Improvement of life time of minority carriers in GaAs epi-layer grown on Ge substrate

A buffer layer structure on Ge substrate was studied for MOCVD growth of a high-quality GaAs layer. The buffer layer structure was designed taking into consideration both lattice constants and thermal expansion coefficients of GaAs and Ge. It consisted of a preliminarily grown thin layer of Al_xGa_1−xAs and a GaAs layer. Photoluminescence (PL) decay of a GaAs layer in an Alo_0.2Ga_0.8As-GaAs-Al_0.2Ga_0.8As double-hetero (DH) structure, which was grown on the buffer layer structure, was observed by time-resolved PL method to estimate the quality of epilayers in the DH structure. The PL decay time strongly depended on Al content (x) of the Al_xGa_1−x As preliminary layer, and the highest value was obtained when the x was 0.25. A PL decay time above 20 ns was successfully obtained for the DH structure grown on the buffer layer structure, which consisted of a 0.05 μm thick Al_0.25Ga_0.75As layer and a 1 μm thick GaAs layer. Although this value was half of that for the DH structure grown on GaAs substrate, it was much longer than the value of 3 ns for the DH structure grown on Ge substrate with a conventional GaAs buffer layer 1 μm thick.     

Novel device structure for Cu(In,Ga)Se2 thin film solar cells using transparent conducting oxide back and front contacts

Cu(In_1−xGa_x)Se₂ (CIGS)-based thin film solar cells fabricated using transparent conducting oxide (TCO) front and back contacts were investigated. The cell performance of substrate-type CIGS devices using TCO back contacts was almost the same as that of conventional CIGS solar cells with metallic Mo back contacts when the CIGS deposition temperatures were below 500 °C for SnO₂:F and 520 °C for ITO. CIGS thin film solar cells fabricated with ITO back contacts had an efficiency of 15.2% without anti-reflection coatings. However, the cell performance deteriorated at deposition temperatures above 520 °C. This is attributed to the increased resistivity of the TCO’s due to the removal of fluorine from SnO₂ or undesirable formation of a Ga₂O₃ thin layer at the CIGS/ITO interface. The formation of Ga₂O₃ was eliminated by inserting an intermediate layer such as Mo between ITO and CIGS. Furthermore, bifacial CIGS thin film solar cells were demonstrated as being one of the applications of semi-transparent CIGS devices. The cell performance of bifacial devices was improved by controlling the thickness of the CIGS absorber layer. Superstrate-type CIGS thin film solar cells with an efficiency of 12.8% were fabricated using a ZnO:Al front contact. Key techniques include the use of a graded band gap Cu(In,Ga)₃Se₅ phase absorber layer and a ZnO buffer layer along with the inclusion of Na₂S during CIGS deposition.     

Multi-junction III–V solar cells: current status and future potential

Our recent R&D activities of III–V compound multi-junction (MJ) solar cells are presented. Conversion efficiency of InGaP/InGaAs/Ge has been improved up to 31–32% (AM1.5) as a result of technologies development such as double hetero-wide band-gap tunnel junction, InGaP–Ge hetero-face structure bottom cell, and precise lattice-matching of InGaAs middle cell to Ge substrate by adding indium into the conventional GaAs layer. For concentrator applications, grid structure has been designed in order to reduce the energy loss due to series resistance, and world-record efficiency InGaP/InGaAs/Ge 3-junction concentrator solar cell with an efficiency of 37.4% (AM1.5G, 200-suns) has been fabricated. In addition, we have also demonstrated high-efficiency and large-area (7000 cm²) concentrator InGaP/InGaAs/Ge 3-junction solar cell modules of an outdoor efficiency of 27% as a result of developing high-efficiency InGaP/InGaAs/Ge 3-junction cells, low optical loss Fresnel lens and homogenizers, and designing high thermal conductivity modules.Future prospects are also presented. We have proposed concentrator III–V compound MJ solar cells as the 3rd generation solar cells in addition to 1st generation crystalline Si solar cells and 2nd generation thin-film solar cells. We are now developing low-cost and high output power concentrator MJ solar cell modules with an output power of 400 W/m² for terrestrial applications.     

Superstrate-type CuInSe2-based thin film solar cells by a low-temperature process using sodium compounds

Superstrate-type solar cells with a Au/CuInSe₂(CIS)/In_xSe_y,/ZnO : Al/glass structure were investigated. The CIS films were deposited by coevaporation method with intentionally incorporated Na₂S at a substrate temperature of 350°C. Even at relatively low substrate temperatures, sodium compounds enhanced the (1 1 2) preferred orientation of the chalcopyrite structure, and also improved the cell performance. The In_xSe_y buffer layers disappeared after CIS deposition by interdiffusion. Preliminary cells yielded an efficiency of 7.5% with V_oc, = 430 mV, J_sc = 29.4 mA/cm² and FF = 0.60. The light soaking and forward bias effects were observed for these cells.     

Large area CIGS2 thin film solar cells on foils: nucleus of a pilot plant

In earlier research, conversion efficiency of 10.4% (AM1.5) and 9.9% (AM0) has been achieved on small area CuIn_xGa_1−xS₂ (CIGS2) solar cell on 127 μm thick stainless steel substrate. The area of research is mainly focused on studying CIGS2 thin films as solar cell absorber material and growing high efficiency cells on ultralightweight and flexible metallic foils such as 127 μm thick stainless steel and SiO₂ coated 25 μm thick Ti foils. This paper presents the scaling up process of CIGS2 thin film substrate from 2.5 × 2.5 cm² to 10 × 10 cm². Initial scaling up efforts focused on achieving uniform thickness and stress-free films. Process of scaling up consisted of refurbishment of selenization/sulfurization furnace, design and fabrication of scrubber and enlargement of new CdS deposition setup. The scaling up from 2.5 × 2.5 cm² to 10 × 10 cm² substrate size has laid the foundation for PV Materials Lab of Florida Solar Energy Center becoming the nucleus of a pilot plant.     

Novel materials for high-efficiency III–V multi-junction solar cells

As a result of developing wide bandgap InGaP double hetero structure tunnel junction for sub-cell interconnection, InGaAs middle cell lattice-matched to Ge substrate, and InGaP-Ge heteroface structure bottom cell, we have demonstrated 38.9% efficiency at 489-suns AM1.5 with InGaP/InGaP/Ge 3-junction solar cells by in-house measurements. In addition, as a result of developing a non-imaging Fresnel lens as primary optics, a glass-rod kaleidoscope homogenizer as secondary optics and heat conductive concentrator solar cell modules, we have demonstrated 28.9% efficiency with 550-suns concentrator cell modules with an area of 5445 cm². In order to realize 40% and 50% efficiency, new approaches for novel materials and structures are being studied. We have obtained the following results: (1) improvements of lattice-mismatched InGaP/InGaAs/Ge 3-junction solar cell property as a result of dislocation density reduction by using thermal cycle annealing, (2) high quality (In)GaAsN material for 4- and 5-junction applications by chemical beam epitaxy, (3) 11.27% efficiency InGaAsN single-junction cells, (4) 18.27% efficiency InGaAs/GaAs potentially modulated quantum well cells, and (5) 7.65% efficiency InAs quantum dot cells.     

High-efficiency InGaP/In0.01Ga0.99As tandem solar cells lattice-matched to Ge substrates

Conversion efficiency (AM1.5G) of more than 30% was achieved by adding a small quantity of Indium into a GaAs bottom cell in the conventional tandem solar cell on Ge substrate. It was found that the lattice-mismatch between GaAs and Ge caused misfit-dislocations in thick GaAs layers and reduced an open-circuit voltage (V_oc) of the cell. An In_0.49Ga_0.51P/In_0.01Ga_0.99As tandem cell lattice-matched to Ge showed a great improvement in efficiency, which was attributed to an increase in the V_oc of the bottom cell and increases in the photocurrents both in the top and bottom cells due to reductions in band-gap energy.     

Preparation of Culn(SxSe1−x)2 thin films by sulfurization and selenization

A CuIn(S_xSe_1−x)₂ alloy thin-film was prepared by selenization of CuInS₂: its composition ratio x can be controlled by the number of selenization cycles implemented. Crystallinity of the films was improved by annealing in vacuum. The resistivity of the film was about 1 Ω cm and increased by one to two orders of magnitude after KCN treatment. An 8.1 % efficiency solar cell was obtained by using this annealed alloy thin-film.     

III–V compound multi-junction solar cells: present and future

As a result of top cell material quality improvement, development of optically and electrically low-loss double-hetero structure tunnel junction, photon and carrier confinements, and lattice-matching between active cell layers and substrate, the last 15 years have seen large improvements in III–V compound multi-junction (MJ) solar cells. In this paper, present status of R&D program for super-high-efficiency MJ cells in the New Sunshine Project in Japan is presented. InGaP/InGaAs/Ge monolithic cascade 3-junction cells with newly recorded efficiency of 31.7% at AM1.5 (1-sun) were achieved on Ge substrates, in addition to InGaP/GaAs//InGaAs mechanically stacked 3-junction cells with world-record efficiency of 33.3%. Future prospects for realizing super-high-efficiency and low-cost MJ solar cells are also discussed.     

用于高效级联太阳电池的ZnSe材料研究

研究了用于高效Znse／GaAs/Ge(硒化锌绅化镓／锗)级联太阳电池顶电池的ZnSe材料。用MBE技术制备了ZnSe p-n结样品，测量了其外量子效率；提出了改进ZnSe顶电池性能的方法；分析了ZnSe／GaAs／Ge结构比GaInP／GaAs／Ge结构的优越之处。     

New ultra thin CIGS structure solar cells using SCAPS simulation program

The present contribution reports on the performances of ultra thin chalcopyrite Cu (In,Ga) Se (CIGS) solar cells. An alternative ZnO/CdS/CIGS/Si structure has been proposed using solar cell capacitance simulator (SCAPS). The main idea behind this analysis is the improvement of the device efficiency using materials cheaper than conventional CIGS. For that purpose, a 1 μm of a new layer p-Si has been added. Various thicknesses of CIGS absorber layer ranging from 0.1 to 1 μm have been used. Our findings showed that the increase of the absorber layer thickness leads to the improvement of the performance of the new CIGS solar cells. It was found that the best structure must have a window layer ZnO, a buffer layer (CdS), an absorbent layer (CIGS) and a Si layer with thicknesses of 0.02, 0.05, 1 and 1 μm, respectively. Cells with these features give conversion efficiency of 21.3%. The present results showed that the new ultra thin CIGS solar cells structure has performance parameters that are comparable to those of the conventional ones with reduced cost.     

Optimizing Gallium Arsenide multiple quantum wells as high-performance photovoltaic devices

We examine the possibility of using gallium arsenide (GaAs) quantum wells, which have significantly high absorption coefficient for photon energies near the energy band gap, as high-performance solar cells. Using a semi-empirical model of the absorption spectrum, we determine the critical well widths at which the efficiencies of solar cells based on the GaAs/Al_xGa_1−xAs quantum well structure can be optimized.     

Catalytic hydrogenation for improvement of GaAs/Ge solar cell efficiency

Hydrogen passivation on MOCVD grown p-GaAs epilayers on Ge substrate have been studied by plasma and catalytic hydrogenation and the results were compared. The conversion efficiency of the GaAs/Ge solar cells was found to increase by 10% after catalytic hydrogenation at AM1.5. This increase in efficiency is probably due to passivation of surface dangling bonds.     

Characterization of Cu(InxGa1−x)2Se3.5 thin films prepared by rf sputtering

Cu(In_xGa_1−x)₂Se_3.5 thin films were fabricated by rf sputtering from CuIn_xGa_1−xSe₂ and Na mixture target by controlling the mixture ratio. X-ray diffraction analyses show that the structure of Cu(In_xGa_1−x)₂Se_3.5, thin films is different from chalcopyrite structure: especially, CuIn₂Se_3.5 thin films have a defect chalcopyrite structure. The lattice parameters for Cu(In_xGa_1−x)₂Se_3.5 thin film are slightly smaller than those for CuIn_xGa_1−xSe₂ thin film and linearly decreased with increasing Ga content. The optical absorption coefficients for Cu(In_xGa_1−x)₂Se_3.5, thin films exceed 2 × 10⁴ cm⁻¹ in energy region above the fundamental band edge. The band gap for Cu(In_xGa_1−x)₂Se_3.5 thin films is larger than that for CuIn.Ga_1−x2Se₂ with the same Ga content and increased with increasing Ga content.     

Thin film GaAs solar cells with increased quantum efficiency due to light reflection

Thin film GaAs solar cells, separated from their substrate using the weight-induced epitaxial lift-off technique, were compared with conventional cells on a substrate. The thin film cells can be illuminated from both sides using a mirror. The thickness of the p-type GaAs layer, which is the base layer for front illumination and the emitter layer for rear illumination, was varied between 0.25 and 2.5 μm. For both front and rear illumination, the cell efficiency shows a maximum at a thickness of 1.5 μm. The rear illuminated cell current is only 10% lower than for front illumination. Light reflection in the thin film cell enhances the external quantum efficiency and the collection efficiency in the higher wavelength region from 0.84 to 0.90 and from 0.82 to 0.95, respectively.     

Development of Cu(InGa)Se2-based thin-film PV modules with a Zn(O,S,OH)x buffer layer

The CBD-Zn(O,S,OH)_x buffer process is reviewed. Applying this buffer, our highest efficiencies are achieved, such as a circuit (or submodule) efficiency of 14.2% at an aperture area of 864 cm² on a 30 cm × 30 cm-sized substrate and module efficiencies of 13.4% at an aperture area of 3459 cm² on a mosaic module in which four 30 cm × 30 cm-sized circuits are connected in parallel and 12.8% at an aperture area of 3456 cm² on a 30 cm × 120 cm-sized substrate. Our module structure is a cover glass/EVA/MOCVD-BZO window/CBD-Zn(O,S,OH)_x buffer/CIGSS surface layer/CIGS absorber/Mo base electrode/soda-lime glass. Development of both the hardware (i.e. CBD apparatus) applicable to the mass production and the suitable control parameters is necessary to establish the robust baseline process for the CBD-Zn(O,S,OH)_x buffer. Finding of %T monitoring and post-deposition light soaking in this buffer process contributes not only to improve the reproducibility, but also to enhance the electrical yield and the I–V performance.     

Quantum dot integration in heterostructure solar cells

InAs self-assembled quantum dots (SA-QDs) were incorporated into GaAlAs/GaAs heterostructure for solar cell applications. The structure was fabricated by molecular beam epitaxy on p-GaAs substrate. After the growth of GaAs buffer layer, multi-stacked InAs QDs were grown by self-assembly with a slow growth rate of 0.01 ML/s, which provides high dot quality and large dot size. Then, the structure was capped with n-GaAs and wide band gap n-GaAlAs was introduced. One, two or three stacks of QDs were sandwiched in the p–n heterojunction. The contribution of QDs in solar cell hetero-structure is the quantized nature and a high density of quantized states. I–V characterization was conducted in the dark and under AM1 illumination with 100 mW/cm² light power density to confirm the solar cell performance. Photocurrent from the QDs was confirmed by spectral response measurement using a filtered light source (1.1-μm wavelength) and a tungsten halogen lamp with monochromator with standard lock-in technique. These experimental results indicate that QDs could be an effective part of solar cell heterostructure. A typical I–V characteristic of this yet-to-be-optimized solar cell, with an active area of 7.25 mm², shows an open circuit voltage V_oc of 0.7 V, a short circuit current I_sc of 3.7 mA, and a fill factor FF of 0.69, leading to an efficiency η of 24.6% (active area).     

GaInP single junction and GaInP/GaAs two junction thin-film solar cell structures by epitaxial lift-off

The epitaxial lift-off (ELO) technique was used in forming a thin-film GaInP/GaAs two-junction monolithic tandem solar cell structure. First, the GaInP single junction solar cell to be used in the tandem cell structure as a top cell was thinned by the ELO process. Although the ELO process and the transfer to the quartz substrate caused a strain in the thin-film cell after separation from the GaAs substrate, the photoluminescence peak intensity was not decreased. This shows that defects, such as those causing carrier loss, were not introduced on the thin-film cell during the thinning process. The key issue for thin-film cell fabrication is to avoid damaging the AlInP window layer during the selective etching (HF etchant), by which the thin-film cell is released from the GaAs substrate. A GaInP/GaAs monolithic tandem structure was also thinned by the same process with a GaInP single junction cell. Characteristics of the single-junction GaInP cell and individual cells in the GaInP/GaAs tandem structure were examined. It was found that the spectral response remains almost the same as that for cells with a GaAs substrate, thus confirming the feasibility of using the ELO process to fabricate thin-film GaInP/GaAs cells.     

Over 27% efficiency GaAs/InGaAs mechanically stacked solar cell

We have applied an InGaAs solar cell (band GAP = 0.75 eV) to the bottom cell of the super-high-efficiency tandem solar cell aiming an over 35% conversion efficiency. The InGaAs cell which is lattice-matched to the InP substrate showed the efficiency of 5.5% under the GaAs substrate with low carrier concentration. Combining with the GaAs cell by means of a mechanically stacking technique, we obtained an efficiency of 28.8% at air mass (AM) 1.5, 1-sun. This result suggests the possibility of the cells with the efficiency of over 35% with combining a GalnP/GaAs monolithic tandem cell and the InGaAs cell (or InGaAsP cell).     

Cu(In,Ga)Se2 solar cells with superstrate structure using lift-off process

Cu(In,Ga)Se₂ (CIGS) solar cells with a superstrate structure were fabricated using a lift-off process. To widen the variety of substrate choices for CIGS solar cells, a lift-off process was developed without an intentional sacrificial layer between the CIGS and Mo back-contact layers. The CIGS solar cells fabricated on Mo/soda-lime glass (SLG) were transferred to an alternative SLG substrate. The conversion efficiency of the CIGS solar cells with the superstrate structure was 5.1%, which was almost half that of the CIGS solar cells with a substrate structure prior to the lift-off process. The low conversion efficiency was caused by the high series resistance and low shunt resistance, which would be due to the junction resistance between the CIGS/back contact and cracks introduced during the lift-off process, respectively.