Microstructured extremely thin absorber solar cells

In this paper we present the realization of extremely thin absorber (ETA) solar cells employing conductive glass substrates functionalized with TiO₂ microstructures produced by embossing. Nanocrystalline or compact TiO₂ films on Indium doped tin oxide (ITO) glass substrates were embossed by pressing a silicon stamp containing a μm size raised grid structure into the TiO₂ by use of a hydraulic press (1 ton/50 cm²). The performance of these microstructured substrates in a ETA cell sensitized by a thermally evaporated or chemical bath deposited PbS film and completed by a PEDOT:PSS hole conductor layer and a Au counter electrode is compared to that of planar substrates. Surprisingly planar films produced better performance than micro-structured films. A simple model implying photoconductive shunting paths revealed by junction breakdown at negative bias under illumination is presented.     

Optical properties and thermal stability of pulsed-sputter-deposited AlxOy/Al/AlxOy multilayer absorber coatings

Spectrally selective Al_xO_y/Al/Al_xO_y multilayer absorber coatings were deposited on copper (Cu) and molybdenum (Mo) substrates using a pulsed sputtering system. The Al targets were sputtered using asymmetric bipolar-pulsed DC generators in Ar+O₂ and Ar plasmas to deposit an Al_xO_y/Al/Al_xO_y coating. The compositions and thicknesses of the individual component layers were optimized to achieve high solar absorptance (α=0.950-0.970) and low thermal emittance (ε=0.05-0.08). The X-ray diffraction data in thin film mode showed an amorphous structure of the Al_xO_y/Al/Al_xO_y coating. The X-ray photoelectron spectroscopy data of the Al_xO_y/Al/Al_xO_y multilayer absorber indicated that the Al_xO_y layers present in the coating were non-stoichiometric. The optical constants (n and k) of the multilayer absorber were determined from the spectroscopic ellipsometric data. Drude's free-electron model was used for generating the theoretical dispersion of optical constants for Al films, while the Tauc-Lorentz model was used for modeling optical properties of the dielectric Al_xO_y layers. In order to study the thermal stability of the Al_xO_y/Al/Al_xO_y coatings, they were subjected to heat treatment (in air and vacuum) at different temperatures and durations. The multilayer absorber deposited on Cu substrates exhibited high solar selectivity (α/ε) of 0.901/0.06 even after heat-treatment in air up to 400 °C for 2 h. At 450 °C, the solar selectivity decreased significantly on Cu substrates (e.g., α/ε=0.790/0.07). The coatings deposited on Mo substrates were thermally stable up to 800 °C in vacuum with a solar selectivity of 0.934/0.05. The structural stability of the absorber coatings heat treated in air (up to 400 °C) and vacuum (up to 800 °C) was confirmed by micro-Raman spectroscopy measurements. Studies on the accelerated aging tests suggested that the absorber coatings on Cu were stable in air up to 75 h at 300 °C and the service lifetime of the multilayer absorber was predicted to be more than 25 years. Further, the activation energy for the degradation of the multilayer absorber heat treated for longer durations in air is of the order of 64 kJ/mol.     

Experimental investigation of Cu(In1−x,Gax)Se2/Zn(O1−z,Sz) solar cell performance

In this study we investigate the performance of Cu(In_1−x,Ga_x)Se₂/Zn(O_1−z,S_z) solar cells by changing the gallium content of the absorber layer in steps from CuInSe₂ to CuGaSe₂ and at each step vary the sulfur content of the Zn(O,S) buffer layer. By incorporating more or less sulfur into the Zn(O,S) buffer layer it is possible to change its morphology and band gap energy. Surprisingly, the best solar cells with Zn(O,S) buffer layers in this study are found for close to or the same Zn(O,S) buffer layer composition for all absorber Ga compositions. In comparison to their CdS references the best solar cells with Zn(O,S) buffer layers have slightly lower open circuit voltage, V_oc, lower fill factor, FF, and higher short circuit current density, J_sc, which result in comparable or slightly lower conversion efficiencies. The exception to this trend is the CuGaSe₂ solar cells, where the best devices with Zn(O,S) have substantially lowered efficiency compared with the CdS reference, because of lower V_oc, FF and J_sc. X-ray photon spectroscopy and X-ray diffraction measurements show that the best Zn(O,S) buffer layers have similar properties independent of the Ga content. In addition, energy dispersive spectroscopy scans in a transmission electron microscope show evidence of lateral variations in the Zn(O,S) buffer layer composition at the absorber/buffer layer interface. Finally, a hypothesis based on the results of the buffer layer analysis is suggested in order to explain the solar cell parameters.     

New trends to grow the n-CdZn (S1−xSex)2/p-CuIn(S1−xSex)2 heterojunction thin films for solar cell applications

The n-CdZn(S_1−xSe_x) and p-CuIn(S_1−xSe_x)₂ thin films have been grown by the solution growth technique (SGT) on glass substrates. Also the heterojunction (p–n) based on n-CdZn (S_1−xSe_x)₂ and p-CuIn (S_1−xSe_x)₂ thin films fabricated by same technique. The n-CdZn(S_1−xSe_x)₂ thin film has been used as a window material which reduced the lattice mismatch problem at the junction with CuIn (S_1−xSe_x)₂ thin film as an absorber layer for stable solar cell preparation. Elemental analysis of the n-CdZn (S_1−xSe_x)₂ and p-CuIn(S_1−xSe_x)₂ thin films was confirmed by energy-dispersive analysis of X-ray (EDAX). The structural and optical properties were changed with respect to composition ‘x’ values. The best results of these parameters were obtained at x=0.5 composition. The uniform morphology of each film as well as the continuous smooth thickness deposition onto the glass substrates was confirmed by SEM study. The optical band gaps were determined from transmittance spectra in the range of 350–1000 nm. These values are 1.22 and 2.39 eV for CuIn(S_0.5Se_0.5)₂ and CdZn(S_0.5Se_0.5)₂ thin films, respectively. J–V characteristic was measured for the n-CdZn(S_1−xSe_x)₂/p-CuIn(S_1−xSe_x)₂ heterojunction thin films under light illumination. The device parameters V_oc=474.4 mV, J_sc=13.21 mA/cm², FF=47.8% and η=3.5% under an illumination of 85 mW/cm² on a cell active area of 1 cm² have been calculated for solar cell fabrication. The J–V characteristic of the device under dark condition was also studied and the ideality factor was calculated which is equal to 1.9 for n-CdZn(S_0.5Se_0.5)₂/p-CuIn(S_0.5Se_0.5)₂ heterojunction thin films.     

Study of Cd-free buffer layers using Inx(OH,S)y on CIGS solar cells

The alternative buffer layer material In_x(OH,S)_y was deposited on Cu(In,Ga)Se₂ (CIGS) thin films by chemical-bath-deposition (CBD). The impurities in In_x(OH,S)_y buffer layers and their atomic concentration were characterized by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) analyses. In addition, AES was used to depth profile the samples. The band-gap energy of the deposited In_x(OH,S)_y was determined from optical absorption data. Both the dark- and photo-current-voltage (I–V) characteristics of the CIGS solar cells with In_x(OH,S)_y buffer layers were measured, and the results were compared to the CIGS cells deposited with CBD CdS buffer layers.     

Growth of Zn1−xMgxO films with single wurtzite structure by MOCVD process and their application to Cu(InGa)(SSe)2 solar cells

The effect of the growth temperature and Mg/(Mg+Zn) molar flow rate ratio of metal organic sources on the crystalline structure of Zn_1−xMg_xO (ZMO) films is investigated in thin films prepared by metal organic chemical vapor deposition (MOCVD) process on fused silica in order to obtain the wide-bandgap ZMO films with single wurtzite structure, which is very important to achieve high-efficiency chalcopyrite solar cells. Based on the measurements and analysis of the fabricated samples, the ZMO films with the controllable bandgap from 3.3 to 3.72 eV can exhibit a single wurtzite phase depending on the growth temperature and Mg content. Furthermore, the resistivity of ZMO films is comparable to that of ZnO film. It is a good indication that ZMO film is superior to CdS or ZnO films as buffer and window layers mainly due to its controllable bandgap energy and safety. As a result, the solar cells with ZMO buffer were fabricated without any surface treatment of Cu(InGa)(SSe)₂ (CIGSSe) absorber or antireflection coating, and the efficiency of 10.24% was obtained.     

Electronic structure and water splitting under visible-light irradiation of Zn and Ag co-doped In(OH)ySz photocatalysts

Zinc and silver co-doped In(OH)_yS_z with nanocubic blocks morphology were prepared by a one-step hydrothermal method and their photocatalytic activities were investigated. The as-synthesized products were characterized by transmission electron microscopy (TEM), powder X-ray diffraction (XRD), scanning electron microscopy (SEM), inductively coupled plasma (ICP) and UV–visible spectroscopy. The electron microscope observations revealed that the particle sizes of Zn-doped In(OH)_yS_z crystals were smaller than that of the non-doped In(OH)_yS_z, which accords with BET results. While Zn–Ag co-doped In(OH)_yS_z showed the nanocubic blocks with different particle sizes. The UV–vis spectra indicate that the single Zn ions doping leads to the absorbance band shifts toward lower wavelength upon increasing the Zn doping. Consequently, the band gap of In(OH)_yS_z also increases gradually with increasing the Zn doping. In contrast, an obvious red-shift is observed for Zn–Ag co-doped In(OH)_yS_z solid solution, which mainly attributed to the transition from Ag 4d + S 3p orbitals to Zn 4s + In 5s orbitals. The sample doped with 4 mol% Ag and Zn was found to have the highest activity, which is 20 times that of the In(OH)_yS_z.     

Effect of Ga incorporation in sequentially prepared CuInS2 thin film absorbers

Thin film CuInS₂:Ga solar cell absorber films were prepared by sequential evaporation of Cu–In–Ga precursors and sulfurization in sulfur vapor. The depth distribution of Ga was found to be highly inhomogeneous caused by CuGaS₂ phase segregation at the back contact. Depending on overall Ga content and sulfurization temperature a quaternary CuGa_xIn_1−xS₂ compound formed exhibiting a shift in absorber lattice constant and band gap. Micro Raman measurements showed that crystal quality was also affected by Ga. Open-circuit voltages well above 800 mV were achieved while sustaining high fill factors of 71%.     

Synthesis of (CuIn)xCd2(1−x)S2 photocatalysts for H2 evolution under visible light by using a low-temperature hydrothermal method

A new series visible-light driven photocatalysts (CuIn)_xCd_2(1−x)S₂ was successfully synthesized by a simple and facile, low-temperature hydrothermal method. The synthesized materials were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) surface area measurement, X-ray photoelectron spectroscopy (XPS) and ultraviolet-visible spectroscopy (UV–Vis DRS). The results show that the morphology of the photocatalysts changes with the increase of x from 0.01 to 0.3 and their band gap can be correspondingly tuned from 2.37 eV to 2.30 eV. The (CuIn)_xCd_2(1−x)S₂ nanocomposite show highly photocatalytic activities for H₂ evolution from aqueous solutions containing sacrificial reagents, SO₃²⁻ and S²⁻ under visible light. Substantially, (CuIn)_0.05Cd_1.9S₂ with the band gap of 2.36 eV exhibits the highest photocatalytic activity even without a Pt cocatalyst (649.9 μmol/(g h)). Theoretical calculations about electronic property of the (CuIn)_xCd_2(1−x)S₂ indicate that Cu 3d and In 5s5p states should be responsible for the photocatalytic activity. Moreover, the deposition of Pt on the doping sample results in a substantial improvement in H₂ evolution than the Pt-loaded pure CdS and the amount of H₂ produced (2456 μmol/(g h)) in the Pt-loaded doping system is much higher than that of the latter (40.2 μmol/(g h)). The (CuIn)_0.05Cd_1.9S₂ nanocomposite can keep the activity for a long time due to its stability in the photocatalytic process. Therefore, the doping of CuInS₂ not only facilitates the photocatalytic activity of CdS for H₂ evolution, but also improves its stability in photocatalytic process.     

Improved performance of Cu(InGa)Se2 thin-film solar cells using evaporated Cd-free buffer layers

Polycrystalline Cu(InGa)Se₂ (CIGS) thin-film solar cells using evaporated In_xSe_y and ZnIn_xSe_y buffer layers are prepared. The purpose of this work is to replace the chemical bath deposited CdS buffer layer with a continuously evaporated buffer layer. In this study, a major effort is made to improve the performance of CIGS thin-film solar cells with these buffer layers. The relationship between the cell performance and the substrate temperature for these buffer layers is demonstrated. Even at the high substrate temperature of about 550°C for the buffer layer, efficiencies of more than 11% were obtained. Furthermore, the I−V characteristics of the cells using these buffer layers are compared with cells using CdS buffer layers fabricated by chemical bath deposition method. We have achieved relatively high efficiencies of over 15% using both the ZnIn_xSe_y and the CdS buffer layers.     

Visible light-active nitrogen-doped TiO2 thin films prepared by DC magnetron sputtering used as a photocatalyst

The visible light-active nitrogen-doped TiO₂ has been prepared by dc-reactive magnetron sputtering using Ti target in an Ar+O₂/N gas mixture. The preparation of highly crystallized anatase TiO_xN_y thin films with various nitrogen concentrations allowed us to identify the optimum nitrogen flow ratio for the photocatalytic oxidation (PCO) of 2-propanol. At higher nitrogen flow rate, nitrogen is found to be difficult to substitute for oxygen having been predicted to contribute the band gap narrowing, giving rise to undesired deep level defects. In addition, Raman spectroscopy and X-ray diffraction (XRD) studies revealed that highly crystallized anatase growth of nitrogen-doped TiO_xN_y thin films are difficult at higher nitrogen flow rate. The optical band gap was found to be lower for the films deposited at 2 sccm of nitrogen flow rate. The PCO of 2-propanol was studied as a function of nitrogen flow rate using in situ FTIR spectroscopy. The PCO of 2-propanol found to proceed along two routes: one was through the chemisorbed species, 2-propoxide to form the CO₂ directly; the other was through conversion of 2-propanol to acetone, followed by formation of formate species, and finally CO₂.     

Fabrication of wide-gap Cu(In1−xGax)Se2 thin film solar cells: a study on the correlation of cell performance with highly resistive i-ZnO layer thickness

The correlation of the cell performance of wide-gap Cu(In_1−xGa_x)Se₂ (CIGS) solar cells with the thickness of highly resistive i-ZnO layers, which are commonly introduced between the buffer layer and the transparent conductive oxide (TCO) layer in CIGS solar cell devices, was studied. It was found that cell parameters, in particular, the fill factor (F.F.) varied with the thickness of the i-ZnO layers and the variation of the F.F. was directly related to cell efficiency. A 16%-efficiency was achieved without use of an anti-reflection coating from wide-gap (E_g1.3 eV) CIGS solar cells by adjusting the deposition conditions of the i-ZnO layers.     

Progress in electrodeposited absorber layer for CuIn(1−x)GaxSe2 (CIGS) solar cells

Thin film solar cells with chalcopyrite CuInSe₂/Cu(InGa)Se₂ (CIS/CIGS) absorber layers have attracted significant research interest as an important light-to-electricity converter with widespread commercialization prospects. When compared to the ternary CIS, the quaternary CIGS has more desirable optical band gap and has been found to be the most efficient among all the CIS-based derivatives. Amid various fabrication methods available for the absorber layer, electrodeposition may be the most effective alternative to the expensive vacuum based techniques. This paper reviewed the developments in the area of electrodeposition for the fabrication of the CIGS absorber layer. The difficulties in incorporating the optimum amount of Ga in the film and the likely mechanism behind the deposition were highlighted. The role of deposition parameters was discussed along with the phase and microstructure variation of an as-electrodeposited CIGS layer from a typical acid bath. Related novel strategies such as individual In, Ga and their binary alloy deposition for applications in CIGS solar cells were briefed.     

Control of conduction band offset in wide-gap Cu(In,Ga)Se2 solar cells

The effects of conduction band offset of window/Cu(In,Ga)Se₂ (CIGS) layers in wide-gap CIGS based solar cells are investigated. In order to control the conduction band offset, a Zn_1−xMg_xO film was utilized as the window layer. We fabricated CIGS solar cells consisting of an ITO/Zn_1−xMg_xO/CdS/CIGS/Mo/glass structure with various CIGS band gaps (E_g≈0.97–1.43 eV). The solar cells with CIGS band gaps wider than 1.15 eV showed higher open circuit voltages and fill factors than those of conventional ZnO/CdS/CIGS solar cells. The improvement is attributed to the reduction of the CdS/CIGS interface recombination, and it is also supported by the theoretical analysis using device simulation.     

Analysis of heterointerface recombination by Zn1−xMgxO for window layer of Cu(In,Ga)Se2 solar cells

An adjustment of a conduction band offset (CBO) of a window/absorber heterointerface is important for high efficiency Cu(In,Ga)Se₂ (CIGS) solar cells. In this study, the heterointerface recombination was characterized by the reduction of the thickness of a CdS layer and the adjustment of a CBO value by a Zn_1−xMg_xO (ZMO) layer. In ZnO/CdS/CIGS solar cells, open-circuit voltage (V_oc) and shunt resistance (R_sh) decreased with reducing the CdS thickness. In constant, significant reductions of V_oc and R_sh were not observed in ZMO/CdS/CIGS solar cells. With decreasing the CdS thickness, the CBO of (ZnO or ZMO)/CIGS become dominant for recombination. Also, the dominant mechanisms of recombination of the CIGS solar cells are discussed by the estimation of an activation energy obtained from temperature-dependent current-voltage measurements.     

Photoelectrochemical properties of CdSxSe1−x films

CdS_xSe_1−x films of different composition (0 < x < 1) were deposited by pulse plating technique at different duty cycles in the range of 10-50%. The films were polycrystalline and exhibited hexagonal structure. The band gap of the films varies from 1.68 to 2.39 eV as the concentration of CdS increases. Energy Dispersive analysis of X-rays (EDAX) measurements indicate that the composition of the films are nearly the same as that of the precursors considered for the deposition. Atomic force microscopy studies indicated that the grain size increased from 20 to 200 nm as the concentration of CdSe increased. Photoelectrochemical (PEC) cell studies indicated that the films of composition CdS_0.9Se_0.1 exhibited maximum photoactivity. Mott-Schottky studies indicated that the films exhibit n-type behaviour. Spectral response measurements indicated that the photocurrent maxima occurred at the wavelength value corresponding to the band gap of the films.     

Optimization of buffer layers for lattice-mismatched epitaxy of GaxIn1−xAs/InAsyP1−y double-heterostructures on InP

We optimize InAs_yP_1−y buffer layers and compositional grades for lattice-mismatched heteroepitaxy of Ga_xIn_1−xAs/InAs_yP_1−y double-heterostructures on InP. The strains of the active and buffer layers depend on the bulk misfit difference between these layers. The misfit difference is adjusted to eliminate strain in the active layer, thus avoiding misfit dislocations and surface topography that would otherwise form to relieve strain. The optimized structure uses an “overshoot” with respect to the conventional design in the misfit and As composition of the InAs_yP_1−y buffer. Nearly optimized heterostructures typically show excellent structural quality and extended minority-carrier lifetimes.     

Effect of high copper and oxygen concentrations on the optical and electrical properties of (CdTe)xCuyOz films

Thin films of (CdTe)_xCu_yO_z have been prepared by reactive RF cosputtering using high concentrations of copper and oxygen. The films were grown at 350 °C on glass and Si substrates. Under these conditions samples of amorphous nature were obtained with some clusters of Cu₂O for the larger concentrations of Cu and O used in this work. The largest band gap variation, from 3.5 to 1.4 eV, was obtained for the samples grown with an oxygen flow of 17 standard cubic centimeters per minute (sccm) in the growth chamber. The samples are highly resistive for most cases, but for high Cu concentrations resistivities of the order of 10³ Ω-cm were obtained in the case of films grown with a flow of 15 sccm of oxygen.     

Potential of Mn doped In1−xGaxN for implementing intermediate band solar cells

In this paper we propose that the incorporation of Mn into In_1−xGa_xN can produce material suitable for intermediate band (IB) solar cells. For x≈0.22 we predicted that the resulting material would have a total bandgap of 1.11 eV, with the IB located at about 0.74 eV from the valence band (VB). The resulting limiting efficiency is 53.4% (maximum light concentration and assuming that the sun is a black body at 6000 K and the cell operates at 300 K). The use of Mn offers an additional advantage of high solubility in the semiconductor host. The concentration of Mn can exceed the critical value of about 6×10¹⁹ cm^-3, which is considered to be the threshold to inhibit non-radiative recombination and create a true intermediate band.     

Sputtered Cd1−xZnxTe films for top junctions in tandem solar cells

Cd_1−xZn_xTe alloy films with 1.6 and 1.7 eV band gaps were deposited by RF magnetron sputtering from targets made either of mixed powders or alloys of CdTe and ZnTe (25% and 40%). High-quality polycrystalline films with the (1 1 1) preferred orientation were obtained. The films were characterized using X-ray diffraction (XRD), scanning electron microscopy, resistivity, optical absorption, Raman, and photoluminescence. The EDS, XRD, and optical absorption analysis indicated that the x-value of the as-grown films were typically 0.20 and 0.30 for films sputtered from 25% and 40% ZnTe containing targets, respectively. The as-deposited alloy films exhibit quite low photovoltaic performance when used to make cells with CdS as the hetero-junction partner. Therefore, we have studied various post-deposition treatments with vapors of chlorine-containing materials, CdCl₂ and ZnCl₂, in dry air or H₂/Ar ambient at 390 °C. The best performance of a Cd_1−xZn_xTe cell (, ) was found for treatment with vapors of the mixed CdCl₂+0.5%ZnCl₂ in an H₂/Ar ambient after pre-annealing at 520 °C in pure H₂/Ar.