Synthesis and electro-optic properties of nanosized-boron doped cadmium oxide thin films for solar cell applications

Boron doped CdO thin films were prepared by sol–gel dip coating technique. Atomic force microscopy results indicate that the boron doped CdO films have the nanostructure. The influence of the boron doping on the film growth is resulted in a change of grain size. The optical band gap of the CdO films was significantly changed by boron dopant. The refractive index dispersion of the films obeys the single oscillator model. The dispersion parameters, oscillator and dispersion energy were changed by boron dopant. The optical absorption results show that the optical band gap of the CdO film can be engineered over a wide range of 2.27–2.45 eV by introducing B dopant. For solar cell applications of the CdO film, a p-Si/1% B doped n-CdO heterojunction solar cell was fabricated and the solar cell shows the best values of open circuit voltage, V_oc = 0.37 and short circuit current density, J_sc = 0.81 mA/cm² under AM1.5 illumination, despite the fact that V_oc and J_sc are lower than those reported in the literature without using frontal grid contacts and or post-deposition annealing. It is evaluated that this work is useful as a basis search for synthesis of the nanosized-boron doped cadmium oxide thin films for solar cell applications and more competitive p-Si/n-CdO based solar cells.     

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.     

Improvement of a-Si solar cell properties by using SnO2:F TCO films coated with an ultra-thin TiO2 layer prepared by APCVD

TiO₂-overcoated SnO₂:F transparent conductive oxide films were prepared by atmospheric pressure chemical vapor deposition (APCVD) and an effect of TiO₂ layer thickness on a-Si solar cell properties was investigated. The optical properties and the structure of the TiO₂ films were evaluated by spectroscopic ellipsometry and X-ray difractometry. a-Si thin film solar cells were fabricated on the SnO₂:F films over-coated with TiO₂ films of various thicknesses (1.0, 1.5 and 2.0 nm) and I–V characteristics of these cells were measured under 1 sun (100 mW/cm² AM-1.5) illumination. It was found that the TiO₂ film deposited by APCVD has a refractive index of 2.4 at 550 nm and anatase crystal structure. The conversion efficiency of the a-Si solar cell fabricated on the 2.0 nm TiO₂-overcoated SnO₂:F film increased by 3%, which is mainly attributed to an increase in open circuit voltage (V_oc) of 30 mV.     

An effective use of nanocrystalline CdO thin films in dye-sensitized solar cells

Thin films of cadmium oxide (CdO) were synthesized by layer-by-layer deposition method on indium doped tin oxide (ITO) substrates. Post-deposition annealing at 250 °C for 24 h produced pure phase CdO films by removal of trace amount of cadmium hydroxide, as confirmed from X-ray diffractogram. First time employment of CdO in place of TiO₂ in dye-sensitized solar cells is reported to check feasibility and cell performance. A dye-sensitized nanocrystalline CdO photo-electrode was obtained by adsorbing cis-dithiocyanato (4,4′-dicarboxylic acid-2,2′-bipyridide) ruthenium (II) (N3) dye by keeping at 45 °C for 20 h. The efficiency of dye-sensitized nanocrystalline CdO thin film solar cell was increased from 0.24% to 2.95% due to dye adsorption. This must be highest reported conversion efficiency for other metal oxides than TiO₂based dye-sensitized solar cells.     

Analysis of multicrystalline silicon solar cells by modified 3-diode equivalent circuit model taking leakage current through periphery into consideration

We proposed a modified 3-diode equivalent circuit model for analysis of multicrystalline silicon (Mc-Si) solar cells. By using this equivalent circuit model, we can precisely evaluate the characteristics of Mc-Si solar cells taking the influence of grain boundaries and large leakage current through the peripheries into consideration and extract electrical properties. The calculated value of current-voltage characteristics for small size (3 mm×3 mm) Mc-Si solar cells using this model completely agreed with the measured value at various cell temperatures. Moreover, the calculated open-circuit voltage (V_oc) obtained by extracted parameters and measured V_oc agreed well.     

Photovoltaic characteristics of phosphorus-doped amorphous carbon films grown by r.f. plasma-enhanced CVD

The phosphorus-doped amorphous carbon (n-C:P) films were grown by r.f. power-assisted plasma-enhanced chemical vapor deposition at room temperature using solid phosphorus target. The influence of phosphorus doping on material properties of n-C:P based on the results of simultaneous characterization are reported. Moreover, the solar cell properties such as series resistance, short circuit current density (J_sc), open circuit current voltage (V_oc), fill factor (FF) and conversion efficiency (η) along with the spectral response are reported for the fabricated carbon based n-C:P/p-Si heterojunction solar cell were measured by standard measurement technique. The cells performances have been given in the dark I–V rectifying curve and I–V working curve under illumination when exposed to AM 1.5 illumination condition (100 mW/cm², 25 °C). The maximum of V_oc and J_sc for the cells are observed to be approximately 236 V and 7.34 mA/cm², respectively for the n-C:P/p-Si cell grown at lower r.f. power of 100 W. The highest η and FF were found to be approximately 0.84% and 49%, respectively. We have observed the rectifying nature of the heterojunction structures is due to the nature of n-C:P films.     

Electrodeposition zinc-oxide inverse opal and its application in hybrid photovoltaics

This article reports the preparation of three-dimensional (3D) mesoporous zinc oxide (ZnO) films and their application in solar cells. The films were obtained through electrochemical deposition in DMSO solutions by using PS colloidal crystal as templates. The ZnO films with inverse opal (IO) structure were obtained after removing the templates by thermolysis. The ordered porous ZnO films were used to prepare hybrid solar cells by infiltrating the films with poly(3-hexylthiophene) (P3HT) or P3HT:ZnO nanocomposite. Results showed that the interpenetrating network of both ZnO(IO) and P3HT can form continuous pathways for electron and hole transport. By infiltrating a P3HT:ZnO nanocomposite into the porous ZnO films, the photocurrent of the solar cell can be dramatically improved. The cell shows the V_oc and I_sc of 462 mV and 444.3 μA/cm², respectively. By using a 420 nm cutoff filter, the cell retains about 80% and 50% of its original V_oc and I_sc after continuous white-light illumination (100 mW/cm²) for 10 h. Stability of the device under above conditions was estimated to be 51 h.     

RF sputter deposition of the high-quality intrinsic and n-type ZnO window layers for Cu(In,Ga)Se2-based solar cell applications

Transparent ZnO films were prepared by rf magnetron sputtering, and their electrical, optical, and structural properties were investigated under various sputtering conditions. Aluminum-doped n-type(n-ZnO) and undoped intrinsic-ZnO (i-ZnO) layers were deposited on a glass substrate by incorporating different targets in the same reaction chamber. The n-ZnO films were strongly affected by argon ambient pressure and substrate temperature, and films deposited at 2 mTorr and 100°C showed superior properties in resistivity, transmission, and figure of merit (FOM). The sheet resistance of ZnO film was less dependent on film thickness when the substrate was heated during deposition. These positive effects of elevated substrate temperature are presumably attributed to the rearrangement of the sputtered atoms by the heat energy. Also, the films are electrically uniform through the 5 cm×5 cm substrate. The maximum deviation in sheet resistance is less than 10%. All of the films showed strong (0 0 2) diffraction peak near 2θ =34°. The undoped i-ZnO films deposited in the mixture of argon and oxygen gases showed high transmission properties in the visible range, independent of the Ar/O₂ ratio, while resistivity rose with increased oxygen partial pressure. The Cu(In,Ga)Se₂ solar cells, incorporating bi-layer ZnO films (n-ZnO/i-ZnO) as window layer, were finally fabricated. The fabricated solar cells showed 14.48% solar efficiency under AM 1.5 conditions (100 mW/cm²).     

p-doped μc-Si:H window layers prepared by hot-wire CVD for amorphous solar cell application

We report on boron-doped μc-Si:H films prepared by hot-wire chemical vapor deposition (HWCVD) using silane as a source gas and trimethylboron (TMB) as a dopant gas and their incorporation into all-HW amorphous silicon solar cells. The dark conductivity of these films was in the range of 1–10 (Ω cm)⁻¹. The open circuit voltage V_oc of the solar cells was found to decrease from 840 mV at low hydrogen dilution H-dil=91% to 770 mV at high H-dil =97% during p-layer deposition which can be attributed to the increased crystallinity at higher H-dil and to subsequent band edge discontinuity between μc-Si:H p- and amorphous i-layer. The short circuit current density J_sc and the fill factor FF show an optimum at an intermediate H-dil and decrease for the highest H-dil. To improve the conversion efficiency and the reproducibility of the solar cells, an amorphous-like seed layer was incorporated between TCO and the bulk p-layer. The results obtained until now for amorphous solar cells with and without the seed layer are presented. The I–V parameters for the best p–i–n solar cell obtained so far are J_sc=13.95 mA/cm², V_oc=834 mV, FF=65% and η=7.6%, where the p-layers were prepared with 2% TMB. High open circuit voltages up to 847 mV could be achieved at higher TMB concentrations.     

Properties of an n-C:P/p-Si carbon-based photovoltaic cell grown by radio frequency plasma-enhanced chemical vapor deposition at room temperature

The phosphorus-doped amorphous carbon (n-C:P) films were grown by radiofrequency (RF) power-assisted plasma-enhanced chemical vapor deposition (PECVD) at room temperature using a solid phosphorus target. The influence of phosphorus doping on the material properties of n-C:P based on the results of simultaneous characterization are reported. Moreover, solar cell properties such as series resistance, short-circuit current density, open-circuit current voltage, fill factor and conversion efficiency along with the spectral response are reported for the fabricated carbon-based n-C:P/p-Si heterojunction solar cells by standard measurement technique. The cells’ performances have been given in the dark I–V rectifying curve and I–V working curve under illumination when exposed to AM 1.5 illumination condition (100 mW/cm², 25 °C). The maximum open-circuit voltage (V_oc) and short-circuit current density (J_sc) for the cells are observed to be approximately 236 V and 7.34 mA/cm², respectively, for the n-C:P/p-Si cell grown at a lower RF power of 100 W. The highest energy conversion efficiency (η) and fill factor (FF) were found to be approximately 0.84% and 49%, respectively. We have observed that the rectifying nature of the heterojunction structures is due to the nature of n-C:P films.     

Investigations on ZnxCd1−xO thin films obtained by spray pyrolysis

Zn_xCd_1−xO thin films were prepared on glass substrates by spray pyrolysis technique. The precursor solutions were obtained by varying the concentration of Zn(NO₃)₂·6H₂O and Cd(NO₃)₂·4H₂O in bi-distilled water. The structural properties have been studied using X-ray diffraction spectra. All the structures include the basic compounds, i.e. ZnO and CdO. The orientation and the crystalline phases of the deposited films were specified. With the addition of Zn to the precursor solution, we can observe the preferential orientation of the CdO in the [2 0 0] direction. The electrical measurements were performed using method of four contacts. Thin films transmittances, in the 1.5–4.3 eV range, for different compositions have been measured and the optical gaps have been determined. The variations are explained considering the gaps of the two pure films. The influence of increased Cd concentration in the films on the structural, electrical and optical properties is investigated in this study.     

Stability of thin film solar cells having less-hydrogenated amorphous silicon i-layers

In this study, highly stabilized hydrogenated amorphous silicon films and their solar cells were developed. The films were fabricated using the triode deposition system, where a mesh was installed between the cathode and the anode (substrate) in a plasma-enhanced chemical vapor deposition system. At a substrate temperature of 250 °C, the hydrogen concentration of the resulting film (Si–H=4.0 at%, Si–H₂<1×10²⁰ cm⁻³) was significantly less than that of conventionally prepared films. The films were used to develop the i-layers of solar cells that exhibited a significantly low degradation ratio of 7.96%.     

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.     

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.     

Solar cells using iodine-doped polythiophene–porphyrin polymer films

Wet-type organic solar cells containing 5,10,15,20-3-tetrathienylporphyrin (TThP) and polythiophene (PTh) films were fabricated. The TThP/PTh film was prepared on indium-tin-oxide (ITO) glass using an electrochemical polymerization method in an n-Bu₄NPF₆/CH₂Cl₂ solution. It was found that a small amount of iodine doping of the film improved the incident photon-to-electron conversion efficiency (IPCE) of a solar cell consisting of a TThP/PTh film and an aqueous electrolyte. A HOMO level measurement suggested that a modified HOMO level of the low iodine-doped TThP/PTh film allowed a fast electron transfer from PTh to a porphyrin moiety. To obtain further improvement, a sandwich-type solar cell using a 5% (w/w) aqueous solution of acetonitrile containing 0.05 M iodine and 0.5 M lithium iodide as an electrolyte was then fabricated. The solar cell absorbed light in the 300–800 nm wavelength range, converting this to a cathodic photocurrent with a maximum IPCE of 32% at 430 nm under irradiation of 5.0×10¹⁴ photon cm⁻² s⁻¹. This value is about 10 times higher than that of the solar cells using an aqueous electrolyte. The total energy conversion efficiency (η) of the solar cell under simulated sunlight reached 0.12% for 2.59 mW cm⁻² at AM1.5 and 0.05% for 100 mW cm⁻² at air mass 1.5.     

Electrodeposited cuprous oxide on indium tin oxide for solar applications

Semiconducting cuprous oxide films were prepared by electrodeposition onto commercial conducting glass coated with indium tin oxide deposited by spraying technique. The cuprous oxide (Cu₂O) films were deposited using a galvanostatic method from an alkaline CuSO₄ bath containing lactic acid and sodium hydroxide at a temperature of 60°C. The film's thickness was about 4–6 μm. This paper includes discussion for Cu₂O films fabrication, scanning electron microscopy and X-ray diffractometry studies, optical properties and experimental results of solar cells. The values of the open circuit voltage V_oc of 340 mV and the short circuit current density I_sc of 245 μA/cm² for ITO/Cu₂O solar cell were obtained by depositing graphite paste on the rear of the Cu₂O layer. It should be stressed that these cells exhibited photovoltaic properties after heat treatment of the films for 3 h at 130°C. An electrodeposited layer of Cu₂O offers wider possibilites for application and production of low cost cells, both in metal–semiconductor and hetero-junction cell structures, hence the need to improve the photovoltaic properties of the cells.     

Deposition of hydrogenated amorphous silicon (a-Si:H) films by hot-wire chemical vapor deposition (HW-CVD) method: Role of substrate temperature

Hydrogenated amorphous silicon (a-Si:H) thin films were deposited from pure silane (SiH₄) using hot-wire chemical vapor deposition (HW-CVD) method. We have investigated the effect of substrate temperature on the structural, optical and electrical properties of these films. Deposition rates up to 15 Å s⁻¹ and photosensitivity 10⁶ were achieved for device quality material. Raman spectroscopic analysis showed the increase of Rayleigh scattering in the films with increase in substrate temperature. The full width at half maximum of TO peak (Γ_TO) and deviation in bond angle (Δθ) are found smaller than those obtained for P-CVD deposited a-Si:H films. The hydrogen content in the films was found <1 at% over the range of substrate temperature studied. However, the Tauc's optical band gap remains as high as 1.70 eV or much higher. The presence of microvoids in the films may be responsible for high value of band gap at low hydrogen content. A correlation between electrical and structural properties has been found. Finally, the photoconductivity degradation of optimized a-Si:H film under intense sunlight was also studied.     

Effect of the Cu underlayer on the optoelectrical properties of ITO/Cu thin films

Sn doped indium oxide (ITO) single layer films and ITO/Copper (Cu) bi-layer films were prepared on polycarbonate substrates by DC and RF magnetron sputtering without intentional substrate heating. In order to consider the influence of the Cu underlayer on the optoelectrical properties and microstructures of the films, the thickness of the Cu bottom layer in the ITO/Cu films was varied from 5 to 20 nm.Conventional ITO films had a constant optical transmittance of 74% and an electrical resistivity of 3.1 × 10⁻³ Ω cm, while ITO/Cu films had different optoelectrical properties that were influenced by the thickness of the Cu bottom layer. The lowest electrical resistivity, 5.7 × 10⁻⁵ Ω cm, was obtained from ITO 80 nm/Cu 20 nm films and the highest optical transmittance of 72%, was obtained from the ITO 95 nm/Cu 5 nm films. From the figure of merit (_TC) which is defined by _TC = T¹⁰/R_s, where T is the optical transmittance at 550 nm and R_s is the sheet resistance, it can be concluded that the most effective Cu thickness in the ITO/Cu films on the optoelectrical properties was 5 nm.     

Photoluminescence characteristics of CdS layers deposited in a chemical bath and their correlation to CdS/CdTe solar cell performance

In this work, we study CdS films processed by chemical bath deposition (CBD) using different thiourea concentrations in the bath solution with post-thermal treatments using CdCl₂. We study the effects of the thiourea concentration on the photovoltaic performance of the CdS/CdTe solar cells, by the analysis of the I–V curve, for S/Cd ratios in the CBD solution from 3 to 8. In this range of S/Cd ratios the CdS/CdTe solar cells show variations of the open circuit voltage (V_oc), the short circuit current (J_sc) and the fill factor (FF). Other experimental data such as the optical transmittance and photoluminescence were obtained in order to correlate to the I–V characteristics of the solar cells. The best performance of CdS–CdTe solar cells made with CdS films obtained with a S/Cd ratio of 6 is explained in terms of the sulfur vacancies to sulfur interstitials ratio in the CBD–CdS layers.     

Anthocyanins and betalains as light-harvesting pigments for dye-sensitized solar cells

We present the photoelectrochemical properties of dye-sensitized solar cells using natural pigments containing betalains and anthocyanins as sensitizers. The dyes extracted from grape, mulberry, blackberry, red Sicilian orange, Sicilian prickly pear, eggplant and radicchio have shown a monochromatic incident photon to current efficiency (IPCE) ranging from 40% to 69%. Short circuit photocurrent densities (J_sc) up to 8.8 mA/cm², and open circuit voltage (V_oc) ranging from 316 to 419 mV, were obtained from these natural dyes under 100 mW/cm² (AM 1.5) simulated sunlight. The best solar conversion efficiency of 2.06% was achieved with Sicilian prickly pear fruits extract. The influence of pH and co-absorbers on natural sensitizers, were investigated and discussed.