Investigations on copper zinc tin sulfide thin films grown through nebulizer assisted spray pyrolysis technique

An attempt is made in this work to synthesize the nontoxic Cu₂ZnSnS₄ (CZTS) thin film on FTO coated glass substrates through aerosol assisted nebulizer spray pyrolysis technique at different annealing temperatures for photovoltaic energy conversion. The deposited thin film is further used to form a heterojunction interface with a cadmium sulfide layer to fabricate a solar cell with Glass/FTO/CdS/CZTS/Ag superstrate structure to reveal its photovoltaic application. Various characterization techniques are utilized to study its inherent properties. X-ray diffraction (XRD) is employed to investigate the structural parameters such as crystallite size, microstrain and dislocation density which shows a preferential peak for (112) plane around 28.5° confirming the formation of kesterite CZTS. Raman measurements establish the peak for CZTS at 336 cm⁻¹ and confirm the absence of parasitic secondary phases for an excitation wavelength of 488 nm. Scanning electron microscope and atomic force microscope used to examine the surface morphology and roughness of the films reveal a good surface morphology with a grain size of 555.9 nm and roughness of 123.7 nm for an annealing temperature of 350°C. The bandgap of the deposited CZTS films is found to be around 1.5 eV. The I-V characteristics of CZTS seem to be better for the 350°C annealed film. The performance of the optimized CZTS absorber layer is tested by forming a solar cell structure. The devised solar cell exhibited an open circuit voltage of 213 mV and a short circuit current density of 490 μA cm⁻² with a conversion efficiency of 0.68% substantiating the usage of the prepared film as an absorber for photovoltaic conversion.     

Deposition and characterization of earth abundant CuZnS ternary thin films by vacuum spray pyrolysis and fabrication of p-CZS/n-AZO heterojunction solar cells

We report fabrication of solar cell device <ITO/AZO/i-ZnO/CZS/Al> with Copper Zinc Sulfide (CZS) thin films as absorber layer. CZS thin films prepared using chemical spray pyrolysis technique at a pressure of 10⁻³ mbar at different substrate temperatures. Structural, morphological, optical, compositional and electrical properties of as prepared films are investigated. Structural analysis shows crystalline nature with mixed phase containing CuS-ZnS binary composite. Atomic Force Microscopy analysis shows the average particle size of 88 nm. Value of work function obtained from ultraviolet photoelectron spectroscopy is 4.58 eV. The band gap of the as-prepared films varies from 1.62 to 2.06 eV. Hall effect measurement proves the p-type nature for all the deposited films. Samples deposited at 350°C shows carrier concentration of 10²¹ cm⁻³ and electrical conductivity of 526 S cm⁻¹. Solar cell device structure of <ITO/AZO/i-ZnO/CZS/Al> has been fabricated using the CZS sample deposited at 350°C. The cell parameters obtained are V_oc = 0.505 V, I_sc = 4.97 mA/cm², FF = 64.28% and η = 1.6 ± 0.05%.     

Schottky solar cells with amorphous carbon nitride thin films prepared by ion beam sputtering technique

This paper reports on the successful deposition of amorphous carbon nitride thin films (a-CN_x) and fabrication of ITO/a-CN_x/Al Schottky thin-film solar cells by using the technique of ion beam sputtering. XPS and Raman spectra are used to characterize the deposited thin films. Nitrogen atoms are incorporated into the films in the form of carbon–nitrogen multiple bands. Their optical properties are also investigated using a spectroscopic ellipsometer and UV/VIS/NIR spectrophotometer. The refraction of the carbon nitride thin films deposited lies in the range of 1.7–2.1. The Tauc optical band gap is about 0.6 eV. The photovoltaic values of the device, short-circuit current and open-circuit voltage are 1.56 μA/cm² and 250 mV, respectively, when exposed to AM1.5 illumination (100 mW/cm², 25°C).     

Hybrid solar cells using PbS nanoparticles

Solution-processed bilayer heterojunction hybrid solar cells have been fabricated using size-quantized PbS nanoparticles and poly (3-hexylthiophene) (P3HT). PbS was used as an electron-transporting layer whereas P3HT was used for hole transport. A photovoltaic device consisting of PbS and P3HT exhibited 3% incident photon to current efficiencies (IPCE) under 550-nm monochromatic irradiation.     

Porous TiO2 thin films synthesized by a spray pyrolysis deposition (SPD) technique and their application to dye-sensitized solar cells

Titanium dioxide (TiO₂) thin films were synthesized on glass substrates from titanium(IV)oxy acetylacetonate 2-butanol solution by a spray pyrolysis deposition (SPD) technique. The films consisted of TiO₂ leaflets and showed the oriented growth along the (2 0 0) direction. The surface area of the film was successfully increased by adding a small amount of aluminum(III) acetylacetonate (AA) in the source solution. This is because AA sublimates easily during the film formation to leave many pores within the film. A dye-sensitized solar cell was constructed with the TiO₂ film which was deposited on the fluorine-doped tin(IV) oxide layer by the SPD technique. The conversion efficiency of the cell was effectively enhanced as high as 3.2% at AA content of 0.6 at% in the source solution, attributing to the fact that the amount of a dye anchored on the surface of TiO₂ layer was the highest at this AA content. Although the conversion efficiency is relatively low, this finding leads to the possibility of an industrial production of a dye-sensitized solar cell in the near future.     

Tin doping in spray pyrolysed indium sulfide thin films for solar cell applications

This paper presents studies carried out on tin-doped indium sulfide films prepared using Chemical Spray Pyrolysis (CSP) technique. Effect of both in-situ and ex-situ doping were analyzed. Ex-situ doping was done by thermal diffusion, which was realized by annealing Sn/In₂S₃ bilayer films. In-situ doping was accomplished by introducing Sn into the spray solution by using SnCl₄·5H₂O. Interestingly, it was noted that by ex-situ doping, conductivity of the sample enhanced considerably without affecting any of the physical properties such as crystallinity or band gap. Analysis also showed that higher percentage of doping resulted in samples with low crystallinity and negative photosensitivity. In-situ doping resulted in amorphous films. In contrast to ex-situ doping, ‘in- situ doping’ resulted in widening of optical band gap through oxygen incorporation; also it gave highly photosensitive films.     

Spray pyrolysis of barrier layers for flexible thin film solar cells on steel

Thin film chalcopyrite solar cells grown on light-weight, flexible substrates are an appealing product. An insulating barrier layer is a requisite for flexible steel substrates to protect the chalcopyrite absorber layer from in-diffusion of iron and also to isolate the solar module, electrically, from the metal substrate. Spray pyrolysis is presented here as a means to deposit an aluminium oxide barrier layer. Optimised spray deposition conditions are investigated and subsequent solar cell results are presented. Resistivity measurements in conjunction with thermography allow assessment of the barrier layer’s insulating properties and occurrence of pin-holes in the layer. Resulting Cu(In,Ga)Se₂ cells, with a barrier layer, reach an efficiency of 14.4%.     

Thin film solar cells of CdS/PbS chemically deposited by an ammonia-free process

A new type of solar cell with structure glass/ITO/CdS/PbS/conductive graphite was constructed and studied. Both window (CdS) and absorption (PbS) layers were deposited by means of the chemical bath deposition (CBD) technique. The maximum temperature employed during the solar cell processing was 70 °C and it did not include any post-treatment. In case of the CdS window layer, complexing agents alternative to ammonia were employed in the CBD process and their effects on the CdS films properties were studied. The solar cells are photosensitive in a large spectral range (all visible and near infrared regions); the cell with the area of 0.16 cm² without any special treatment has shown the values of open-circuit voltage V_oc of 290 mV and short circuit current J_sc of 14 mA/cm² with the efficiency η=1.63% (fill factor FF is 0.36) under illumination intensity of 900 W/m². It was found that the CBD-made PbS layer has a certain degree of porosity, which favorably affects its applicability in solar cell construction. The possible ways of device optimization, and in particular, the effect of the PbS grain size on its performance are discussed.     

Novel etching method on high rate ZnO:Al thin films reactively sputtered from dual tube metallic targets for silicon-based solar cells

Highly transparent and conductive aluminum-doped zinc oxide thin films (ZnO:Al) were reactively sputtered from metallic targets at high rate of up to 90 nm m/min. For the application as transparent light scattering front contact in silicon thin film solar cells, a texture etching process is applied. Typically, it is difficult to achieve appropriate etch features in hydrochloric acid as the deposition process must be tuned and the interrelation is not well understood. We thus introduce a novel two-step etching method based on hydrofluoric acid. By tuning the etch parameters we varied the surface morphology and achieved a regular distribution of large craters with the feature size of 1-2 μm in diameter and about 250 nm in depth. Microcrystalline silicon single junction solar cells (μc-Si:H) and amorphous/microcrystalline silicon (a-Si:H/μc-Si:H) tandem solar cells with high efficiency of up to 8.2% and 11.4%, respectively, were achieved with optimized ZnO:Al films as light scattering transparent front contact.     

PbS nanocrystal solar cells fabricated using microwave-assisted chemical bath deposition

n-CdS/p-PbS heterojunction solar cell was fabricated using microwave-assisted Chemical Bath Deposition (CBD). The CdS window layer (340 nm thickness) was deposited on ITO-glass. The PbS absorber layer (685–1250 nm thickness) with different molar concentration (0.02, 0.05, 0.075 and 0.1 M) was then grown on ITO/CdS to fabricate the p–n junction. X-ray diffraction analysis confirms the formation of pure and nanocrystalline CdS and PbS phases with a preferred orientation depending on molarity; (111) or (200). Scanning electron microscopy observations show a uniform surface morphology with gatherings. UV–Vis spectrophotometer and FTIR was used to estimate the optical properties. Optical measurements gave an energy gap of 2.6 eV for CdS whereas that for PbS thin films were found to vary in a narrow range 0.40–0.47 eV, depending on the molar concentration. The photovoltaic properties under 30 mW/cm² solar radiation including J–V characteristics, short-circuit current (I_sc), open-circuit voltage (V_oc), fill factor (ff), efficiency (η) of CdS/PbS heterojunction cells have been as well examined. The results show that changing the molar concentration improved the performances of the fabricated photovoltaic cells; a high efficiency was observed at 0.1 M. However, high series resistance and poor crystallinity of PbS lead to low efficiency at lower molarity.     

Enhanced efficiency of thin film GaAs solar cells with plasmonic metal nanoparticles

In the present work, a thin film solar cell structure consisting of thin GaAs layer, metallic nanoparticle array and aluminum back reflector is proposed and studied to calculate optical absorption and current density using finite difference time domain (FDTD) numerical simulation method. Simulation results show that in comparison to other metallic nanoparticles, aluminum nanoparticles have strong plasmonic scattering effect at optimized period of 100nm and radius 40nm to improve the efficiency of thin film GaAs solar cells through enhancement of current density integrated over solar spectrum by 31% compared to bare thin film GaAs solar cells.     

Structural,optical, and H2 gas sensing analyses of Cr doped CuO thin films grown by ultrasonic spray pyrolysis

Here, a specific metal oxide (CuO) and its impurity (Cr) added composites were grown onto glass substrates as nanostructured thin films by executing ultrasonic spray pyrolysis method. The effects of the varied Cr dopant concentration on the morphological, structural, optical and H₂ gas sensor properties of the synthesized CuO thin films were determined by conducting scanning electron microscopy, X-ray Diffraction, X-ray photoelectron spectroscopy, photoluminescence spectroscopy, ultraviolet–visible spectroscopy, and gas detection analyses. The X-Ray Diffraction analysis revealed the presence of CuO crystals with predominant (111) plane and it changed to (002) orientation for the doped samples, where crystallite sizes varied between 32 and 46 nm. The structural studies disclosed that the crystalline structure modified due to the added impurities. The scanning electron microscopy observations unveiled polyhedron-like shape formations of the synthesized nanostructures which also showed clear indications of changed morphology due to the impacts of different Cr doping percentages. Besides, the presence of copper, oxygen, and chromium was confirmed by EDX elemental analysis as well as X-ray photoelectron spectroscopy. The optical examination concluded that absorbance values followed a random trend with respect to the increased impurity contents while bandgap decreased with the increase of doping concentration. And, it was also noted that the luminescent emission peaks decreased in the photoluminescence spectroscopy as a result of introduced impurity levels. Finally, H₂ responsivity was detected for the grown films and found out that the impurity doping notably increased the sensitivity of the gas sensor based on the prepared CuO nanostructures.     

Surface texturing of sputtered ZnO:Al/Ag back reflectors for flexible silicon thin-film solar cells

Al-doped zinc oxide/silver (ZnO:Al/Ag) back reflectors for silicon thin-film solar cells with an n-i-p configuration were prepared on flexible stainless steel substrates by dc magnetron sputtering. The surface morphologies of the back reflectors were modified by changing the deposition temperature of the Ag films to improve the light-scattering properties on the back reflectors, resulting in the enhancement of the light-trapping effect in the solar cells. By elevating the deposition temperature from room temperature to 500 °C, the surface roughness of the Ag films increased from 6.62 to 46.64 nm. The films at 500 °C had coarse surface features with irregular grain size distributions between 200 and 900 nm, whereas the films produced at low temperatures below 100 °C had smooth surfaces consisting of small grains between 100 and 200 nm. Even after the 100-nm thick ZnO:Al films were deposited on the modified Ag surfaces, the surface microstructure of the ZnO:Al/Ag bilayers was similar to that of the Ag films. The surface roughness of bilayers increased from 7.12 to 39.30 nm with coarsening the Ag surfaces. Haze factor (a ratio of diffuse reflectance to total reflectance) of Ag films was enhanced remarkably from 59% to 74% in a wide wavelength range from 350 to 1100 nm with increasing the surface roughness of the Ag films from 6.62 nm to 46.64 nm. Enhancement in the haze factor was due to the increase of diffuse reflectance on the Ag films, because the total reflectance did not change much with increasing surface roughness of the Ag films. This increasing roughness indicated that the light scattering from the rough surface of the back reflectors improved. The enhanced light scattering from the back reflectors influenced the performance of the solar cells mainly in terms of the short-circuit current density (J_sc). Compared to the back reflectors with smooth surface features, leading to a J_sc value of 9.94 mA/cm², the back reflectors with large surface roughness improved the J_sc value of the solar cells to 13.36 mA/cm² without detrimental changes in the fill factor (FF) and open circuit voltage (V_oc); they eventually increased the conversion efficiency of the solar cells from 5.59% to 7.60%.     

TiO2 thin films as protective material for transparent-conducting oxides used in Si thin film solar cells

Nb-doped TiO₂ films have been fabricated by RF magnetron sputtering as protective material for transparent-conducting oxide (TCO) films used in Si thin film solar cells. It is found that TiO₂ has higher resistance against hydrogen radical exposure, utilizing the hot-wire CVD (catalytic CVD) apparatus, compared with SnO₂ and ZnO. Further, the minimum thickness of TiO₂ film as protective material for TCO was experimentally investigated. Electrical conductivity of TiO₂ in the as-deposited film is found to be 10⁻⁶ S/cm due to the Nb doping. Higher conductivity of 10⁻² S/cm is achieved in thermally annealed films. Nitrogen treatments of Nb-doped TiO₂ film have been also performed for improvements of optical and electric properties of the film. The electrical conductivity becomes 4.5×10⁻² S/cm by N₂ annealing of TiO₂ films at 500 °C for 30 min. It is found that the refractive index n of Nb-doped TiO₂ films can be controlled by nitrogen doping (from n=2.2 to 2.5 at λ = 550 nm) using N₂ as a reactive gas. The controllability of n implies a better optical matching at the TCO/p-layer interface in Si thin film solar cells.     

Deposition of transparent and conductive Al-doped ZnO thin films for photovoltaic solar cells

The effect of the substrate temperature on the optoelectronic properties of ZnO-based thin films prepared by rf magnetron sputtering has been studied. Three different targets (Zn/Al 98/2 at%, ZnO:Al 98/2 at% and ZnO:Al₂O₃ 98/2 wt%) have been investigated in order to compare resulting samples and try to reduce the substrate temperature down to room temperature. From the ZnO:Al₂O₃ target, transparent conductive zinc oxide has been obtained at 25°C with the average optical transmission in the 400–800 nm wavelength range, T = 80–90% and resistivity, = 3−5 × 10⁻³ Ωcm. In Al:Zn0 layers, the spatial distribution of the electrical properties across the substrate placed parallel to the target has been improved by depositing at high substrate temperatures, above 200°C. Besides, owing to diffusion processes of CuInSe₂ and CdS take place at 200°C, an AI:ZnO/CdS/CuInSe₂ polycrystalline solar cell made with the Al:ZnO deposited at 25°C as the transparent conductive oxide, has shown a more efficient photovoltaic response, η = 6.8%, than the one measured when the aluminium-doped zinc oxide has been prepared at 200°C, η = 1.8%.     

Photoconductivity in Cd1−xMnxS thin films prepared by spray pyrolysis technique

The growth and study of Mn-doped CdS films on glass substrate using spray pyrolysis technique upto 15% of Mn doping level has been done. Structural changes from wurtzite to zinc blend is observed with increase in Mn concentration. Surface morphology of undoped films is found to possess self-assembled noodle-like alignment of grains, which dissociates on increasing Mn concentration. The photoconductivity measurements of these films in light are done in a homemade setup where light-emitting diode (LED) is used to illuminate the sample. In this setup usual complex arrangements needed for photoconductivity measurements are reduced to a great extent. The persistent photocurrent decays faster in Mn-doped CdS.     

Transparent conductive Sn-doped indium oxide thin films deposited by spray pyrolysis technique

Films of indium oxide doped with tin (ITO) are prepared using the low cost spray pyrolysis technique. The effect of tin doping on the physical properties of In2O3 are studied. In this study the polycrystalline ITO films with the different Sn concentration of 1 to 100-wt% SnCl₂ were prepared on Corning 7059 glass substrate. These films were confirmed to show the high crystallinity by X-ray diffraction technique. Low sheet resistance (25Ω/▪) and high visible transmission (˜82%) were obtained when the films were deposited at the tin concentration of 2-wt%.     

2-Ethyl-1-hexanol based screen-printed titania thin films for dye-sensitized solar cells

Nanocrystalline titania thin films were prepared by screen printing in order to efficiently control and optimize the main step of the dye-sensitized solar cells (DSSCs) fabrication process. Different compositions of nanocrystalline titanium dioxide screen-printing pastes are described, based on 2-ethyl-1-hexanol solvent and commercial Degussa P25 TiO₂. The rheological properties of the prepared pastes are presented as the crucial parameter of the deposition procedure. The produced titania thin films are extensively characterized by means of spectroscopy (Raman, XRD) and microscopy (SEM, AFM). The performance (induced photon-to-current efficiency—IPCE% and overall energy conversion efficiency—η%) of the corresponding DSSCs is also reported.     

Characterization of some metal-free organic dyes as photosensitizer for nanocrystalline ZnO-based dye sensitized solar cells

We report the photoelectrochemical characteristics of some biologically used dye: Bromophenol, Ponceau S, Sudan IV, Giemsa, and Acridine Orange as sensitizers. The J_SC from 2.5 to 0.47 mA cm⁻² with the order Bromophenol > Ponceau S > Sudan IV > Giemsa > Acridine orange, the V_OC from 642 to 384 mV, the fill factor (FF) from 0.61 to 0.40, and P_max from 855 to 84 μW cm⁻² were obtained from the DSSCs sensitized with these metal free organic dyes. Among these dyes, Bromophenol gave the best performance as sensitizer with maximum current, which is due to the better interaction between the hydroxyl groups of the dye on the surface of ZnO porous film. Incident photon- to-current conversion efficiency (IPCE) achieved with the use of these dyes follows the order Ponceau S > Sudan IV > Bromophenol > Giemsa > Acridine orange.     

High efficiency, magnetron sputtered CdS/CdTe solar cells

Polycrystalline II–VI semiconductor materials show great promise for efficient, low-cost photovoltaics. Large-area deposition of the II–VI semiconductors such as CdTe is possible by a variety of methods but the use of a plasma-based method such as magnetron sputtering can have significant advantages. Here we present recent results in the fabrication of CdS/CdTe cells using rf magnetron sputtering and discuss some of the advantages that accrue from the use of sputtering methods in this class of materials. Some of these advantages are particularly relevant as the polycrystalline thin-film PV community addresses issues related to the fabrication of tandem cells with efficiencies over 25%. Our best results have been obtained with sputtered ZnO:Al to achieve a CdTe solar cell having 14.0% efficiency at one sun with an air mass 1.5 global spectrum. We have also studied reactive sputtering of ZnTe:N which shows promise for use as a transparent back contact or as a recombination junction with ZnO:Al for II–VI based alloy top cells in a tandem solar-cell configuration. Finally, some advances have been made in substrate-configuration CdTe cells on Mo using sputter deposition that hold promise for flexible CdTe-based PV.