Microstructural properties of (In,Ga)2Se3 precursor layers for efficient CIGS thin-film solar cells

(In,Ga)₂Se₃ thin films were deposited on Mo-coated glass substrates by a conventional MBE system. To control the preferred orientation of Cu(In,Ga)Se₂ (CIGS) layers, the deposition temperature dependence T_depo of the (In,Ga)₂Se₃ layer was investigated including observations of both surface morphology and cross-sectional structure, Raman scattering and preferred orientation in the range 50–500 °C. γ-phase (In,Ga)₂Se₃ films exhibited (1 1 0) and (3 0 0) X-ray diffraction lines with a little or no (0 0 6) line contribution for T_depo>300 °C. It was revealed that a (3 0 0) preferred orientation of the (In,Ga)₂Se₃ layer could promote a (2 2 0/2 0 4) orientation of subsequently grown CIGS films, which were obtained only at the moderate temperatures of 300–400 °C during (In,Ga)₂Se₃ deposition.     

Preparation of Cu2ZnSnS4 thin films by sulfurizing electroplated precursors

Cu₂ZnSnS₄ (CZTS) thin films were prepared by sulfurizing precursors deposited by electroplating. The precursors (Cu/Sn/Zn stacked layers) were deposited by electroplating sequentially onto Mo-coated glass substrates. Aqueous solutions containing copper sulfate for Cu plating, tin sulfate for Sn plating and zinc sulfate for Zn plating were used as the electrolytes. The precursors were sulfurized by annealing with sulfur at temperatures of 300, 400, 500 and 600 °C in an N₂ gas atmosphere. The X-ray diffraction peaks attributable to CZTS were detected in thin films sulfurized at temperatures above 400 °C. A photovoltaic cell using a CZTS thin film produced by sulfurizing an electroplated Sn-rich precursor at 600 °C exhibited an open-circuit voltage of 262 mV, a short-circuit current of 9.85 mA/cm² and an efficiency of 0.98%.     

A novel Al and Y codoped ZnO/n-Si heterojunction solar cells fabricated by pulsed laser deposition

Al and Y codoped ZnO (AZOY) transparent conducting oxide (TCO) thin films were first deposited on n-Si substrates by pulsed laser deposition (PLD) to form AZOY/n-Si heterojunction solar cells. However, the properties of the AZOY emitter layers are critical to the performance of AZOY/n-Si heterojunction solar cells. To estimate the properties of AZOY thin films, films deposited on glass substrates with various substrate temperatures (T_s) were analyzed. Based on the experimental results, optimal electrical properties (resistivity of 2.8 ± 0.14 × 10^?4 Ω cm, carrier mobility of 27.5 ± 0.55 cm²/Vs, and carrier concentration of 8.0 ± 0.24 × 10²⁰ cm^?3) of the AZOY thin films can be achieved at a T_s of 400 °C, and a high optical transmittance of AZOY is estimated to be >80% (with glass substrate) in the visible region under the same T_s. For the AZOY/n-Si heterojunction solar cells, the AZOY thin films acted not only as an emitter layer material, but also as an anti-reflected coating thin film. Thus, a notably high short-circuit current density (J_sc) of 31.51 ± 0.186 mA/cm² was achieved for the AZOY/n-Si heterojunction solar cells. Under an AM1.5 illumination condition, the conversion efficiency of the cells is estimated at only approximately 4% (a very low open-circuit voltage (V_oc) of 0.24 ± 0.001 V and a fill factor (FF) of 0.51 ± 0.011) without any optimization of the device structure.     

Deposition of ZrO2 film by liquid phase deposition

In this study, undoped ZrO₂ thin films were deposited on single-crystal silicon substrates using liquid phase deposition. The undoped films were formed by hydrolysis of zirconium sulfate (Zr(SO₄)₂·4H₂O) in the presence of H₂O. A continuous oxide film was obtained by controlling adequate (NH₄)₂S₂O₈ concentration. The deposited films were characterized by SEM, FT-IR, XRD and DTA. Typically, the films showed excellent adhesion to the substrate with uniform particle diameter about 150 nm. The thicknesses of ZrO₂ film were about 200 nm after 10 h deposition at 30 °C. These films shows single tetragonal phase after heat treated at 600 °C. High annealing temperature (e.g. 750 °C) may result in the phase transformation of (t)-ZrO₂ into (m)-ZrO₂.     

Thin film silicon solar cells by AIC on foreign substrates

This paper presents the fabrication of thin film crystalline silicon solar cells on foreign substrates like alumina, glass–ceramic (GC) and metallic foils (ferritic steel—FS) using seed layer approach, which employs aluminium induced crystallisation (AIC) of amorphous silicon. Effect of hydrogen content in a-Si:H precursor films on the AIC process has been studied and the results showed that defects in the AIC grown films increased with increase of hydrogen content. At the optimal thermal annealing conditions, the AIC grown poly-Si films showed an average grain size of 7.6, 26, and 8.1 μm for the films synthesised on alumina, GC, and FS, respectively. The grains were (1 0 0) oriented with a sharp Raman peak around 520 cm^?1. Similarly, n-type seed layers were also fabricated by over-doping of as-grown AIC layers using a highly phosphorus doped glass solution. The resistivity of as-grown films reduced from 8.4×10^?2 Ω cm (p-type) to 4.1×10^?4 Ω cm (n-type) after phosphorus diffusion. These seed layers of n-type/p-type were thickened to form an absorber layer by vapour phase epitaxy or solid phase epitaxy. The passivation step was applied before the heterojunction formation, while it was after in the case of homojunction. Open circuit voltage of the junctions showed a strong dependence on the hydrogenation temperature and microwave (μW) power of electron cyclotron resonance (ECR) plasma of hydrogen. Effective passivation was achieved at a μW power of 650 W and hydrogenation temperature of 400 °C. Higher values of solar conversion efficiencies of 5% and 2.9% were achieved for the n-type and p-type heterojunction cells, respectively fabricated on alumina substrates. The analysis of the results and limiting factors are discussed in detail.     

Solar sintering of alumina ceramics: Microstructural development

Alumina powders were lab-synthesized and then sintered on a solar furnace (SF) in order to test the capability of these solar devices to produce dense ceramic bodies. The special configuration of the SF at Plataforma Solar de Almería (PSA-CIEMAT) in Spain, allowed to perform several experiments using high temperatures (up to 1780 °C), fast heating rates (50 and 100 °C min^?1) and different atmospheres (air, Ar and 95N₂:5H₂). For comparison, similar alumina samples were sintered in an electric furnace (EF) using standard conditions (5 °C min^?1 at 1600 °C during 240 min in air). An exhaustive microstructural characterization by scanning (SEM) and transmission (TEM) electron microscopies were performed on the sintered materials. Results for SF-samples showed a well-sintered alumina matrix of polyhedral grains even using shorter dwell times and higher heat-up rates than the conventional sintering. Obtained microstructures are in agreement with the presence of some impurities (mainly SiO₂, CaO, ZrO₂ and MgO) which are distributed at grain boundaries, triple points and matrix voids. For solar treatments, the variations of sintering parameters produced significant changes on matrix grain size, porosity and distribution of second phases. An important grain growth and density increase was observed after solar sintering on those tests performed at 1780 °C and under N₂:H₂ sintering atmosphere. The gathered data point out once more the convenience of SFs as sintering reactors to obtain ceramic materials with improved grain sizes.     

Solid-phase crystallization of amorphous silicon on ZnO:Al for thin-film solar cells

The suitability of ZnO:Al thin films for polycrystalline silicon (poly-Si) thin-film solar cell fabrication was investigated. The electrical and optical properties of 700 -nm-thick ZnO:Al films on glass were analyzed after typical annealing steps occurring during poly-Si film preparation. If the ZnO:Al layer is covered by a 30 nm thin silicon film, the initial sheet resistance of ZnO:Al drops from 4.2 to 2.2 Ω after 22 h annealing at 600 °C and only slightly increases for a 200 s heat treatment at 900 °C. A thin-film solar cell concept consisting of poly-Si films on ZnO:Al coated glass is introduced. First solar cell results will be presented using absorber layers either prepared by solid-phase crystallization (SPC) or by direct deposition at 600 °C.     

Effects of step-deposition on structures and properties of transparent conducting aluminum-doped zinc oxide films prepared by DC magnetron sputtering

The 2 wt% aluminum-doped zinc oxide films (AZO) was sputtered on corning glass plate at temperatures of 30–200 °C by DC magnetron sputtering using ceramic target. The microstructures and electrical resistivity of thin films were investigated by scanning electron microscope (SEM) and the van der Pauw method. The optical transmittances of films were measured by UV visible spectrophotometer in the wavelength of 300–900 nm. It was found that the average optical transmittances of specimens were 88%. Highly oriented AZO films in the (0 0 2) direction was observed in specimens as increasing of the substrate temperature. The dense film increased as the temperature increases. In addition, craters of greater depth with more compactness were obtained by step-deposition. The lowest resistivity of 9×10⁻⁴ Ω cm with film thickness of 700 nm was found in specimen grown by step-deposition at 200 °C.     

Ion-implantation modification of lithium–phosphorus oxynitride thin-films

Among various solid electrolytes, the lithium–phosphorus oxynitride (Lipon) electrolyte synthesized by sputtering of Li₃PO₄ in pure N₂ has a good ionic conductivity of 2(±1)×10⁻⁶ S cm⁻¹ at 25° C. As the nitrogen concentration increases in the Lipon electrolyte, the ionic conductivity is reported to increase as a result of a higher degree of cross-links. When Lipon films are deposited by sputtering, however, it is reported that the maximum nitrogen concentration saturates approximately at 6 at.%. By non-equilibrium processes, such as ion-implantation, nitrogen concentration can be controlled over 6 at.%. This study investigates the effect of nitrogen concentration on the ionic conductivity in Lipon films by using ion-implantation. Impedance measurements at 25° C show that the nitrogen-implanted Lipon films enhance or retard the ionic conductivity over a wide range after nitrogen-implantation, when compared with as-deposited thin-films.     

Optimized fabrication of sputter deposited Cu2ZnSnS4 (CZTS) thin films

An effective synthesis strategy is employed to fabricate Cu₂ZnSnS₄ (CZTS) thin films using radio frequency (rf) magnetron sputtering technique on soda lime glass substrates. The as-grown films are annealed at different temperatures ranging between 350 and 550 °C, and their chemical compositions and structural properties are investigated. The as-grown films have poor Cu/(Zn + Sn) ratios ranging between 0.39 and 0.44 and S/(Cu + Zn + Sn) ratios ranging between 0.97 and 1.21. The Cu/(Zn + Sn) ratio is improved by growing a thin additional Cu-capping layer on the as-grown film followed by annealing. An improved Cu/(Zn + Sn) ratio of ∼0.71 is obtained and the S/(Cu + Zn + Sn) ratio is slightly reduced to ∼0.85. The formation of a kesterite type CZTS is confirmed using X-ray diffraction and Raman spectroscopy measurements. Absorption measurements and band-gap energy determination of the CZTS films are carried out in order to confirm applicability to solar cells.     

Fabrication of copper–indium–gallium–diselenide absorber layer by quaternary-alloy nanoparticles for solar cell applications

Copper–indium–gallium–diselenide (CIGS) thin films were fabricated using precursor nanoparticle-ink and sintering technology. The precursor uses quaternary compound composition ratios of Cu/(In + Ga) = 0.95, Ga/(In + Ga) = 0.39, and Se/(Cu + In + Ga) = 0.75, respectively. The nanoparticles were fabricated by a rotary ball milling technique. After milling, the agglomerated CIGS powder to a particle size smaller than 100 nm. The nanoparticle-ink was fabricated by mixture of CIGS nanoparticles, solution, and organic polymer. Crystallographic, morphological, stoichiometric, and photovoltaic properties of films were obtained by sintering the precursor CIGS sample in a non-vacuum environment with selenization. Analytical results indicate that the CIGS absorption layer prepared with a nanoparticle-ink polymer, through sintering, has a chalcopyrite structure and favorable compositions. In this sample, the mole ratio of Cu:In:Ga:Se is equal to 0.95:0.69:0.38:1.99, and related ratios of Ga/(In + Ga) and Cu/(In + Ga) are 0.35 and 0.89, respectively. Analysis of a performance of the obtained solar cell under standard air mass 1.5 global illumination revealed a conversion efficiency of 2.392%.     

CdS1−yTey thin films: Production and bandgap investigation

In CdS/CdTe solar cells it is necessary to determine the efficiency limitations related with the intermixing at the interface between the CdS window layer and CdTe absorber layer. So understanding the properties of the solid solution (CdS_xTe_1?x on the CdTe side which is CdTe rich and CdS_1?yTe_y on the CdS side which is CdS rich) that is always formed in this region is essential. We produced thin films of CdS_1?yTe_y solid solution-which is CdS rich – by first producing CdS:In thin films on glass substrates by the spray pyrolysis technique and then annealing the films in nitrogen atmosphere at 400 °C in the presence of Te vapor. We are the first who produce this solid solution by this simple and low cost method. The composition and morphology of the films were determined by energy dispersive X-ray detection (EDAX) measurements and scanning electron microscopy (SEM) observations respectively. Eight values of y in the range 0 ? y ? 0.2845 were obtained. The transmittance was measured and used to investigate the optical bandgap energy by using the second derivative of the absorbance. It is found that the films show a single hexagonal phase for y ? 0.0852 and then a mixed (hexagonal and cubic) phase for 0.0997 ? y ? 0.2845. Bandgap energies in the range 2.259 ? E_g ? 2.528 eV were obtained. Urbach tailing in the bandgap was also investigated.     

Comparative studies of nickel oxide films on different substrates for electrochemical supercapacitors

Thin nickel oxide (NiO) films were obtained by post-heating of the corresponding precursor films of nickel hydroxide (Ni(OH)₂) cathodically deposited onto different substrates, i.e., nickel foils, and graphite at 25 °C from a bath containing 1.5 mol L⁻¹ Ni(NO₃)₂ and 0.1 mol L⁻¹ NaNO₃ in a solvent of 50% (v/v) ethanol. The surface morphology of the obtained films was observed by scanning electron microscope (SEM). Electrochemical characterization was performed using cyclic voltammetrty (CV), chronopotentiometry (CP) and electrochemical impedance analysis (EIS). When heated at 300 °C for 2 h in air, the specific capacitance of the prepared NiO films on nickel foils and graphite, with a deposition charge of 250 mC cm⁻², were 135, 195 F g⁻¹, respectively. When the deposition charge is less than 280 mC cm⁻², the capacitance of both appears to keep the linear relationship with the deposition charge. The specific capacitance, cyclic stability of the NiO/graphite hybrid electrodes in 1 mol L⁻¹ KOH solution were superior to those on nickel foils mainly due to the favorable adhesion, the good interface behavior between graphite and the NiO films, and the extra pseudo-capacitance of the heated graphite substrates.     

Effect of annealing temperature on electrochemical performance of thin-film LiMn2O4 cathode

Spinel LiMn₂O₄ thin-film cathodes were obtained by spin-coating the chitosan-containing precursor solution on a Pt-coated silicon substrate followed by a two-stage heat-treatment procedure. The LiMn₂O₄ film calcined at 700 °C for 1 h showed the highest Li-ion diffusion coefficient, 1.55 × 10⁻¹² cm² s⁻¹ (PSCA measurement) among all calcined films. It is attributed to the larger interstitial space and better crystal perfection of LiMn₂O₄ film calcined at 700 °C for 1 h. Consequently, the 700 °C-calcined LiMn₂O₄ film exhibited the best rate performance in comparison with the ones calcined at other temperatures.     

Wide-optical bandgap with improved conductivity p-μc-Si:Ox:H films prepared by Cat-CVD

Boron-doped hydrogenated microcrystalline silicon oxide (p-μc-Si:O_x:H) films have been deposited using catalytic chemical vapor deposition (Cat-CVD). The single-coiled tungsten catalyst temperature (T_fil) was varied from 1850 to 2100 °C and films were deposited on glass substrates at the temperatures (T_sub) of 100–300 °C. Different catalyst-to-substrate distances of 3–5 cm and deposition pressures from 0.1 to 0.6 Torr were considered.Optical and electrical characterizations have been made for the deposited samples. The sample transmittance measurement shows an optical-bandgap (Eg_opt) variation from 1.74 to 2.10 eV as a function of the catalyst and substrate temperatures. One of the best window materials was obtained at T_sub=100 °C and T_fil=2050 °C, with Eg_opt=2.10 eV, dark conductivity of 3.0×10^?3 S cm^?1 and 0.3 nm s^?1 deposition rate.     

Lithium cobalt oxide cathode film prepared by rf sputtering

Thin films of LiCoO₂ prepared by radio frequency magnetron sputtering on Pt-coated silicon are investigated under various deposited parameters such as working pressure, gas flow rate of Ar to O₂, and heat-treatment temperature. The as-deposited film was a nanocrystalline structure with (1 0 4) preferred orientation. After annealing at 500–700 °C, single-phase LiCoO₂ is obtained when the film is originally deposited under an oxygen partial pressure (P_O2) from 5 to 10 mTorr. When the sputtering process is performed outside these P_O2 values, a second phase of Co₃O₄ is formed in addition to the HT-LiCoO₂ phase. The degree of crystallization of the LiCoO₂ films is strongly affected by the annealing temperature; a higher temperature enhances the crystallization of the deposited LiCoO₂ film. The grain sizes of LiCoO₂ films annealed at 500, 600 and 700 °C are about 60, 95, and 125 nm, respectively. Cyclic voltammograms display well-defined redox peaks. LiCoO₂ films deposited by rf sputtering are electrochemically active. The first discharge capacity of thin LiCoO₂ films annealed at 500, 600 and 700 °C is about 41.77, 50.62 and 61.16 μAh/(cm² μm), respectively. The corresponding 50th discharge capacities are 58.1, 72.2 and 74.9% of the first discharge capacity.     

Liquid sodium versus Hitec as a heat transfer fluid in solar thermal central receiver systems

Selection of an appropriate HTF is important for minimising the cost of the solar receiver, thermal storage and heat exchangers, and for achieving high receiver and cycle efficiencies. Current molten salt HTFs have high melting points (142–240 °C) and degrade above 600 °C. Sodium’s low melting point (97.7 °C) and high boiling point (873 °C) allow for a much larger range of operational temperatures. Most importantly, the high temperatures of sodium allow the use of advanced cycles (e.g. combined Brayton/Rankine cycles). In this study, a comparison between the thermophysical properties of two heat transfer fluids (HTFs), Hitec (a ternary molten salt 53% KNO₃ + 40% NaNO₂ + 7% NaNO₃) and liquid sodium (Na), has been carried out to determine their suitability for use in high-temperature concentrated solar thermal central-receiver systems for power generation. To do this, a simple receiver model was developed to determine the influences of the fluids’ characteristics on receiver design and efficiency. While liquid sodium shows potential for solar thermal power systems due to its wide range of operation temperatures, it also has two other important differences – a high heat transfer coefficient (～an order of magnitude greater than Hitec) and a low heat capacity (30–50% lower than Hitec salt). These issues are studied in depth in this model. Overall, we found that liquid sodium is potentially a very attractive alternative to molten salts in next generation solar thermal power generation if its limitations can be overcome.     

Quantitative structural analysis of the transition from LT-LixCoO2 to HT-LixCoO2 using the rietveld method: correlation between structure and electrochemical performance

A quantitative phase analysis was made of Li_xCoO₂ powders obtained by two distinct chemical methodologies at different temperatures (from 400 to 700 °C). A phase analysis was made using Rietveld refinements based on X-ray diffraction data, considering the Li_xCoO₂ powders as a multiphase system that simultaneously contained two main phases with distinct, layered and spinel-type structures. The results showed the coexistence of both structures in Li_xCoO₂ obtained at low temperature (400 and 500 °C), although only the layered structure was detected at higher temperatures (600 and 700 °C), regardless of the chemical powder process employed. The electrochemical performance, evaluated mainly by the cycling reversibility of Li_xCoO₂ in the form of cathode insertion electrodes, revealed that there is a close correlation between structural features and the electrochemical response, with one of the redox processes (3.3 v/3.9 v) associated only with the presence of the spinel-type structure.     

Selective hydrogen generation from real biomass through hydrothermal reaction at relatively low temperatures

The effect of additives, such as an inorganic alkali and a nickel catalyst, on the hydrothermal process was examined to generate hydrogen from biomass with high selectivity at relatively low temperatures around 400 °C. At first, a cellulose sample as model biomass was subjected to the hydrothermal process at 400 °C under 25 MPa in the presence of an alkali (Na₂CO₃) and a nickel catalyst (Ni/SiO₂). The combination of these two additives led not only to highly efficient generation of hydrogen but also to effective dissolution of CO₂ into an alkaline liquid layer. Here the molar yields of gas products from the cellulose sample were compared with the equilibrium quantities obtained using a thermodynamics calculation software. Furthermore, the hydrothermal process of real biomass, such as wood chips, organic fertilizer and food waste, in the presence of both the two additives resulted in highly selective production of hydrogen even at 400 °C.     

A thermo-economical optimization of a domestic solar heating plant with seasonal storage

In this study, the thermo-economic optimization analysis to determinate economically optimal dimensions of collector area and storage volume in domestic solar heating systems with seasonal storage is presented. For this purpose, a formulation based on the simplified P₁ and P₂ method is developed and solved by using MATLAB optimization Toolbox for five climatically different locations of Turkey. The results showed that the required optimum collector area in Adana (37 °N) for reaching maximum savings is 36 m²/house and 65 m²/house in Erzurum (39 °N) for same storage volume (1000 m³). The effects of collector efficiency on solar fraction and savings are investigated. The simulation results showed that the solar fraction and savings of the selective flat plate collector systems are higher than the other black paint flat plate collector systems.