CdO/Cu2O solar cells by chemical deposition

CdO and Cu₂O thin films have been grown on glass substrates by chemical deposition method. Optical transmittances of the CdO and Cu₂O thin films have been measured as 60–70% and 3–8%, respectively in 400–900 nm range at room temperature. Bandgaps of the CdO and Cu₂O thin films were calculated as 2.3 and 2.1 eV respectively from the optical transmission curves. The X-ray diffraction spectra showed that films are polycrystalline. Their resistivity, as measured by Van der Pauw method yielded 10⁻²–10⁻³ Ω cm for CdO and approximately 10³ Ω cm for Cu₂O. CdO/Cu₂O solar cells were made by using CdO and Cu₂O thin films. Open circuit voltages and short circuit currents of these solar cells were measured by silver paste contacts and were found to be between 1–8 mV and 1–4 μA.     

Absorption coefficient of bulk and thin film Cu2O

The optical absorption coefficient of thin film and bulk Cu₂O at room temperature is obtained from an accurate analysis of their transmittance and reflectance spectra. These absorption spectra are modeled, together with the low temperature data reported in the literature, using an analytical expression to assess and quantify the role of the different absorption mechanisms. The results suggest that direct forbidden transitions and indirect transitions play an almost equally relevant role. A table of the optical constants of Cu₂O single crystal is given for reference.     

Nano-structured Cu2O solar cells fabricated on sparse ZnO nanorods

Nano-structured Cu₂O/ZnO nanorod (NR) heterojunction solar cells fabricated on indium tin oxide (ITO)-coated glass are studied. Substrate film and NR density have a strong influence on the preferred growth of the Cu₂O film. The X-ray diffractometer (XRD) analysis results show that highly (2 0 0)-preferred Cu₂O film was formed when plating on plain ITO substrate. However, a highly (1 1 1)-preferred Cu₂O film was obtained when plating on sparse ZnO NRs. SEM, TEM and XRD studies on sparse NR samples indicate that the Cu₂O nano-crystallites mostly initiate its nucleation on the peripheral surfaces of the ZnO NRs, and are also highly (1 1 1)-oriented. Solar cells with ZnO NRs yielded much higher efficiency than those without. In addition, ZnO NRs plated on a ZnO-coated ITO glass significantly improve the shunt resistance and open-circuit voltage (V_oc) of the devices, with consistently much higher efficiency obtained than when ZnO NRs are directly plated on ITO film. However, longer NRs do not improve the efficiency due to low short-circuit current (J_sc) and slightly higher series resistance. The best conversion efficiency of 0.56% was obtained from a Cu₂O/ZnO NRs heterojunction solar cell fabricated on a 80 nm ZnO-coated ITO glass with V_oc=0.514 V, J_sc=2.64 mA/cm² and 41.5% fill factor.     

Effect of Cu2O coating on graphite as anode material of lithium ion battery in PC-based electrolyte

Cuprous oxide-coated graphite was synthesized by a polyol reduction process and analyzed by scanning electron microscopy, charge–discharge measurements and cyclic voltammetry. Cu₂O exists at the surface of graphite in the form of nanoparticles and nanorods. The coated cuprous oxide layer acts as a protective layer separating graphite from the propylene carbonate (PC)-based electrolyte solution, and greatly suppresses PC decomposition and graphite exfoliation in PC-based electrolyte systems.     

Investigation of n-type Cu2O layers prepared by a low cost chemical method for use in photo-voltaic thin film solar cells

A low cost and simple chemical method of boiling copper plates in CuSO₄ solution is used to prepare Cu₂O layers. X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), glow discharge optical emission spectroscopy (GDOES) and optical absorption have been used to characterise these layers. It has been found that the layers consist of Cu₂O phase with a thickness of about 1.4 μm for 60 minutes boiling in CuSO₄ solution. The largest grain sizes are in the order of 1 μm and the layers contain cubic Cu₂O phases. The layers are n-type in electrical conduction and the optical band gap observed is 2.2 eV.     

Nanostructured SrTiO3 thin films sensitized by Cu2O for photoelectrochemical hydrogen generation

We prepared nanostructured thin films of pristine SrTiO₃, Cu₂O and SrTiO₃/Cu₂O heterojunction with varying the thickness of Cu₂O. SrTiO₃ and Cu₂O thin films were deposited on ITO (Sn:In₂O₃) glass substrate using sol–gel spin-coating technique and spray pyrolysis method respectively. Samples were characterized using XRD (X-ray diffractometry), SEM (Scanning electron microscopy), and UV–Visible absorption spectroscopy. Nanostructured thin films of pristine SrTiO₃, Cu₂O and SrTiO₃/Cu₂O heterojunction systems were used as photoelectrode in the Photoelectrochemical (PEC) cell for water splitting reaction. Maximum photocurrent density value of 2.44 mA cm⁻² at 0.95 V/SCE were observed for SrTiO₃/Cu₂O heterojunction photoelectrode with 454 nm thickness, which was approximately 34 times higher than pristine SrTiO₃ thin film. Increased photocurrent density observed for the heterojunction can be attributed to the improved conductivity and better separation of the photogenerated charge carriers at the SrTiO₃/Cu₂O interface.     

Solar hydrogen generation with H2O/ZnO/MnFe2O4 system

The hydrogen generation reaction in the H₂O/ZnO/MnFe₂O₄ system was studied to clarify the possibility of whether this reaction system can be used for the two-step water splitting to convert concentrated solar heat to chemical energy of H₂. At 1273 K, the mixture of ZnO and MnFe₂O₄ reacted with water to generate H₂ gas in 60% yield. X-ray diffractometry and chemical analysis showed that 48 mol% of Mn^II (divalent manganese ion) in the A-site of MnFe₂O₄ was substituted with Zn^II (divalent zinc ion) and that chemical formula of the solid product was estimated to be Zn_0.58Mn^II_0.42Mn^III_0.39Fe_1.61O₄ (Mn^III: trivalent manganese ion). Its lattice constant was smaller than that of the MnFe₂O₄ (one of the two starting materials). From the chemical composition, the reaction mechanism of the H₂ generation with this system was discussed. Since the Mn ions in the product solid after the H₂ generation reaction are oxidized to Mn³⁺, which can readily release the O²⁻ ions as O₂ gas around 1300 K, the two-step of H₂ generation and O₂ releasing seem to be cyclic.     

Stability of a Cu2O photoelectrode in an electrochemical cell and the performances of the photoelectrode coated with Au and SiO thin films

The photoresponse and stability of Cu₂O films have been examined. Thermodynamic calculations showed that, for Cu₂O, there exists a region of chemical stability potential between −0.218 and −0.489 V(S.C.E) for oxidation and reduction potential, respectively. In an aqueous solution, a deterioration in power output occurs at a rate of 50% per day. To stabilize the photocurrent, thin deposits of Au and SiO films onto Cu₂O electrodes have been studied. For the Au deposition, the photocurrent was either quenched or reduced. For the SiO deposited photoelectrode, its effect was to decrease the quantum efficiency of Cu₂O. However, the deposition does not affect the band gap at 2.11 eV (which ensued for an uncoated sample).     

Electrodeposited p-type Cu2O as photocatalyst for H2 evolution from water reduction in the presence of WO3

Different p-type Cu₂O powders were prepared from electrodeposition and subjected to analysis of their photocatalytic activity in water reduction. The electrodeposited Cu₂O powders were obtained by scraping the deposited films off the substrate. Under illumination the Cu₂O powders alone were not able to catalyze H₂ generation from water reduction. However, these Cu₂O powders exhibited photocatalytic activity in H₂ generation when they were coupled with n-type WO₃ in suspensions. The coupling was made to avoid back reactions of the photo-induced charges. The electrodeposited Cu₂O powders showed higher photocatalytic activity than a commercially available Cu₂O powder. The suspension containing electrodeposited Cu₂O with a strong [1 1 1] orientation gave a larger amount of H₂ evolution than that containing Cu₂O with a [1 1 0] orientation. Appropriate crystalline-texture tuning, as well as charge delocalization promotion, is looked to as the key issue for efficient H₂ generation from water reduction over p-type Cu₂O photocatalysts.     

Methods of observation and elimination of semiconductor defect states

A method of observation of interface states for ultrathin insulating layer/semiconductor interfaces is developed by use of X-ray photoelectron spectroscopy (XPS) measurements under bias. The analysis of the energy shift of the semiconductor core level as a function of the bias voltage gives energy distribution of interface states. When the atomic density of SiO₂ layers is low (e.g., SiO₂ layers formed at 350 °C), only one interface state peak is observed near the midgap, and it is attributed to isolated Si dangling bonds at the interface. For SiO₂ layers with a high atomic density (e.g., SiO₂ layers formed at 700 °C), on the other hand, two interface state peaks, one above and the other below the midgap, are observed, and they are attributed to Si dangling bonds interacting weakly with a Si or oxygen atom in SiO₂. Interface states can be passivated by cyanide treatment which simply involves the immersion in cyanide solutions such as KCN and HCN solutions. When the cyanide treatment is applied to indium tin oxide/SiO₂/mat-textured single crystalline Si metal-oxide-semiconductor (MOS) solar cells, the photovoltage is greatly increased, leading to a high conversion efficiency of 16.2%. When the cyanide treatment is performed on polycrystalline Si (poly-Si)-based MOS diodes, a greater effect in comparison to that for single crystalline Si-based MOS diodes is observed due to the elimination of defect states in poly-Si as well as Si/SiO₂ interface states. The cyanide treatment can also increase the conversion efficiency of pn-junction single crystalline and poly-Si solar cells.     

Preparation of ZnO thin films using MOCVD technique with D2O/H2O gas mixture for use as TCO in silicon-based thin film solar cells

Zinc oxide (ZnO) thin films have been successfully grown by metal organic chemical vapor deposition (MOCVD) technique using deuterium water (D₂O) and water (H₂O) mixtures as oxidants for diethylzinc (DEZ). B₂H₆ was also employed as a dopant gas. It was found that the crystal orientation of ZnO films strongly depends on D₂O/H₂O ratio. As a result, the surface morphology of ZnO changed from textured surface morphology to smooth surface morphology with increase in the ratio of D₂O/H₂O. Moreover, it was also observed that the carrier concentration of ZnO films did not change with the ratio of D₂O/H₂O, while the mobility of these films was strongly dependent on the D₂O/H₂O ratio. Without D₂O addition, the resistivity of films had its lowest value and the minimum sheet resistance was 10 Ω/square. All films showed transmittance higher than 80% in the visible region. Moreover, the haze values of these films could be controlled by the ratio of D₂O/H₂O. These results indicate that the crystal orientation and surface morphology of the low resistivity ZnO films can be modified by using a mixture of D₂O and H₂O without changing the deposition temperature. Thus, the obtained ZnO films are promising for use as a front TCO layer in Si-based thin film solar cells.     

Chemical composition dependence of morphological and optical properties of Cu2ZnSnS4 thin films deposited by sol-gel sulfurization and Cu2ZnSnS4 thin film solar cell efficiency

The properties of Cu₂ZnSnS₄ (CZTS) thin films deposited by sol-gel sulfurization were investigated as a function of the chemical composition of the sol-gel solutions used. The chemical composition ratio Cu/(Zn+Sn) of the sol-gel solution was varied from 0.73 to 1.00, while the ratio Zn/Sn was kept constant at 1.15. CZTS films deposited using sol-gel solutions with Cu/(Zn+Sn)<0.80 exhibited large grains. In addition, the band gaps of these Cu-poor CZTS thin films were blue shifted. Solar cells with the structure Al/ZnO:Al/CdS/CZTS/Mo/soda lime glass were fabricated under non-vacuum conditions. The solar cell with the CZTS layer deposited using the sol-gel solution with Cu/(Zn+Sn)=0.80 exhibited the highest conversion efficiency of 2.03%.     

Improved performance of MEH-PPV/ZnO solar cells by addition of lithium salt

The paper reports the improved performance by addition of lithium bis(trifluoromethanesulfonyl)amide (LiTFSI) to poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV) in the hybrid solar cells consisting of MEH-PPV as an electron donor and vertically aligned ZnO nanorod array as an electron acceptor. Results show that, with increasing the weight ratio R of LiTFSI/MEH-PPV, the charge transfer efficiency at MEH-PPV/ZnO interface, the device short circuit current (J_sc) and open circuit voltage (V_oc) get increased for R ? 2/10, but decreased when R > 2/10, resulting in a peak power conversion efficiency of η = 0.48% for R = 2/10 at AM 1.5 illumination (100 mW/cm²). It is revealed that the increased J_sc is due to the improved charge transfer between the MEH-PPV and ZnO as a result of the interaction between LiTFSI and MEH-PPV, while the increased V_oc and the decreased charge recombination are attributed to the increased hole mobility of MEH-PPV; moreover, the decreased J_sc and V_oc at high R values are attributed to the morphology degradation in the active layer due to the high LiTFSI content.     

New materials and deposition techniques for highly efficient silicon thin film solar cells

This paper reviews recent efforts to provide the scientific and technological basis for cost-effective and highly efficient thin film solar modules based on amorphous (a-Si:H) and microcrystalline (μc-Si:H) silicon. Textured ZnO:Al films prepared by sputtering and wet chemical etching were applied to design optimised light-trapping schemes. Necessary prerequisite was the detailed knowledge of the relationship between film growth, structural properties and surface morphology obtained after etching. High rate deposition using plasma enhanced chemical vapour deposition at 13.56 MHz plasma excitation frequency was developed for μc-Si:H solar cells yielding efficiencies of 8.1% and 7.5% at deposition rates of 5 and 9 Å/s, respectively. These μc-Si:H solar cells were successfully up-scaled to a substrate area of 30×30 cm² and applied in a-Si:H/μc-Si:H tandem cells showing initial test cell efficiencies up to 11.9%.     

Hydrolysis rate of submicron Zn particles for solar H2 synthesis

The hydrolysis rate of Zn particles by up to 50 mol% water vapor in Ar gas was measured by thermogravimetric analysis at atmospheric pressure and 330–360 °C and quantified by a core-shell model. An initial ZnO layer led to an initially linear conversion profile attributed to a fast surface reaction (half-order with respect to water vapor mole fraction, y) followed by a parabolic conversion profile independent of y but dependent on Zn ion diffusion through a ZnO layer. The latter is most important for solar H₂ formation by the Zn/ZnO water-splitting cycle as it determines the required process residence time for Zn hydrolysis. A ready-to-use equation for calculation of ZnO and H₂ formation during Zn hydrolysis is proposed and compared to literature data revealing enhanced hydrolysis rates for submicron Zn particles.     

Hybrid solar cells based on MEH-PPV and thin film semiconductor oxides (TiO2, Nb2O5, ZnO, CeO2 and CeO2–TiO2): Performance improvement during long-time irradiation

Performance improvement of hybrid solar cells (HSC) applying five different thin film semiconductor oxides has been observed during long-time irradiation in ambient atmosphere. This behavior shows a direct relation between HSC and oxygen content from the environment. Photovoltaic devices were prepared as bi-layers of thin film semiconducting oxides (TiO₂, Nb₂O₅, ZnO, CeO₂–TiO₂ and CeO₂) and the polymer MEH-PPV, with a final device configuration of ITO/Oxide_{thin film}/MEH-PPV/Ag. The oxides were prepared as thin transparent films from sol–gel solutions. The photovoltaic cells were studied in ambient atmosphere by recording the initial values of open circuit voltage (V_oc) and current density (I_sc). Solar decay curves presented as the measurement of the short circuit current as a function of time, IV curves and photophysical analyses were also carried out for each type of device. Solar cells with TiO₂ thin films showed the best performance with maximum V_oc as high as −0.74 V and I_sc of 0.4 mA/cm². Solar decay analyses showed that the devices require a stabilization period of several hours in order to reach maximum performance. In the case of TiO₂, Nb₂O₅ and CeO₂–TiO₂, the maximum current density was observed after 15 h; for CeO₂, the maximum performance was observed after 30 h. The only exception was observed with devices applying ZnO in which the current density decreased drastically and degraded the polymer in just a couple of hours.     

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.     

CO2 and H2O reduction by solar thermochemical looping using SnO2/SnO redox reactions: Thermogravimetric analysis

The thermochemical dissociation of CO₂ and H₂O from reactive SnO nanopowders is studied via thermogravimetry analysis. SnO is first produced by solar thermal dissociation of SnO₂ using concentrated solar radiation as the high-temperature energy source. The process targets the production of CO and H₂ in separate reactions using SnO as the oxygen carrier and the syngas can be further processed to various synthetic liquid fuels. The global process thus converts and upgrades H₂O and captured CO₂ feedstock into solar chemical fuels from high-temperature solar heat only, since the intermediate oxide is not consumed but recycled in the overall process. The objective of the study was the kinetic characterization of the H₂O and CO₂ reduction reactions using reactive SnO nanopowders synthesized in a high-temperature solar chemical reactor. SnO conversion up to 88% was measured during H₂O reduction at 973 K and an activation energy of 51 ± 7 kJ/mol was identified in the temperature range of 798-923 K. Regarding CO₂ reduction, a higher temperature was required to reach similar SnO conversion (88% at 1073 K) and the activation energy was found to be 88 ± 7 kJ/mol in the range of 973-1173 K with a CO₂ reaction order of 0.96. The SnO conversion and the reaction rate were improved when increasing the temperature or the reacting gas mole fraction. Using active SnO nanopowders thus allowed for efficient and rapid fuel production kinetics from H₂O and CO₂.     

Semiconductor-sensitized solar cells based on nanocrystalline In2S3/In2O3 thin film electrodes

A possibility of semiconductor-sensitized thin film solar cells have been proposed. Nanocrystalline In₂S₃-modified In₂O₃ electrodes were prepared with sulfidation of In₂O₃ thin film electrodes under H₂S atmosphere. The band gap (E_g) of In₂S₃ estimated from the onset of the absorption spectrum was approximately 2.0 eV. The photovoltaic properties of a photoelectrochemical solar cell based on In₂S₃/In₂O₃ thin film electrodes and I⁻/I₃⁻ redox electrolytes were investigated. This photoelectrochemical cell could convert visible light of 400–700 nm to electron. A highly efficient incident photon-to-electron conversion efficiency (IPCE) of 33% was obtained at 410 nm. The solar energy conversion efficiency, η, under AM 1.5 (100 mW cm⁻²) was 0.31% with a short-circuit photocurrent density (J_sc) of 3.10 mA cm⁻², a open-circuit photovoltage (V_oc) of 0.26 V, and a fill factor ( ff ) of 0.38.     

Development of highly efficient thin film silicon solar cells on texture-etched zinc oxide-coated glass substrates

ZnO films prepared by magnetron sputtering on glass substrates and textured by post-deposition chemical etching are applied as substrates for p–i–n solar cells. Using both rf and dc sputtering, similar surface textures can be achieved upon etching. Excellent light trapping is demonstrated by high quantum efficiencies at long wavelengths for microcrystalline silicon solar cells. Applying an optimized microcrystalline/amorphous p-layer design, stacked solar cells with amorphous silicon top cells yield similarly high stabilized efficiencies on ZnO as on state-of-the-art SnO₂ (9.2% for a-Si/a-Si). The efficiencies are significantly higher than on SnO₂-coated float glass as used for module production.