects from 7% to 6.4–6.5%. The analysis of the magnetic properties in the paramagnetic phase in the framework of the Curie–Weiss law agrees well with the combination of Ni²⁺ (S = 1), Ni³⁺ (S = 1/2) and Mn⁴⁺ (S = 3/2) spin-only values. Delithiation has been made by the use of K₂S₂O₈. According to this process, known to be softer than the electrochemical one, the nickel ions in the (3b) sites are converted into Ni⁴⁺ in the high spin configuration, while Ni²⁺(3a)–Mn⁴⁺(3b) ferromagnetic pairs remain, as the Li⁺(3b) ions linked to the Ni²⁺(3a) ions in the antisite defects are not removed. The results show that the antisite defect is surrounded by Mn⁴⁺ ions, implying the nonuniform distribution of the cations in agreement with previous NMR and neutron experiments.     

Resistance switching properties of In2O3 nanocrystals memory device with organic and inorganic hybrid structure

A memory device with In₂O₃ nanocrystals embedded in a biphenyl-tertracarboxylic dianhydride-phenylen diamine (BPDA-PDA) polyimide layer on a ZnO layer was fabricated, and its electrical properties were evaluated. Then, the transmittance efficiency in the structure of the BPDA-PDA polyimide/In₂O₃ nanocrystals/ZnO/ITO/double polishing sapphire substrate was measured to be about 80% between 440 to 800 nm by ultraviolet-visible transmittance spectroscopy. A bipolar switching current bistability by difference resistance appeared in the sweep voltage rage from −7 to 7 V. It was considered that the bipolar behavior of current-voltage may originate from a resistance fluctuation because of the electron charging effect in In₂O₃ nanocrystals by voltage sweeping, Fowler–Nordheim tunneling, space-charge-limited current, and the migration of O²⁻ ions.     

Formation of excited states of atoms and ions in laser plasma from CuInS2

Emission spectra and the energy distribution of the excited-state population density of atoms and ions in erosion laser plasma from CuInS₂ with various crystal-structure orderings are analyzed. It is shown that increased ordering of the target crystal structure causes the excited-state energies of indium atoms generated in the laser erosion plume to increase and that sulfur atoms always emit only in transitions from highly excited states. The ratio of relative ion concentrations in the laser plasma plume is Cu⁺/In⁺/S⁺ = 0.3/0.08/2, which corresponds neither to the atomic ratio of Cu/In/S (1/1/2) in the target nor to the ratio of ionization energies. The results are explained by recombination processes for ions and by the atomization specifics of the CuInS₂ target exposed to long-wavelength radiation. The atomization consists essentially of dissociative processes expressed by CuInS₂ → CuInS + S and CuInS₂ → Cu + InS + S. The electron temperature of polycrystal (single-crystal) plasma at a distance of 1 mm from the target is 0.3 eV (0.4 eV) for atoms and 1.3 eV (2.7 eV) for ions and varies negligibly for plasma up to a distance of 7 mm from the target. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 2, pp. 217–223, March–April, 2008.     

Synthesis, crystal structure, thermal and dielectric properties of bis(p-phenylenediammonium) chloride hexachlorobismuthate(III) monohydrate [C6H4(NH3)2]2ClBiCl6.H2O

Synthesis, crystal structure, and dielectric properties of [C₆H₄(NH₃)₂]₂ClBiCl₆.H₂O are reported. The compound crystallizes in the monoclinic system with space group P2₁/n. The unit cell dimensions are a = 9.836(5), b = 19.582(5), c = 13.082(5) ?, β = 104.731(5)° with Z = 4. The atomic arrangement can be described by an alternation of organic and inorganic layers. The anionic layer is built up of octahedral of [BiCl₆]^3- arranged in sandwich between the organic layers. The crystal packing is governed by means of the ionic N–H···Cl hydrogen bonds, forming a three-dimensional network. The dielectric properties have been investigated at temperature range from 297 to 410 K at various frequencies (10 Hz–100 kHz). Dielectric studies were performed to confirm results obtained with thermal analysis. The evolution of dielectric constant as a function of temperature and frequency of single crystal has been investigated in order to determine some related parameters.     

Preferential regrowth of indium–tin oxide (ITO) films deposited on GaN (0001) by rf-magnetron sputter

Effects of thermal treatments on the electrical properties and microstructures of indium–tin oxide (ITO)/GaN contacts have been investigated using a rf-magnetron sputter deposition followed by rapid thermal annealing. ITO films annealed at 800 °C revealed Schottky contact characteristics with a barrier height corresponding to ITO’s work function of 4.62 eV. The evolution of electrical properties of ITO/GaN contacts was attributed to the preferential regrowth of In₂O₃ (222)//GaN (0001) with an ideal metal–semiconductor Schottky contact. The feasible use of ITO/GaN as a transparent Schottky contact would be realized by the enhanced regrowth of In₂O₃ at high temperature. Received: 1 September 2000 / Accepted: 15 November 2000 / Published online: 28 February 2001     

Preparation of LaGaO<Subscript>3</Subscript> thin film for intermediate temperature SOFC by screen printing method (I)

La-doped ceria (Ce_0.6La_0.4O_1.8 [LDC]) has been reported to be an effective buffer layer material for preventing the chemical reaction between Sr- and Mg-doped LaGaO₃ (LSGM) electrolyte and Ni-based anode during sintering. However, it seems difficult to achieve a high power density on the cell using LDC buffer layer because of its low sintering and electrical conducting properties. In this study, effects of various sintering additives such as MgO, SrO, In₂O₃, Ga₂O₃, ZrO₂, and LSGM oxide powders were studied for improving sintering density and electrical conductivity of LDC. Sintering property, phase formation, and electrical conductivity varied with the sintering agents. Addition of SrO, Ga₂O₃, or LSGM enhanced the sintering density of LDC while LSGM addition was effective to increase the electrical conductivity. LSGM sintering aid was inert with LDC accompanying no chemical reaction after sintering at 1,623 K. Therefore, it was considered that a small amount of LSGM addition as a sintering agent was desirable for improving sintering and electrical properties of LDC. Furthermore, a single cell using LSGM-added LDC buffer layer and LSGM electrolyte film was fabricated by a screen printing method after co-firing at 1,623 K. The obtained cell showed an almost theoretical open circuit voltage and a high maximum power density (0.725 W cm⁻²) at 973 K.     

Absolute frequency and isotope shift measurements of the cooling transition in singly ionized indium

We report greater than two orders of magnitude improvements in the absolute frequency and isotope shift measurements of the In⁺ 5s^{2 1}S₀ (F = 9/2)–5s5p ³P₁ (F = 11/2) transition near 230.6 nm. The laser-induced fluorescence from a single In⁺ in a radio-frequency trap is detected. The fourth-harmonic of a semiconductor laser is used as the light source. The absolute frequency is measured with the help of a frequency comb referenced to a Cs atomic clock. The resulting transition frequencies for isotopes ¹¹⁵In⁺ and ¹¹³In⁺ are measured to be 1 299 648 954.54(10) MHz and 1 299 649 585.36(16) MHz, respectively. The deduced cooling transition frequency difference is 630.82(19) MHz. By taking into account of the hyperfine interaction, the isotope shift is calculated to be 695.76(1.68) MHz.     

Effect of post annealing on the characteristics of In2S3 buffer layer grown by chemical bath deposition on a CIGS substrate

In₂S₃ as an alternative Cd-free buffer in Cu(In,Ga)Se₂ (CIGS) solar cells was deposited on CIGS substrate by a chemical bath deposition and characterized after post annealing to optimize film properties for CIGS solar cells. A uniform and pinhole-free In₂S₃ film was deposited on a CIGS substrate by H₂O₂ treatment prior to chemical bath deposition. The In₂S₃ layer was an amorphous state due to the co-existence of In–S, In–O, and In–OH bonds. Annealing at 200 °C induced copper diffusion from CIGS into In₂S₃ layer and lowered the band gap from 3.3 to 1.9 eV, leading to phase change from amorphous state to crystalline state. The conduction band alignment at the In₂S₃/CIGS interface can be controlled by the post annealing. The shunt current through In₂S₃ film was prevented down to the thickness of 30 nm and a 1.15 eV shallow defect was eliminated by the annealing. The results indicated that post annealing in air is a critical to fabricate CIGS solar cells with a sub-30 nm CBD-In₂S₃ buffer layer.     

Development of solar cell material by PAC:111In probes in CuInS2 and related phases

Using metallic indium doped with radioactive¹¹¹In as one of the starting materials samples of stoichiometric CuInS₂, CuInS₂ with excess of indium and sulphur, and stoichiometric CuIn₅S₈ were prepared. Perturbed angular correlations of γ rays emitted by¹¹¹Cd are utilized to analyse the produced crystalline phases.     

Characterisation of Ba2In2 − x Sn x O5 + x/2 oxide ion conductors

The Ba₂In_2 − x Sn _x O_5 + x/2 solid solution was confirmed up to x = 1 by solid-state reaction. X-ray diffraction at room and at elevated temperatures, Raman scattering and impedance spectroscopy were used to characterise the samples. The structure refinement of the composition x = 0.1 from neutron diffraction data reveals that tin is preferentially located in the tetrahedral layers of the brownmillerite. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007     

Band alignments in the Cu(In,Ga)(S,Se)2 alloy system determined from deep-level defect energies

The composition dependence of defect energies in polycrystalline Cu(In_1-xGa_x)(Se_1-yS_y)₂ chalcopyrite semiconductor thin films is investigated by admittance spectroscopy. Alloying CuInSe₂ with S increases the energy of the dominant acceptor from 300 meV to approximately 380 meV in CuIn(Se_0.4S_0.6)₂, whereas in the alloy system Cu(In_1-xGa_x)Se₂, the acceptor energy remains unchanged over the whole composition range 0≤x≤1. Using the acceptor energy as a reference, we extrapolate the valence-band offsets ΔE_V=-0.23 eV for the combination CuInSe₂/CuInS₂ and ΔE_V=-0.04 eV for CuInSe₂/CuGaSe₂. Received: 19 July 2001 / Accepted: 27 July 2001 / Published online: 2 October 2001     

A Novel Fluorescent Cesium Ion-Selective Optode Membrane based on 15-Crown-5-Anthracene

An optode system based on a plasticized polymer membrane containing cesium ion-selective fluoroionophore and lipophilic anions for the determination of cesium ions has been developed. In this work, 15-crown-5 derivative including anthracene was used as a fluoroionophore. Emission intensity of the optode membrane incorporating 15-crown-5-anthracene was measured at 500 nm with excitation at 360 nm in the presence of Tris-HCl buffer solution. Under optimum experimental condition, the relative fluorescence intensity was linear with the concentration of cesium ion in the range of 1.0 × 10^-4 M to 1.0 × 10^-1 M and the detection limit was obtained 4.2 × 10^-5 M, as defined by LOD = 3 × S_b/m (where S_b=standard deviation of blank signal and, m=slope of the calibration curve). The effect of pH of sample solution on the fluorescent response, the selectivity, response time and reproducibility of the optode membrane were also discussed. The fluorescent optode system shows a high selectivity and sensitivity for cesium ion with respect to other cations such as K⁺, Na⁺ and Li⁺.     

Photoluminescence of CuInS<Subscript>2</Subscript> single crystals grown by traveling heater and chemical vapor transport methods

Photoluminescence of CuInS₂ single crystals grown by both the traveling heater method (THM) and chemical vapor transport (CVT) has been investigated at 4.2, 78, and 300 K. Intense emission in the near-band-edge region caused by free and bound excitons has been detected for both types of crystals. Taking into account the energy position of the luminescence line of the ground (n = 1) and first excited (n = 2) states, the binding energy for free A excitons has been estimated to be about 19.7 and 18.5 meV for CuInS₂ grown by CVT and THM, respectively. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 2, pp. 232–236, March–April, 2009.     

Fluorescent Method for the Determination of Sulfide Anion with ZnS:Mn Quantum Dots

Water-soluble Mn²⁺-doped ZnS quantum dots (QDs) were prepared using mercaptoacetic acid as the stabilizer. The optical properties and structure features were characterized by X-Ray, absorption spectrum, IR spectrum and fluorescence spectrum. In pH 7.8 Tris-HCl buffer, the QDs emitted strong fluorescence peaked at 590 nm with excitation wavelength at 300 nm. The presence of sulfide anion resulted in the quenching of fluorescence and the intensity decrease was proportional to the S²⁻ concentration. The linear range was from 2.5 × 10⁻⁶ to 3.8 × 10⁻⁵ mol L⁻¹ with detection limit as 1.5 × 10⁻⁷ mol L⁻¹. Most anions such as F⁻, Cl⁻, Br⁻, I⁻, CH₃CO₂ ⁻, ClO₄ ⁻, CO₃ ²⁻, NO₂ ⁻, NO₃ ⁻, S₂O₃ ²⁻, SO₃ ²⁻ and SO₄ ²⁻ did not interfere with the determination. Thus a highly selective assay was proposed and applied to the determination of S²⁻ in discharged water with the recovery of ca. 103%.     

Inelastic x-ray scattering measurements of dynamical cross-over in liquid As2Se3 at high temperature and high pressure

Liquid As₂Se₃ undergoes the semiconductor-metal transition with increasing temperature when pressure is applied to avoid evaporation of the liquid. To investigate the atomic dynamics of liquid As₂Se₃, we have carried out inelastic x-ray scattering experiments of this system at 1073 K and 6 MPa and obtained the dynamic structure factor S(Q,E), from approximately 1.6 nm⁻¹ to 11 nm⁻¹, where Q and E are momentum and energy transfer, respectively. The excitation energy in the semiconducting state at 1073 K disperses as fast as the ultrasonic sound velocity at Q < 2.5 nm⁻¹ but at Q > 2.9 nm⁻¹ it disperses approximately 1.8 times faster. We analyzed S(Q,E) at 1073 K using a simple viscoelastic model and discussed Q dependence of the propagation of the acoustic mode.