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1.
Fabrication of Zn1−xMgxO films by atomic layer deposition (ALD) has been studied for use as buffer layers in Cu(In,Ga)Se2 (CIGS)‐based solar cell devices. The Zn1−xMgxO films were grown using diethyl zinc, bis‐cyclopentadienyl magnesium and water as precursors in the temperature range from 105 to 180°C. Single‐phase ZnO‐like films were obtained for x < 0·2, followed by a two phase region of ZnO‐ and MgO‐like structures for higher Mg concentrations. Increasing optical band gaps of up to above 3·8 eV were obtained for Zn1−xMgxO with increasing x. It was found that the composition of the Zn1−xMgxO films varied as an effect of deposition temperature as well as by increasing the relative amount of magnesium precursor pulses during film growth. Completely Cd‐free CIGS‐based solar cells devices with ALD‐Zn1−xMgxO buffer layers were fabricated and showed efficiencies of up to 14·1%, which was higher than that of the CdS references. Copyright © 2006 John Wiley & Sons, Ltd.  相似文献   

2.
CuIn1‐xGaxSe2 (CIGS) thin films were grown on Mo/soda lime glass using a reactive sputtering process in which a Se cracker was used to deliver reactive Se molecules. The Cu0·6 Ga0·4 and Cu0·4In0·6 targets were simultaneously sputtered under the delivery of reactive Se. The effects of Se flux on CIGS film deposition were investigated. The CIGS film growth rate decreased, and the surface roughness of a film increased as the Se flux increased. The [112] crystal orientation was dominant, and metallic crystal phases such as Cu9Ga4 and Cu16In9 in a film were disappearing with increasing Se flux. A solar cell fabricated using a 900‐nm CIGS film showed the power conversion efficiency of 8·6%, the highest value found in a sub‐micron thick CIGS solar cell related to a reactive sputtering process with metallic targets. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

3.
In the present work we have studied the effect of Na on the properties of graded Cu(In1−xGax)Se2 (CIGS) layer. Graded CIGS structures were prepared by chemical spray pyrolysis at a substrate temperature of 350 °C on soda lime glass. Sodium chloride is used as a dopant along with metal (Cu/In/Ga) chlorides and n, n-dimethyl selenourea precursors. The addition of Na exhibited better crystallinity with chalcopyrite phase and an improvement in preferential orientation along the (112) plane. Energy dispersive analysis of X-rays (line/point mapping) revealed a graded nature of the film and percentage incorporation of Na (0.86 at%). Raman studies showed that the film without sodium doping consists of mixed phase of chalcopyrite and CuAu ordering. Influence of sodium showed a remarkable decrease in electrical resistivity (0.49–0.087 Ω cm) as well as an increase in carrier concentration (3.0×1018–2.5×1019 cm−3) compared to the un-doped films. As carrier concentration increased after sodium doping, the band gap shifted from 1.32 eV to 1.20 eV. Activation energies for un-doped and Na doped films from modified Arrhenius plot were calculated to be 0.49 eV and 0.20 eV, respectively. Extremely short carrier lifetimes in the CIGS thin films were measured by a novel, non-destructive, noncontact method (transmission modulated photoconductive decay). Minority carrier lifetimes of graded CIGS layers without and with external Na doping are found to be 3.0 and 5.6 ns, respectively.  相似文献   

4.
This study reports the inkjet printing of Ag front contacts on Aluminum doped Zinc Oxide (AZO)/intrinsic Zinc Oxide (i‐ZnO)/CdS/Cu(In1−xGax)Se2 (CIGS)/Mo thin film photovoltaic cells. The printed Ag contacts are being developed to replace the currently employed evaporated Ni/Al bi‐layer contacts. Inkjet deposition conditions were optimized to reduce line resistivity and reduce contact resistance to the Al:ZnO layer. Ag lines printed at a substrate temperature of 200°C showed a line resistivity of 2.06 µΩ · cm and a contact resistance to Al:ZnO of 8.2 ± 0.2 mΩ · cm2 compared to 6.93 ± 0.3 mΩ · cm2 for thermally evaporated contacts. These deposition conditions were used to deposit front contacts onto high quality CIGS thin film photovoltaic cells. The heating required to print the Ag contacts caused the performance to degrade compared to similar devices with evaporated Ni/Al contacts that were not heated. Devices with inkjet printed contacts showed 11.4% conversion efficiency compared to 14.8% with evaporated contacts. Strategies to minimize heating, which is detrimental for efficiency, during inkjet printing are proposed. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

5.
The gallium gradient in Cu(In,Ga)Se2 (CIGS) layers, which forms during the two industrially relevant deposition routes, the sequential and co‐evaporation processes, plays a key role in the device performance of CIGS thin‐film modules. In this contribution, we present a comprehensive study on the formation, nature, and consequences of gallium gradients in CIGS solar cells. The formation of gallium gradients is analyzed in real time during a rapid selenization process by in situ X‐ray measurements. In addition, the gallium grading of a CIGS layer grown with an in‐line co‐evaporation process is analyzed by means of depth profiling with mass spectrometry. This gallium gradient of a real solar cell served as input data for device simulations. Depth‐dependent occurrence of lateral inhomogeneities on the µm scale in CIGS deposited by the co‐evaporation process was investigated by highly spatially resolved luminescence measurements on etched CIGS samples, which revealed a dependence of the optical bandgap, the quasi‐Fermi level splitting, transition levels, and the vertical gallium gradient. Transmission electron microscopy analyses of CIGS cross‐sections point to a difference in gallium content in the near surface region of neighboring grains. Migration barriers for a copper‐vacancy‐mediated indium and gallium diffusion in CuInSe2 and CuGaSe2 were calculated using density functional theory. The migration barrier for the InCu antisite in CuGaSe2 is significantly lower compared with the GaCu antisite in CuInSe2, which is in accordance with the experimentally observed Ga gradients in CIGS layers grown by co‐evaporation and selenization processes. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

6.
In2S3−xSex and (In2S3)x(In2O3)y thin films have been prepared on glass substrates using appropriate heat treatments of In evaporated thin films. X-ray analysis shows that In thin films which were annealed under sulfur atmosphere at 350 °C were mainly formed by In2S3. A heat treatment of this binary in air at 400 °C during one hour leads to (In2S3)x(In2O3)y ternary material which has a tetragonal structure with a preferred orientation of the crystallites along the (109) direction. Similarly, a heat treatment of In2S3 in selenium atmosphere at 350 °C during six hours leads to a new In2S3−xSex ternary material having tetragonal body centered structure with a preferred orientation of the crystallites along the (109) direction. Optical band gap, refractive index and extinction coefficient values of In2S3−xSex and (In2S3)x(In2O3)y thin films have been reached. Moreover, correlations between optical conductivity, XRD, AFM and Urbach energy of such ternary thin films have been discussed. Finally, the recorded formation disparity between the quaternary (In2S3)x(In2O3)y and ternary In2S3−xSex compounds has been discussed in terms of the Simha–Somcynsky and Lattice Compatibility theories.  相似文献   

7.
We report on improvements to the energy conversion efficiency of wide bandgap (Eg > 1.2 eV) solar cells on the basis of CuIn1−xGaxSe2. Historically, attaining high efficiency (>16%) from these types of compound semiconductor thin films has been difficult. Nevertheless, by using (a) the alkaline‐containing high‐temperature EtaMax glass substrates from Schott AG, (b) elevated substrate temperatures of 600–650 °C, and (c) high vacuum evaporation from elemental sources following National Renewable Energy Laboratory's three‐stage process, we have been able to improve the performance of wider bandgap solar cells with 1.2 < Eg < 1.45 eV. The current density–voltage (J–V) data we present includes efficiencies >18% for absorber bandgaps of ~1.30 eV and efficiencies of ~16% for bandgaps up to ~1.45 eV. In comparing J–V parameters in similar materials, we establish gains in the open‐circuit voltage and, to a lesser degree, the fill factor value, as the reason for the improved performance. The higher voltages seen in these wide gap materials grown at high substrate temperatures are due to reduced recombination. We establish the existence of random and discrete grains within the CIGS absorbers that yield limited or no generation/collection of minority carriers. We also show that interfacial recombination is the main mechanism limiting additional enhancements to open‐circuit voltage and therefore performance. Solar cell results, absorber materials characterization, and experimental details and discussion are presented. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

8.
We report on the progress that we have made in the quality of our baseline process for the production of high efficiency soda lime glass/Mo/Cu(In,Ga)Se2 (CIGS)/CdS/i‐ZnO/ZnO:Al/MgF2 solar cells. The enhancement of the average performance level has enabled us to reach conversion efficiencies of up to 19·3% (internal measurement). The new quality initiative uses process control, optical and electrical modelling, and the critical revision of all process steps as tools for the attainment of the 19% efficiency level. Our experiments show that the compositional process window for CIGS solar cells that have an efficiency of η ≈ 19% is very wide. Accordingly, we suggest that an efficiency of 19·0–19·5% is achievable in the following compositional process windows: 0·69 ≤ Cu/(Ga + In) ≤ 0·98 and 0·21 ≤ Ga/(Ga + In) ≤ 0·38. In addition, our results show that large CIGS grains are not a necessary requirement for high efficiencies up to 19%. These findings and the partly lacking ability to correlate certain aspects of our progress with experimental parameters lead us to the conclusion that there are still some important process variables undiscovered. From this conclusion and from the evaluation of the available data we infer that there is a potential for the enhancement of CIGS solar cell efficiencies beyond 20%. Copyright © 2007 John Wiley & Sons, Ltd.  相似文献   

9.
Compared with rigid glass, manufacturing of Cu(In,Ga)Se2 (CIGS) solar cells on flexible stainless steel (SS) substrates has potential to reduce production cost because of the application of roll‐to‐roll processing. Up to now, high‐efficiency cells on SS could only be achieved when the substrate is coated with a barrier layer (e.g. SiOx or Si3N4) for hindering the diffusion of impurities, especially Fe, into the CIGS layer. In this paper, the effect of these impurities on the electronic transport properties of the device is investigated. Using admittance spectroscopy, the presence of a deep defect level at around 320 meV is observed, which deteriorates the efficiency of the solar cells. Furthermore, it is shown that reducing substrate temperature during CIGS deposition is an effective alternative to a barrier layer for reducing diffusion of detrimental Fe impurities into the absorber layer. By applying a CIGS growth process for deposition at low substrate temperatures, an efficiency of 17.7%, certified by Fraunhofer Institute ISE, Freiburg, was achieved on Mo/Ti‐coated SS substrate without an additional metal‐oxide or metal‐nitride impurity diffusion barrier layer. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

10.
Cu(In,Ga)Se2 (CIGS) films on soda‐lime glass and stainless steel (SUS) substrates with several [Ga]/([Ga] + [In]), GGI, and Fe concentrations are fabricated by so‐called “multi‐layer precursor method”. From optical deep‐level transient spectroscopy, deep‐level defect located at 0.8 eV from valence band maximum (EV) is observed. This defect becomes recombination center when GGI is over 0.4, thereby decreasing cell performances. Fe‐related deep‐level defect is moreover detected in CIGS film on SUS substrate situated at 0.45 eV from EV. Its density is consistent with Fe concentration in CIGS films. According to SCAPS simulation and experimental results, Fe concentration of above threshold (1.0 × 1016 atom/cm3) decreases carrier lifetime and carrier density and has more harmful influence on cell performances with GGI of above 0.4. On the other hand, Fe concentration of below threshold (1.0 × 1016 atom/cm3) has no detrimental impact on cell performances. Namely, conversion efficiency (η) is slightly changed by below 2%. CIGS solar cell on SUS substrate with η of 17.5% is fabricated by decreasing Fe concentration to approximately 5.2 × 1016 atom/cm3 although higher than the threshold value. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

11.
Among different process routes for Cu(In,Ga)Se2 (CIGS) solar cells, sufficient Se supply is commonly required to obtain high‐quality CIGS films. However, supplying extra Se increases the cost and the complexity. In this work, we demonstrate that extra Na incorporation can substantially increase efficiency of Se‐deficient CIGS solar cells, fabricated by sputtering from a quaternary CIGS target without extra Se supply, from 1.5% to 11.0%. The Se‐deficient CIGS device without extra NaF reveals a roll‐over I–V curve at room temperature as well as significantly reduced Jsc and fill factor at low temperatures. The electrical characteristics of Se‐deficient CIGS films are well explained and modeled by the low p‐type doping due to high density of compensating donors and the presence of deep defects possibly originating from the anti‐bonding levels of Se vacancies. The significant improvement after extra Na incorporation is attributable to the Na‐induced passivation of Se vacancies and the increased p‐type doping. Our result suggests that extra Na addition can effectively compensate the Se deficiency in CIGS films, which provides a valuable tuning knob for compositional tolerance of absorbers, especially for the Se‐deficient CIGS films. We believe that our findings can shine light on the development of novel CIGS processes, distinct from previous ones fabricated in Se‐rich atmosphere. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

12.
β‐In2S3 is a natural defective III–VI semiconductor attracting considerable interests but lack of efficient method for its 2D form fabrication. Here, for the first time, this paper reports controlled synthesis of ultrathin 2D β‐In2S3 flakes via a facile space‐confined chemical vapor deposition method. The natural defects in β‐In2S3 crystals, clearly revealed by optical spectra and optoelectronic measurement, strongly modulate the (opto)‐electronic of as‐fabricated β‐In2S3 and render it a broad detection range from visible to near‐infrared. Particularly, the as‐fabricated β‐In2S3 photodetector shows a high photoresponsivity of 137 A W?1, a high external quantum efficiency of 3.78 × 104%, and a detectivity of 4.74 × 1010 Jones, accompanied with a fast rise and decay time of 6 and 8 ms, respectively. In addition, an interesting linear response to the testing power intensities range is observed, which can also be understood by the presence of natural defects. The unique defective structure and intrinsic optical properties of β‐In2S3, together with its controllable growth, endow it with great potential for future applications in electronics and optoelectronics.  相似文献   

13.
In this work, the impacts of surface sulfurization of high‐quality Cu(In1−x,Gax)Se2 (CIGS) thin films deposited by three‐stage process on the film properties and the cell performance were investigated. The CIGS thin films were sulfurized at 550 °C for 30 min using H2S gas. The X‐ray photoelectron spectroscopy analysis revealed that sulfur atoms diffused into the CIGS surface layer and that the valence band minimum was lowered by the film sulfurization. The open circuit voltage (Voc) drastically increased from 0.590 to 0.674 V as a result of the sulfurization process. Temperature‐dependent current–voltage and capacitance–frequency measurements also revealed that interface recombination was drastically decreased by the lowering of the defect's activation energy level at the vicinity of the buffer/CIGS interface after the sulfurization. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

14.
Texture and morphology variations in co‐evaporated (In,Ga)2Se3 and Cu(In,Ga)Se2 (CIGS) films grown with various Se source conditions during growth were studied. The Se species of simply evaporated, large molecular Se (E‐Se, low‐sticking coefficient), and RF‐plasma cracked atomic Se (R‐Se, high sticking coefficient) were used in the present work. (In,Ga)2Se3 precursor films, which were prepared during the first stage of CIGS film growth by the three‐stage process, showed systematic variations in texture and Na distribution profile with varying evaporative Se (E‐Se) flux. The properties of CIGS films and solar cells also showed systematic variations, and the open‐circuit voltage (Voc) and fill factor were found to be especially sensitive to the E‐Se flux. R‐Se grown (In,Ga)2Se3 precursor films featured granular morphology with strong (105) and (301) peaks in the diffraction pattern, and the texture was very similar to an E‐Se grown film fabricated with a Se to group III metal (In + Ga) flux ratio (P[Se]/[In + Ga]) of about 6, although the nominal P[Se]/[In + Ga] used for an R‐Se source was very small and less than 0.5. The R‐Se grown CIGS films displayed, however, highly dense surfaces and larger grain sizes than E‐Se grown CIGS films. The controllability of film morphology and the Na diffusion profile in (In,Ga)2Se3 and CIGS films with various Se source conditions are discussed. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

15.
The use of Ga1−xInxAs instead of GaAs as a bottom solar cell in a GayIn1−yP/Ga1−xInxAs tandem structure increases the flexibility of choosing the optimum bandgap combination of materials for a multijunction solar cell. Higher theoretical efficiencies are calculated and different cell concepts are suggested for space and terrestrial concentrator applications. Various GayIn1−yP/Ga1−xInxAs material combinations have been investigated for the first time and efficiencies up to 24·1% (AM0) and 27·0% (AM1·5 direct) have been reached under one-sun conditions. An efficiency of 30·0–31·3% was measured for a Ga0·35In0·65P/Ga0·83In0·17As tandem concentrator cell with prismatic cover at 300 suns. The top and bottom cell layers of this structure are grown lattice-matched to each other, but a large mismatch is introduced at the interface to the GaAs substrate. This cell structure is well suited for the use in next-generation terrestrial concentrators working at high concentration ratios. For the first time a cell efficiency up to 29–30% has been measured at concentration levels up to 1300 suns. A small prototype concentrator with Fresnel lenses and four tandem solar cells working at C = 120 has been constructed, with an outdoor efficiency of 23%. Copyright © 2001 John Wiley & Sons, Ltd.  相似文献   

16.
The influences of process parameters and Fe diffusing into Cu(In,Ga)Se2 (CIGS) films on the orientation of CIGS absorbers grown on the stainless steel (SS) foils are investigated. The structural properties, morphology, and elemental profiles are characterized using X‐ray diffraction, scanning electron microscopy, and second ion mass spectroscopy, respectively. The orientation of CIGS thin films on the SS substrates strongly depends on the texture of the (In,Ga)2Se3 precursor, determined by the substrate temperature at the first stage (Ts1) and the flux ratio of Se to (In + Ga). Among these factors, Ts1 is the prerequisite to achieve [300]‐oriented IGS layer, which will yield [200]‐oriented CIGS thin film in the later process. The results indicate that through the comparison of CIGS thin films on the Mo/SS substrates and on the Mo/ZnO/SS substrates and combined with simply calculation, Fe diffusing into the CIGS layer will hinder the growth of the CIGS grains along [112] orientation. The grazing‐incidence X‐ray diffraction results suggest that the surface of the [220]‐textured CIGS thin film on the SS substrate still has [220] predominance, whereas the surface texture of the [220]‐texture CIGS thin film on the Mo/soda‐lime glass substrate became [112] predominant, which is due to the different compensation ability between Fe and Na elements. Finally, the relations between the device parameters and the degrees of the preferred orientation of CIGS absorbers are investigated. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

17.
We have determined the activation energies of sodium diffusion from the soda‐lime glass substrate through the Mo back‐contact layer, as well as through copper indium gallium diselenide (CIGS) deposited on the Mo back‐contact layer of CIGS thin‐film solar cells. The activation energies were determined by X‐ray photoelectron spectroscopy (XPS) to measure surface sodium concentrations before and after thermally induced diffusion. The activation energies were found to be similar for the diffusion of Na through the Mo/glass and CIGS/Mo/glass thin films, approximately 8·6 and 9·6 kcal/mol, respectively. Furthermore, the sodium diffusion was found to occur by annealing in an environment of 1·0×10−5 Torr of air, oxygen, or water vapor, but not in vacuum of less than 1×10−8 Torr. In addition, the diffusion of Na was found to occur faster in the presence of oxygen than in water under identical annealing conditions. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   

18.
Undoped zinc oxide (ZnO) films have been grown on a moving glass substrate by plasma‐enhanced chemical vapor deposition at atmospheric pressure. High deposition rates of ~7 nm/s are achieved at low temperature (200 °C) for a substrate speed from 20 to 60 mm/min. ZnO films are highly transparent in the visible range (90%). By a short (~minute) post‐deposition exposure to near‐ultraviolet light, a very low resistivity value of 1.6·10−3 Ω cm for undoped ZnO is achieved, which is independent on the film thickness in the range from 180 to 1200 nm. The photo‐enhanced conductivity is stable in time at room temperature when ZnO is coated by an Al2O3 barrier film, deposited by the industrially scalable spatial atomic layer deposition technique. ZnO and Al2O3 films have been used as front electrode and barrier, respectively, in Cu(In,Ga)Se2 (CIGS) solar cells. An average efficiency of 15.4 ± 0.2% (15 cells) is obtained that is similar to the efficiency of CIGS reference cells in which sputtered ZnO:Al is used as electrode. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

19.
Single layers and combined layer systems with Cu(In,Ga)(S,Se)2, ZnS‐nanodot (nd) and In2S3 layers were investigated by surface photovoltage spectroscopy in the Kelvin‐probe arrangement and compared with the open‐circuit voltage (VOC) of solar cells. The In2S3 and ZnS‐nd layers were prepared by the spray ion layer gas reaction (ILGAR) technique from Indium chloride (InCl3), Indium acetylacetonate (In(acac)3) and Zinc acetylacetonate, respectively. The surface photovoltage signals of Cu(In,Ga)(S,Se)2 were larger for the Cu(In,Ga)(S,Se)2/ZnS‐nd/In2S3 than for the Cu(In,Ga)(S,Se)2/In2S3 layer system showing that a ZnS‐nd layer additionally passivated the Cu(In,Ga)(S,Se)2 surface. ILGAR In2S3 deposition from InCl3 precursor solution led to a modification of surface defects of ZnS‐nd and to generation of defect states below the band gap of Cu(In,Ga)(S,Se)2, which has not been observed for deposition from Indium acetylacetonate precursor. Defect generation during ILGAR In2S3 deposition with InCl3 precursor resulted in a lower VOC of Cu(In,Ga)(S,Se)2/ZnS‐nd/In2S3/ZnO : Al solar cells. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

20.
The effect of atomic layer deposition temperature of Zn1‐xMgxO buffer layers for Cu(In,Ga)Se2 (CIGS) based solar cell devices is evaluated. The Zn1‐xMgxO films are grown using diethyl zinc, bis‐cyclopentadienyl magnesium and water as precursors in a temperature range of 105 to 180°C. High efficiency devices are produced in the region from 105 up to 135°C. At a Zn1‐xMgxO deposition temperature of 120°C, a maximum cell efficiency of 15·5% is reached by using a Zn1‐xMgxO layer with an x‐value of 0·2 and a thickness of 140 nm. A significant drop in cell efficiency due to large losses in open circuit voltage and fill factor is observed for devices grown at temperatures above 150°C. No differences in chemical composition, structure and morphology of the samples are observed, except for the samples prepared at 105 and 120°C that show elemental selenium present at the buffer/absorber interface. The selenium at the interface does not lead to major degradation of the solar cell device efficiency. Instead, a decrease in Zn1‐xMgxO resistivity by more than one order of magnitude at growth temperatures above 150°C may explain the degradation in solar cell performance. From energy filtered transmission electron microscopy, the width of the CIGS/Zn1‐xMgxO chemical interface is found to be thinner than 10 nm without any areas of depletion for Cu, Se, Zn and O. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

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