Study on inverse spinel zinc stannate, Zn2SnO4, as transparent conductive films deposited by rf magnetron sputtering

Inverse spinel zinc stannate (Zn₂SnO₄, ZTO) films were deposited onto fused quartz glass substrates heated at 800 °C by rf magnetron sputtering using a ceramic ZTO target (Zn:Sn = 2:1). H₂ flow ratios [H₂/(Ar + H₂)] were controlled from 0 to 30% during the depositions. ZTO films deposited at 800 °C possessed a polycrystalline inverse spinel structure. The lowest resistivity of 1.1 × 10^− 2 Ω cm was obtained for a ZTO film deposited at 20% H₂ flow ratio. The transmittance of the ZTO film was approximately 80% in the visible region.     

Nanocrystalline SnO2 and Au:SnO2 thin films prepared by direct current magnetron reactive sputtering

Nanocrystalline pure and gold doped SnO₂(Au:SnO₂) films were prepared on unheated glass substrates by dc magnetron reactive sputtering and, subsequently, the as deposited films were annealed in air. The films structure, surface morphology, photoluminescence, electrical and optical properties were investigated. After annealing the as deposited SnO₂ films, crystallinity increased and the surface roughness decreased. The intensity of PL peaks increases sharply with the annealing temperature. The optical transmittance of the films was around 89% after annealing the as deposited SnO₂ films at 450 °C. The as deposited Au:SnO₂ films show better crystallinity than the as deposited SnO₂ films, the average grain size was around 4.4 nm. The emission peaks of Au:SnO₂ films are slightly blue shifted as compare to undoped SnO₂ films. The Au:SnO₂ films show the lowest electrical resistivity of 0.001 Ωcm with optical transmittance of 76%, after annealing at 450 °C.     

Anatase TiO2 films crystallized on SnO2:F substrates in an aqueous solution

Anatase TiO₂ films were fabricated on SnO₂:F substrates in an aqueous solution. The films were constructed of assemblies of nano-TiO₂. Surface of the films showed large roughness due to nano/micro-asperity of the assemblies. The thickness was increased to 260 nm, 360 nm, 600 nm and 760 nm with the deposition time of 2 h, 5 h, 25 h and 48 h, respectively. The films showed strong intensity of 004 X-ray diffraction possibly because the needles, i.e., nano-TiO₂, elongated along the c-axis. Low-temperature synthesis of crystalline anatase TiO₂ films has a great deal of potential in the development of electronic devices, optical devices, dye-sensitized solar cells, photocatalytic devices and biomolecule sensors.     

F-doped SnO2 thin films grown on flexible substrates at low temperatures by pulsed laser deposition

Fluorine-doped tin oxide (SnO₂:F) films were deposited on polyethersulfone plastic substrates by pulsed laser deposition. The electrical and optical properties of the SnO₂:F films were investigated as a function of deposition conditions such as substrate temperature and oxygen partial pressure during deposition. High quality SnO₂:F films were achieved under an optimum oxygen pressure range (7.4-8 Pa) at relatively low growth temperatures (25-150 °C). As-deposited films exhibited low electrical resistivities of 1-7 mΩ-cm, high optical transmittance of 80-90% in the visible range, and optical band-gap energies of 3.87-3.96 eV. Atomic force microscopy measurements revealed a reduced root mean square surface roughness of the SnO₂:F films compared to that of the bare substrates indicating planarization of the underlying substrate.     

Thermally evaporated thin films of SnS for application in solar cell devices

SnS (tin sulphide) is of interest for use as an absorber layer and the wider energy bandgap phases e.g. SnS₂, Sn₂S₃ and Sn/S/O alloys of interest as Cd-free buffer layers for use in thin film solar cells. In this work thin films of tin sulphide have been thermally evaporated onto glass and SnO₂:coated glass substrates with the aim of optimising the properties of the material for use in photovoltaic solar cell device structures. In particular the effects of source temperature, substrate temperature, deposition rate and film thickness on the chemical and physical properties of the layers were investigated. Energy dispersive X-ray analysis was used to determine the film composition, X-ray diffraction to determine the phases present and structure of each phase, transmittance and reflectance versus wavelength measurements to determine the energy bandgap and scanning electron microscopy to observe the surface topology and topography and the properties correlated to the deposition parameters. Using the optimised conditions it is possible to produce thin films of tin sulphide that are pinhole free, conformal to the substrate and that consist of densely packed columnar grains. The composition, phases present and the optical properties of the layers deposited were found to be highly sensitive to the deposition conditions. Energy bandgaps in the range 1.55 eV-1.7 eV were obtained for a film thickness of 0.8 μm, and increasing the film thickness to > 1 μm resulted in a reduction of the energy bandgap to less than 1.55 eV. The applicability of using these films in photovoltaic solar cell device structures is also discussed.     

Study of CdS-sensitized solar cells, prepared by ammonia-free chemical bath technique

In this study, cadmium sulfide (CdS)-sensitized solar cells have been fabricated, where nanoporous titanium oxide (TiO₂) photoelectrode of equal thickness has been prepared on SnO₂:F coated glass substrate using TiO₂ paste. Different amounts of CdS have been deposited by an ammonia-free chemical bath deposition technique with various deposition times. The CdS-sensitized TiO₂ photoelectrodes show polycrystalline nature. The optical measurement reveals that absorbance edge of the CdS-sensitized TiO₂ photoelectrode extends up to 540 nm and the amount of absorbance increases with the enhancement of CdS-deposition time. The CdS solar cell, with deposition time of 12 min, shows impressive photocurrent and moderate solar cell efficiency.     

Electrodeposition of wide band gap InGaxSyOz thin films for solar cell applications

Indium-Gallium-sulfide-oxide thin films were deposited onto F-doped SnO₂-coated glass by electrochemical deposition from an aqueous bath. The films were deposited at three different ratios of gallium to indium in the precursor bath; namely [Ga/In] = 2/8, 5/5 and 8/2. The impact of the gallium content on the composition, optical transmission, structure, photosensitivity, electrical resistivity and morphology of the deposited films was investigated. The films deposited at [Ga/In] = 5/5 and 8/2 had an energy gap as high as 3.5 eV. The X-ray diffraction spectrum of the film deposited at [Ga/In] = 2/8 contained weak peaks of indium metal, but the In peaks were absent in the spectra of the films deposited at [Ga/In] = 5/5 and 8/2. The photosensitivity of the film was observed by means of photoelectrochemical measurements, which confirmed that all the films showed n-type conduction. Finally, the film has been used as a buffer layer to fabricate a SnS-based thin film solar cell.     

Growth and characterization of transparent conducting nanostructured zinc indium oxide thin films

Transparent conductive oxide (TCO) films have been widely used in various applications, such as for transparent electrodes in flat-panel displays, and in solar cells, optoelectronic devices, touch panels and IR reflectors. Among these, tin doped zinc oxide (ZTO) and indium doped zinc oxide (ZIO) have attracted considerable attention. Particularly, IZO thin film is the best candidate for high-quality transparent conducting electrodes in OLEDs and flexible displays. In this work zinc indium oxide (ZIO) thin films were deposited on glass substrate with varying concentration (ZnO:In₂O₃ — 100:0, 90:10, 70:30 and 50:50 wt.%) at room temperature by flash evaporation technique. These deposited ZIO films were annealed in vacuum to study the thermal stability and to see the effects on the physical properties. The XRF spectra revealed the presence of zinc and indium with varying concentration in ZIO thin films, while the surface composition and oxidation state were analyzed by X-ray photoelectron spectroscopy. The core level spectra were deconvoluted to see the effect of chemical changes, while the valance band spectra manifest the electronic transitions. The surface morphology studies of the films using atomic force microscopy (AFM) revealed the formation of nanostructured ZIO thin films. The optical band gap was also found to be decreased for both types of films with increasing concentration of In₂O₃.     

Molecular Synergistic Passivation for Efficient Perovskite Solar Cells and Self-Powered Photodetectors

The interface between the perovskite and electron-transporting material is often treated for defect passivation to improve the photovoltaic performance of devices. A facile 4-Acetamidobenzoic acid (containing an acetamido, a carboxyl, and a benzene ring)-based molecular synergistic passivation (MSP) strategy is developed here to engineer the SnO_x/perovskite interface, in which dense SnO_x are prepared using an E-beam evaporation technology while the perovskite is deposited with vacuum flash evaporation deposition method. MSP engineering can synergistically passivate defects at the SnO_x/perovskite interface by coordinating with Sn⁴⁺ and Pb²⁺ with functional group  CO in the acetamido and carboxyl. The optimized solar cell devices can achieve the highest efficiency of 22.51% based on E-Beam deposited SnO_x and 23.29% based on solution-processed SnO₂, respectively, accompanied by excellent stability exceeding 3000 h. Further, the self-powered photodetectors exhibit a remarkably low dark current of 5.22 × 10⁻⁹ A cm⁻², a response of 0.53 A W⁻¹ at zero bias, a detection limit of 1.3 × 10¹³ Jones, and a linear dynamic range up to 80.4 dB. This work proposes a molecular synergistic passivation strategy to enhance the efficiency and responsivity of solar cells and self-powered photodetectors.     

Antimony sulfide thin films in chemically deposited thin film photovoltaic cells

Antimony sulfide thin films of thickness ≈ 500 nm have been deposited on glass slides from chemical baths constituted with SbCl₃ and sodium thiosulfate. Smooth specularly reflective thin films are obtained at deposition temperatures from − 3 to 10 °C. The differences in the film thickness and improvement in the crystallinity and photoconductivity upon annealing the film in nitrogen are presented. These films can be partially converted into a solid solution of the type Sb₂S_xSe_3 − x, detected in X-ray diffraction, through heating them in contact with a chemically deposited selenium thin film. This would decrease the optical band gap of the film from ≈ 1.7 eV (Sb₂S₃) to ≈ 1.3 eV for the films heated at 300 °C. Similarly, heating at 300 °C of sequentially deposited thin film layers of Sb₂S₃-Ag₂Se, the latter also from a chemical bath at 10 °C results in the formation of AgSb(S/Se)₂ with an optical gap of ≈ 1.2 eV. All these thin films have been integrated into photovoltaic structures using a CdS window layer deposited on 3 mm glass sheets with a SnO₂:F coating (TEC-15, Pilkington). Characteristics obtained in these cells under an illumination of 850 W/m² (tungsten halogen) are as follows: SnO₂:F-CdS-Sb₂S₃-Ag(paint) with open circuit voltage (V_oc) 470 mV and short circuit current density (J_sc) 0.02 mA/cm²; SnO₂:F-CdS-Sb₂S₃-CuS-Ag(paint), V_oc ≈ 460 mV and J_sc ≈ 0.4 mA/cm²; SnO₂:F-CdS-Sb₂S_xSe_3 − x-Ag(paint), V_oc ≈ 670 mV and J_sc ≈ 0.05 mA/cm²; SnO₂:F-CdS-Sb₂S₃-AgSb(S/Se)₂-Ag(paint), V_oc ≈ 450 mV and J_sc ≈ 1.4 mA/cm². We consider that the materials and the deposition techniques reported here are promising toward developing ‘all-chemically deposited solar cell technologies.’     

Influence of SnO2 films with high resistance on the performance of CdTe solar cells

In this paper, we report the SnO₂ thin films with high resistance prepared by magnetic reactive sputtering on the transparent conductive glass covered with SnO₂:F layers, and study the structural, optical, and electrical properties of the films before and after annealing, as well as the influence of the annealing on the performance of CdTe solar cells. The results have shown that SnO₂ thin films almost have the same structure as SnO₂:F, and SnO₂ high resistance transparent (HRT) insertion layer between transparent conductive oxide (TCO) and CdS affects little on light transmittance. After introducing the HRT layer, the tunneling leakage caused by the pinholes can be avoided, which effectively protects the p–n junction (Wu et al. Proceedings of NCPV program review meeting AIP, New York, 22–26, 2001). Meanwhile, higher parallel resistivity, fill factor (FF), short-wave response, carrier concentration, and lower dark saturation current density have been achieved. As a result, the conversion efficiency is improved by 14.5%, from 10.3% to 11.8%.     

Atmospheric pressure chemical vapor deposition of transparent conducting films of fluorine doped zinc oxide and their application to amorphous silicon solar cells

Transparent conducting ZnO:F was deposited as thin films on soda lime glass substrates by atmospheric pressure chemical vapor deposition (CVD) deposition at substrate temperatures of 480–500 °C. The precursors diethylzinc, tetramethylethylenediamine and benzoyl fluoride were dissolved in xylene. The solution was nebulized ultrasonically and then flash vaporized by a carrier gas of nitrogen preheated to 150 °C. Ethanol was vaporized separately, and these vapors were then mixed to form a homogeneous vapor mixture. Good reproducibility was achieved using this new CVD method. Uniform thicknesses were obtained by moving the heated glass substrates through the deposition zone. The best electrical and optical properties were obtained when the precursor solution was aged for more than a week before use. The films were polycrystalline and highly oriented with the c-axis perpendicular to the substrate. The electrical resistivity of the films was as low as 5 × 10⁻⁴ Ωcm. The mobility was about 45 cm²/Vs. The electron concentration was up to 3 × 10²⁰/cm³. The optical absorption of the films was about 3–4% at a sheet resistance of 7 Ω/square. The diffuse transmittance was about 10% at a thickness of 650 nm. Amorphous silicon solar cells were deposited using the textured ZnO:F films as the front electrode. The short circuit current was increased over similar cells made with fluorine doped tin oxide, but the voltages and fill factors were reduced. The voltage was restored by overcoating the ZnO:F with a thin layer of SnO₂:F.     

Fabrication of resistive CO gas sensor based on SnO2 nanopowders via low frequency AC electrophoretic deposition

A resistive CO gas sensor has been fabricated using AC electrophoretic deposition (ACEPD) technique. SnO₂ thick films are deposited by applying low frequency (0.01–1,000 Hz) AC electric field to a stable suspension of SnO₂ nanoparticles in acetyl acetone. A carbon film base electrode is used as deposit substrate. Effect of CO gas exposure on conductivity of the SnO₂ film at 300 °C is investigated. Results show that the sensor is sensitive and its response is repeatable. This work shows that ACEPD can be used as an easy and cheap technique for fabrication of electronic devices such as ceramic gas sensors.     

Analysis of single junction a-Si:H solar cells grown on different TCO’s

In consequence of previous investigation of individual transparent conductive oxide (TCO) and absorber layers a study was carried out on hydrogenated amorphous silicon (a-Si:H) solar cells with diluted intrinsic a-Si:H absorber layers deposited on glass substrates covered with different TCO films. The TCO film forms the front contact of the super-strata solar cell and has to exhibit good electrical (high conductivity) and optical (high transmittance) properties. In this paper we focused our attention on the influence of using different TCO’s as a front contact in solar cells with structure as follows: Corning glass substrate/TCO (800, 950 nm)/p-type μc-Si:H (∼5 nm)/p-type a-Si:H (10 nm)/a-SiC:H buffer layer (∼5 nm)/intrinsic a-Si:H absorber layer with dilution R = [H₂]/[SiH₄] = 20 (300 nm)/n-type a-Si:H layer (20 nm)/Ag + Al back contact (100 + 200 nm). Diode sputtered ZnO:Ga, textured and non-textured ZnO:Al [3] and commercially fabricated ASAHI (SnO₂:F) U-type TCO’s have been used. The morphology and structure of ZnO films were altered by reactive ion etching (RIE) and post-deposition annealing.It can be concluded that the single junction a-Si:H solar cells with ZnO:Al films achieved comparable parameters as those prepared with commercially fabricated ASAHI U-type TCO’s.     

Influence of Zn doping on electrical and optical properties of multilayered tin oxide thin films

In this study, the electrical and optical properties of Zn doped tin oxide films prepared using sol-gel spin coating process have been investigated. The SnO² : Zn multi-coating films were deposited at optimum deposition conditions using a hydroalcoholic solution consisting of stannous chloride and zinc chloride. Films with Zn doping levels from 0–10 wt% in solution are developed. The results of electrical measurements indicate that the sheet resistance of the deposited films increases with increasing Zn doping concentration and several superimposed coatings are necessary to reach expected low sheet resistance. Films with three coatings show minimum sheet resistance of 1–479 kΩ/ in the case of undoped SnO₂ and 77 kΩ/ for 5 wt% Zn doped SnO₂ when coated on glass substrate. In the case of single layer SnO₂ film, absorption edge is 3.57 eV and when doped with Zn absorption edge shifts towards lower energies (longer wavelengths). The absorption edge lies in the range of 3.489-3.557 eV depending upon the Zn doping concentration. The direct and indirect transitions and their dependence on dopant concentration and number of coatings are presented.     

Recent advances in very high frequency plasma enhanced CVD process for the fabrication of thin film silicon solar cells

We have deposited amorphous silicon (a-Si) and nanocrystalline silicon (nc-Si) materials and the total p-i-n configurations for solar cells in a high vacuum multichamber system ASTER using very high frequency plasma enhanced chemical vapour deposition (VHF PECVD) process. The deposition process is monitored and controlled by in-situ diagnostic tools to maintain reproducibility of the material quality. In this paper we show our recent results on single junction (amorphous silicon) and tandem (a-Si/nc-Si) cells on plastic foil using the Helianthos concept. The tandem cell efficiency on Asahi U-type SnO₂:F coated glass is ~ 12% and this is achieved by employing nc-Si deposited at high pressure (p) conditions of 5 mbar and a small inter-electrode distance (d) of 5 mm. The deposition scheme of this cell on glass was adapted for the SnO₂:F coated Al foil substrates from Helianthos b.v., especially taking into account the expansion of the foil during deposition. The inter-electrode distance d was one of the variables for this optimisation process. Depositions at four inter-electrode distances of 6 mm, 8 mm, 10 mm and 12 mm (keeping the pressure-distance product constant) revealed that the deposition rate increases at higher distances, reaching 0.6 nm/s at a d of 10 mm and pressure p of 3.0 mbar. The Raman crystalline ratio showed a monotonic increase with the combination of higher d and lower p. Tandem cells with an area of 2.5 cm² on plastic foil fabricated by the Helianthos concept and employing the above mentioned nc-Si made at 0.6 nm/s in the bottom cell and a-Si in the top cell, showed an efficiency of 8.12%, with a short circuit current density of 10 mA/cm². The combined deposition time of the photoactive silicon layers of the top and bottom cells amounted to only 85 min.     

Synthesis and properties of epitaxial SnO2 films deposited on MgO (100) by MOCVD

Epitaxial tin oxide (SnO₂) thin films have been prepared on MgO (100) substrates at 500-600 °C by metalorganic chemical vapor deposition method. Structural and optical properties of the films have been investigated in detail. The obtained films were pure SnO₂ with the tetragonal rutile structure. An in-plane orientation relationship of SnO₂ (110) [010]//MgO (200) [110] between the film and substrate was determined. Two variant structure of SnO₂ were analyzed. The structure of the film deposited at 600 °C was investigated by high-resolution transmission electron microscopy, and an epitaxial structure was observed. The absolute average transmittance of the SnO₂ film at 600 °C in the visible range exceeded 90%. The optical band gap of the film was about 3.93 eV.     

Characterization of zinc-tin-oxide films deposited by thermal co-evaporation

The structural, electrical, and optical properties of zinc-tin-oxide (ZTO) films with different compositions prepared by thermal co-evaporation using ZnO and SnO₂ sources were investigated. The as-deposited films were amorphous but opaque. The lowest resistivity, ~ 8 × 10^− 5 Ω cm, was obtained for ZTO with 33 at.% Sn. Upon post-annealing in air, a sharp increase in transparency was observed between 350 and 550 °C, accompanying with a marked decrease in conductivity. This was attributed to re-oxidation of partially reduced oxides, leading to a lower density of oxygen vacancies. Our study showed that conductive and transparent ZTO films with low Sn content may be prepared by co-evaporation deposition, and suitable for use in devices as transparent electrodes.     

Effect of copper doping on physical properties of nanocrystallized SnS zinc blend thin films grown by chemical bath deposition

SnS: Cu thin films have been successfully prepared on Pyrex substrates using low cost chemical bath deposition (CBD) technique with different copper doped concentration (y = [Cu]/[Sn] = 5%, 6%, 8%, 9% and 10%). The structure, the surface morphology and the optical properties of the SnS:Cu films were studied by X-ray diffraction (XRD), atomic force microscopy (AFM) and spectrophotometer measurements, respectively. To obtain a thickness of the order of 780 ± 31 nm for absorber material in solar cell devices, a system of multilayer has been prepared. It is found that the physical properties of tin sulphide are affected by Cu-doped concentration. In fact, X-ray diffraction study showed that better cristallinity in zinc blend structure with preferential orientations (111)^ZB and (200)^ZB, was obtained for y equal to 6%. According to the AFM analysis we can remark that low average surface roughness (RMS)value of SnS(ZB) thin film obtained with Cu-doped concentrations equal to y = 6%, is about of 54 nm. Energy dispersive spectroscopy (EDS) showed the existence of Cu in the films. Optical analyses by means of transmission T(λ) and reflection R(λ) measurements show 1.51 eV as a band gap value of SnS:Cu(6%) which is nearly equal to the theoretical optimum value of 1.50 eV for efficient light absorption. On the other hand, Cu-doped tin sulphide exhibits a high absorption coefficient up to 2 × 10⁶ cm⁻¹, indicating that SnS:Cu can be used as an absorber thin layer in photovoltaic structure such as SnS:Cu/ZnS/SnO₂:F and SnS:Cu/In₂S₃/SnO₂:F, where ZnS and In₂S₃ are chemically deposited in a previous studies.     

Effect of temperature on glass-ceramic films prepared by impregnation of commercial float glass surfaces with oxide powders under pressure

SnO₂ samples were prepared as ultrafine powder by a chemical synthesis method and deposited on the surface of commercial float glass substrates. The glass surface was impregnated with these powders under high gas pressure (1.6-1.8 MPa) and heating to below the glass transition temperature in a designed pressurized chamber, forming SnO₂ films on glass surface. Phases were analyzed by X-ray diffraction and the results confirmed the SnO₂ powders as a single-phase tetragonal structure. Analysis of the chemical composition of glass substrates before and after powder impregnation revealed an ion exchange process caused by the substitution of sodium ions by tin ions on the glass surface. Differences in the surface morphology of SnO₂ films on glass surface were related to the morphology of synthesized powders for deposition and impregnation. The mechanism of SnO₂ films on glass surface was based on mass transfer between the glass substrates and SnO₂ powders as a function of the treatment temperature.