Preparation and evaluation of Cu2ZnSnS4 thin films by sulfurization of E---B evaporated precursors

By sulfurization of E---B evaporated precursors, CZTS(Cu₂ZnSnS₄) films could be prepared successfully. This semiconductor does not consist of any rare-metal such as In. The X-ray diffraction pattern of CZTS thin films showed that these films had a stannite structure. This study estimated the optical band gap energy as 1.45 eV. The optical absorption coefficient was in the order of 10⁴cm⁻¹. The resistivity was in the the order of 10⁴ Ω cm and the conduction type was p-type. Fabricated solar cells, Al/ZnO/CdS/CZTS/Mo/Soda Lime Glass, showed an open-circuit voltage up to 400 mV.     

Enhanced performance of solid oxide fuel cells with Ni/CeO2 modified La0.75Sr0.25Cr0.5Mn0.5O3−δ anodes

The optimization of electrodes for solid oxide fuel cells (SOFCs) has been achieved via a wet impregnation method. Pure La_0.75Sr_0.25Cr_0.5Mn_0.5O_3−δ (LSCrM) anodes are modified using Ni(NO₃)₂ and/or Ce(NO₃)₃/(Sm,Ce)(NO₃)_x solution. Several yttria-stabilized zirconia (YSZ) electrolyte-supported fuel cells are tested to clarify the contribution of Ni and/or CeO₂ to the cell performance. For the cell using pure-LSCrM anodes, the maximum power density (P_max) at 850 °C is 198 mW cm⁻² when dry H₂ and air are used as the fuel and oxidant, respectively. When H₂ is changed to CH₄, the value of P_max is 32 mW cm⁻². After 8.9 wt.% Ni and 5.8 wt.% CeO₂ are introduced into the LSCrM anode, the cell exhibits increased values of P_max 432, 681, 948 and 1135 mW cm⁻² at 700, 750, 800 and 850 °C, respectively, with dry H₂ as fuel and air as oxidant. When O₂ at 50 mL min⁻¹ is used as the oxidant, the value of P_max increases to 1450 mW cm⁻² at 850 °C. When dry CH₄ is used as fuel and air as oxidant, the values of P_max reach 95, 197, 421 and 645 mW cm⁻² at 750, 800, 850 and 900 °C, respectively. The introduction of Ni greatly improves the performance of the LSCrM anode but does not cause any carbon deposit.     

New trends to grow the n-CdZn (S1−xSex)2/p-CuIn(S1−xSex)2 heterojunction thin films for solar cell applications

The n-CdZn(S_1−xSe_x) and p-CuIn(S_1−xSe_x)₂ thin films have been grown by the solution growth technique (SGT) on glass substrates. Also the heterojunction (p–n) based on n-CdZn (S_1−xSe_x)₂ and p-CuIn (S_1−xSe_x)₂ thin films fabricated by same technique. The n-CdZn(S_1−xSe_x)₂ thin film has been used as a window material which reduced the lattice mismatch problem at the junction with CuIn (S_1−xSe_x)₂ thin film as an absorber layer for stable solar cell preparation. Elemental analysis of the n-CdZn (S_1−xSe_x)₂ and p-CuIn(S_1−xSe_x)₂ thin films was confirmed by energy-dispersive analysis of X-ray (EDAX). The structural and optical properties were changed with respect to composition ‘x’ values. The best results of these parameters were obtained at x=0.5 composition. The uniform morphology of each film as well as the continuous smooth thickness deposition onto the glass substrates was confirmed by SEM study. The optical band gaps were determined from transmittance spectra in the range of 350–1000 nm. These values are 1.22 and 2.39 eV for CuIn(S_0.5Se_0.5)₂ and CdZn(S_0.5Se_0.5)₂ thin films, respectively. J–V characteristic was measured for the n-CdZn(S_1−xSe_x)₂/p-CuIn(S_1−xSe_x)₂ heterojunction thin films under light illumination. The device parameters V_oc=474.4 mV, J_sc=13.21 mA/cm², FF=47.8% and η=3.5% under an illumination of 85 mW/cm² on a cell active area of 1 cm² have been calculated for solar cell fabrication. The J–V characteristic of the device under dark condition was also studied and the ideality factor was calculated which is equal to 1.9 for n-CdZn(S_0.5Se_0.5)₂/p-CuIn(S_0.5Se_0.5)₂ heterojunction thin films.     

Structural and electrical properties of CuGaS2 thin films by electron beam evaporation

Single phase CuGaS₂ thin film with a highest diffraction peak of (1 1 2) at a diffraction angle (2θ) of 28.8° was made at a substrate temperature of 70°C, an annealing temperature of 350°C and an annealing time of 60 min. Second highest (2 0 4) peak was shown at diffraction angle of (2θ) 49.1°. Lattice constant of a and c of that CuGaS₂ thin film was 5.37 and 10.54 Å, respectively. The greatest grain size of the thin film was about 1 μm. The (1 1 2) peak of single phase of CuGaS₂ thin film at an annealing temperature of 350°C with excess S supply appeared at a little higher about 10% than that of no excess S supply. The resistivity, mobility and hole density at room temperature of p-type CuGaS₂ thin film was 1.4 Ω cm, 15 cm²/V s and 2.9×10¹⁷ cm⁻³, respectively. It was known that carrier concentration had considerable effect than mobility on a variety of resistivity of the fabricated CuGaS₂ thin film, and the polycrystalline CuGaS₂ thin films were made at these conditions were all p-type.     

Improved Cu(In,Ga)(S,Se)2 thin film solar cells by surface sulfurization

Surface sulfurization was developed as a technique for fabricating efficient ZnO : Al/CdS/graded Cu(In,Ga)(S,Se)₂/ Mo/glass solar cells. Prior to the sulfurization, single-graded Cu(In,Ga)Se₂ (CIGS) films were deposited by a multi-stage process. The sulfurization of CIGS films was carried out using a H₂S---Ar mixture at elevated temperatures. The crystallographic and compositional properties of the absorber layers were investigated by XRD, SEM and AES analyses. After sulfurization, sulfur atoms were substituted for selenium atoms at the surface layer of CIGS films to form a Cu(In,Ga)(S,Se)₂ absorber layer. The diffusion of sulfur depends strongly on the grain structure of CIGS film. The cell efficiency of the 8–11% range before sulfurization was improved dramatically to 14.3% with V_oc = 528 mV, J_sc = 39.9 mA/cm² and FF = 0.68 after the sulfurization process.     

Stable, easily sintered BaCe0.5Zr0.3Y0.16Zn0.04O3−δ electrolyte-based protonic ceramic membrane fuel cells with Ba0.5Sr0.5Zn0.2Fe0.8O3−δ perovskite cathode

A stable, easily sintered perovskite oxide BaCe_0.5Zr_0.3Y_0.16Zn_0.04O_3−δ (BCZYZn) as an electrolyte for protonic ceramic membrane fuel cells (PCMFCs) with Ba_0.5Sr_0.5Zn_0.2Fe_0.8O_3−δ (BSZF) perovskite cathode was investigated. The BCZYZn perovskite electrolyte synthesized by a modified Pechini method exhibited higher sinterability and reached 97.4% relative density at 1200 °C for 5 h in air, which is about 200 °C lower than that without Zn dopant. By fabricating thin membrane BCZYZn electrolyte (about 30 μm in thickness) on NiO–BCZYZn anode support, PCMFCs were assembled and tested by selecting stable BSZF perovskite cathode. An open-circuit potential of 1.00 V, a maximum power density of 236 mW cm⁻², and a low polarization resistance of the electrodes of 0.17 Ω cm² were achieved at 700 °C. This investigation indicated that proton conducting electrolyte BCZYZn with BSZF perovskite cathode is a promising material system for the next generation solid oxide fuel cells.     

Bulk p-CuInSe2 photo-electrochemical solar cells

Dense CuInSe₂ of high quality, prepared by the fusion technique in evacuated quartz ampoule from stoichiometric melt, crystallizes in the chalcopyrite structure. Compositional analysis carried out by secondary ion mass spectrometry (SIMS) and energy dispersive spectroscopy (EDS) indicates a uniform distribution of elements through the depth and a composition close to the stoichiometry. The diffuse reflectance spectrum gives a band gap at 0.94 eV. The electrical conductivity follows an Arrhenius-type law with activation energy of 23 meV in conformity with polarons hopping. Above 320 °C, CuInSe₂ undergoes an irreversible oxidation. The thermal variation of the thermopower indicates p-type behavior attributed to copper deficiency and a hole mobility μ_300 K of 0.133 cm² V⁻¹ s⁻¹, thermally activated. In KCl media, the compound exhibits an excellent chemical stability with a corrosion rate of 8 μmol cm⁻² month⁻¹. The photo-electrochemical properties, investigated for the first time on the ingots, confirm the p-type conductivity. From the capacitance measurements, the flat band potential (V_fb=−0.62V_SCE) and the holes density (N_A=4×10¹⁷ cm⁻³) were determined. The valence band, located at 4.43 eV below vacuum, is made up of mainly Se orbital with little admixture of Cu character. The change of the electrolyte causes a variation in the potential V_fb (dV_fb/dpH=−0.058 V pH⁻¹) indicating strong OH⁻ adsorption. The fill factor in S²⁻ media was found to be 0.54; such result was corroborated by semi-logarithmic plots.     

Preparation of CuIn1−xGaxSe2 thin films by sputtering and selenization process

CuIn_1−xGa_xSe₂ polycrystalline thin films were prepared by a two-step method. The metal precursors were deposited either sequentially or simultaneously using Cu–Ga (23 at%) alloy and In targets by DC magnetron sputtering. The Cu–In–Ga alloy precursor was deposited on glass or on Mo/glass substrates at either room temperature or 150°C. These metallic precursors were then selenized with Se pellets in a vacuum furnace. The CuIn_1−xGa_xSe₂ films had a smooth surface morphology and a single chalcopyrite phase.     

Some physical investigations on AgInS2 sprayed thin films

AgInS₂ thin films have been prepared on glass substrates by the spray pyrolysis process using an aqueous solution which contains silver acetate (AgCH₃CO₂), thiourea (SC(NH₂)₂) and indium chloride (InCl₃) as precursors. The depositions were carried out in the range of the substrate temperature from 260 to 420 °C. The value of the concentration ratio in the spray solution of indium and silver elements x=[Ag⁺]/[In³⁺] was varied from 1 to 1.5 with [In³⁺]=10⁻² M and [S²⁻]/[In³⁺] was taken constant, equal to 4. The structural study shows that AgInS₂ thin film, prepared at 420 °C using optimal concentration ratio x=1.3 crystallizes in the chalcopyrite phase with a strong (1 1 2) X-ray diffraction line. Moreover, microprobe analysis (EPMA) shows that a nearly stoichiometric composition is obtained for these experimental conditions. Indeed, the atomic percentage of elements were. 24.5, 25.0, 49.5 for Ag, In and S, respectively. On the other hand from transmission and reflectance spectra, the obtained band gap energy is 1.83 eV for such film.     

The obstructed diffusion of the I3 ion in mesoscopic TiO2 membranes

The diffusional permeability of I⁻₃ ion in acetonitrile in free standing TiO₂ membrane with a porosity of 55% was examined. The apparent diffusion coefficient, D_app at 25°C of the ion was found to be 3.4×10⁻⁶ cm^{2 −1}, an order of magnitude smaller than the free diffusion at the same temperature. The temperature dependency of D_app was measured in the range 0–30°C and analysed in terms of the Walden product. The diffusional activation energy was found to be 13.5 kJ/mol. The parameters of interest for the efficiency of mesoscopic wet solar cells are discussed. A back of an envelope calculation shows that although the obstructed diffusion coefficient of the I⁻₃ ion was an order of magnitude smaller than the free diffusion the diffusional flux is still sufficient to meet a current density of 50 mA cm⁻². At incident photon flux of 1 kW m⁻² and at a photopotential of 0.6 V this would correspond to a solar energy efficiency of approximately 30%.     

Photoelectrochemical behavior of In2S3 formed on sintered In2O3 pellets

Microcrystals of In₂S₃ were formed on sintered In₂O₃ pellets by sulfurizing in H₂S atmosphere. The flat band potential of compound In₂S₃|In₂O₃ electrodes was evaluated as −1.0 V vs Ag|AgCl in 1 M KOH, 1 M Na₂S, 10⁻² M S. Significantly enhanced photocurrent was observed on compound In₂S₃|In₂O₃ electrodes with a lower degree of sulfurization to that of compound In₂S₃|In₂O₃ electrodes with higher degree of sulfurization. Photocurrent generation of compound In₂S₃|In₂O₃ electrodes was explained from the viewpoint of semiconductor sensitization.     

Optical and photoelectrical properties of β-In2S3 thin films prepared by two-stage process

β-In₂S₃ films were grown on glass as well as on quartz substrates by rapid heating of metallic indium films in H₂S atmosphere. The effect of sulfurization temperature and time on the growth, structural, electrical and photoelectrical properties of β-In₂S₃ films has been investigated. Highly oriented single-phase β-In₂S₃ films were grown by the sulfurization technique. The morphology and composition of films have been characterized. The optical band gap of β-In₂S₃ is found to vary from 1.9 to 2.5 eV when the sulfurization temperature is varied from 300 to 600 °C or by increasing the sulfurization time. The electrical properties of the thin films have also been studied; they have n-type electrical conductivity. The photoelectrical properties of the β-In₂S₃ films are also found to depend on the sulfurizing temperature. A high photoresponse is obtained for films prepared at a sulfurizing temperature of 600 °C. β-In₂S₃ can be used as an alternative to toxic CdS as a window layer in photovoltaic technology.     

Fabrication of CuInSe2 films and solar cells by the sequential evaporation of In2Se3 and Cu2Se binary compounds

Cu₂Se/In_xSe(x≈1) double layers were prepared by sequentially evaporating In₂Se₃ and Cu₂Se binary compounds at room temperature on glass or Mo-coated glass substrates and CuInSe₂ films were formed by annealing them in a Se atmosphere at 550°C in the same vacuum chamber. The In_xSe thickness was fixed at 1 μm and the Cu₂Se thickness was varied from 0.2 to 0.5 μm. The CuInSe₂ films were single phase and the compositions were Cu-rich when the Cu₂Se thickness was above 0.35 μm. And then, a thin CuIn₃Se₅ layer was formed on the top of the CuInSe₂ film by co-evaporating In₂Se₃ and Se at 550°C. When the thickness of CuIn₃Se₅ layer was about 150 nm, the CuInSe₂ cell showed the active area efficiency of 5.4% with V_oc=286 mV, J_sc=36 mA/cm² and FF=0.52. As the CuIn₃Se₅ thickness increased further, the efficiency decreased.     

Effect of Ga incorporation in sequentially prepared CuInS2 thin film absorbers

Thin film CuInS₂:Ga solar cell absorber films were prepared by sequential evaporation of Cu–In–Ga precursors and sulfurization in sulfur vapor. The depth distribution of Ga was found to be highly inhomogeneous caused by CuGaS₂ phase segregation at the back contact. Depending on overall Ga content and sulfurization temperature a quaternary CuGa_xIn_1−xS₂ compound formed exhibiting a shift in absorber lattice constant and band gap. Micro Raman measurements showed that crystal quality was also affected by Ga. Open-circuit voltages well above 800 mV were achieved while sustaining high fill factors of 71%.     

Synthesis and assessment of La0.8Sr0.2ScyMn1−yO3−δ as cathodes for solid-oxide fuel cells on scandium-stabilized zirconia electrolyte

Perovskite-type La_0.8Sr_0.2Sc_yMn_1−yO_3−δ oxides (LSSMy, y = 0.0–0.2) were synthesized and investigated as cathodes for solid-oxide fuel cells (SOFCs) containing a stabilized zirconia electrolyte. The introduction of Sc³⁺ into the B-site of La_0.8Sr_0.2MnO_3−δ (LSM) led to a decrease in the oxides’ thermal expansion coefficients and electrical conductivities. Among the various LSSMy oxides tested, LSSM0.05 possessed the smallest area-specific cathodic polarization resistance, as a result of the suppressive effect of Sc³⁺ on surface SrO segregation and the optimization of the concentration of surface oxygen vacancies. At 850 °C, it was only 0.094 Ω cm² after a current passage of 400 mA cm⁻² for 30 min, significantly lower than that of LSM (0.25 Ω cm²). An anode-supported cell with a LSSM0.05 cathode demonstrated a peak power density of 1300 mW cm⁻² at 850 °C. The corresponding value for the cell with LSM cathode was 450 mW cm⁻² under the same conditions. The LSSM0.05 oxide may potentially be a good cathode material for IT-SOFCs containing doped zirconia electrolytes.     

Formation of ultrafast-switching viologen-anchored TiO2 electrochromic device by introducing Sb-doped SnO2 nanoparticles

Ultrafast-switching viologen-anchored TiO₂ electrochromic device (ECD) was developed by introducing Sb-doped SnO₂ (Sb_xSn_1−xO₂, ATO) as counter electrode (CE), and the switching behavior of the fabricated ECD was investigated as a function of Sb-doping concentration. About 9-nm-sized Sb_xSn_1−xO₂ (x=0–0.3) nanoparticles were synthesized by a solvothermal reaction of tin (IV) chloride and antimony (III) chloride at 240 °C, and employed to fabricate 2.4-μm-thick transparent CE. Working electrode (WE) was formed from the 7-nm-sized TiO₂ nanoparticle by a doctor blade method, and the thickness of the nanoporous TiO₂ electrode was 4.5 μm. The phosphonated viologen, bis(2-phosphonylethyl)-4,4′-bipyridinium dibromide, was then adsorbed on the prepared films for the construction of the ECD. The response time was strongly dependent on the doping concentration of Sb in ATO, and the fastest switching response was observed at 3 mol%. At this composition, the coloration time was 5.7 ms, and the bleaching time was 14.4 ms, which is regarded as one of the best results so far reported.     

Photoconductivity of Cu(In, Ga) Se2 films

Polycrystalline CuIn_{1 − x}Ga_xSe₂ (0 ≤ x < 0.3) films (CIGS) were deposited by coevaporating the elements from appropriate sources onto glass substrates (substrate temperature 720 to 820 K). Photoconductivity of the polycrystalline CIGS films with partially depleted grains were studied in the temperature range 130–285 K at various illumination levels (0–100 mW/cm²). The data at low temperature (T < 170 K) were analyzed by the grain boundary trapping model with monovalent trapping states. The grain boundary barrier height in the dark and under illumination were obtained for different x-values of CuIn_1−xGa_xSe₂ films. Addition of Ga in the polycrystalline films resulted in a significant decrease in the barrier height. Variation of the barrier height with incident intensity indicated a complex recombination mechanism to be effective in the CIGS films.     

Influence of H2S concentration on the properties of Cu2ZnSnS4 thin films and solar cells prepared by sol-gel sulfurization

Cu₂ZnSnS₄ (CZTS) thin films prepared by a non-vacuum process based on the sulfurization of precursor coatings, consisting of a sol-gel solution of Cu, Zn, and Sn, under H₂S+N₂ atmosphere were investigated. The structure, microstructure, and electronic properties of the CZTS thin films as well as solar cell parameters were studied in dependence on the H₂S concentration. The sulfurization process was carried out at 500 °C for 1 h in an H₂S+N₂ mixed-gas atmosphere with H₂S concentrations of 3%, 5%, 10%, and 20%. As the H₂S concentration decreased from 20% to 5%, the S content of the CZTS thin films decreased. However, when the H₂S concentration was decreased below 3%, the S content of the films began to increase. A CZTS thin film prepared with an H₂S concentration of 3% had grains in the order of 1 μm in size, which were larger than those of films prepared at other H₂S concentrations. Furthermore, the most efficient solar cell, with a conversion efficiency of 2.23%, was obtained from a sample sulfurized at an H₂S concentration of 3%.     

New hybrid inorganic–organic polymer electrolytes based on Zr(O(CH2)3CH3)4, glycerol and EMIm-TFSI ionic liquid

This report presents detailed studies on the elemental analysis, vibrational spectroscopy, thermal stability and electrical spectroscopy of two new hybrid inorganic–organic polymers which have been synthesised by a sol–gel method using glycerol and zirconium(IV)butoxide as precursors. These materials have been doped by means of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIm-TFSI) ionic liquid (IL), which is insoluble in water. The elemental composition of the obtained polymers [Zr(C₆O₅H₁₁)] (1) and [Zr(C₁₁O₄H₃₁)] (2) has been determined by CHN analysis and by ICP-AES measurements. FT-IR and FT-Raman spectroscopy investigations have been performed to study the molecular structure of the polymers and the interactions of EMIm-TFSI with the host networks. Differential scanning calorimetry measurements show the presence of at least one glass transition temperature (T_g) in both 1 and 2 materials. The broadband dielectric spectroscopic measurements have been carried out between 10⁻² Hz to 10 MHz from −100 °C to 100 °C with a 5 °C step. The conductivities of the polymers 1 and 2 have been found to be in the order of 10⁻⁸ to 10⁻¹¹ S cm⁻¹ at 25 °C, so they can be defined as dielectric materials. After doping 2 with EMIm-TFSI, the conductivity at 25 °C of the obtained complex [Zr(C₁₁O₄H₃₁)]₁₅/(EMIm-TFSI) (2′) increased three orders of magnitude resulting ca. 10⁻⁵ S cm⁻¹. The permittivity spectra revealed two relaxation bands which were attributed to the α relaxation modes of the polymer networks.     

Multi Fermi level pinning at metal/Cu(InGa)(SeS)2 interfaces

Metal contacts to chemically etched Cu(InGa)(SeS)₂ layers have been investigated using current–voltage and capacitance–voltage techniques. Oxidising chemicals enhance the Fermi level pinning at metal/Cu(InGa)(SeS)₂ interfaces. The formation of a Schottky barrier at metal/p-Cu(InGa)(SeS)₂ interface is dominated by Fermi level pinning at one of the four levels, 0.77±0.02, 0.84±0.02, 0.93±0.02 and 1.03±0.02 eV above the valence band maximum. These observed levels determined from current–voltage measurements show a good agreement with some of the previously published photoluminescence, deep level transient spectroscopy and photo acoustic spectroscopy observations. The capacitance–voltage measurements showed that this material has near ideal doping concentration of 1.0×10¹⁶ cm⁻³ for fabricating solar cell devices.