Surface engineering in Cu(In,Ga)Se2 solar cells

Surface modifications of three‐stage co‐evaporated Cu(In,Ga)Se₂ (CIGS) thin films are investigated by finishing the evaporation with gallium‐free (CuInSe₂, CIS) stages of various lengths. Secondary‐ion mass spectrometry shows substantial interdiffusion of indium and gallium, smearing out the Ga/(Ga + In) profile so that the addition of a CIS layer merely lowers the gallium content at the surface. For the thinnest top layer, equivalent to 20 nm of pure CIS, X‐ray photoelectron spectroscopy does not detect any compositional difference compared with the reference device. The modifications are evaluated electrically both by temperature‐dependent characterisation of actual solar‐cell devices and by modelling, using the latest version of scaps‐1d (Electronics and Information Systems, Ghent University, Belgium). The best solar‐cell device from this series is obtained for the 20 nm top layer, with an efficiency of 16.6% after antireflective coating. However, we observe a trend of decreasing open‐circuit voltage for increasingly thick top layers, and we do not find direct evidence that the lowering of the gallium concentration at the CIGS surface should generally be expected to improve the device performance. A simulated device with reduced bulk and interface defect levels achieves nearly 20% efficiency, but the trends concerning the CIS top layer remain the same. Copyright © 2011 John Wiley & Sons, Ltd.     

A stacked chalcopyrite thin‐film tandem solar cell with 1.2 V open‐circuit voltage

CuGaSe₂ (CGS) thin films were prepared on tin‐doped indium oxide (ITO) coated soda‐lime glass substrates by thermal co‐evaporation to fabricate transparent solar cells. The films consisted of columnar grains with a diameter of approximately 1 μm. Some deterioration of the transparency of the ITO was observed after deposition of the CGS film. The CGS solar cells were electrically connected in series with Cu(In,Ga)Se₂ (CIGS) solar cells and mechanically stacked on the CIGS cells to construct tandem cells. The tandem solar cell with the CGS cell as the top cell showed an efficiency of 7.4% and an open‐circuit voltage of 1.18 V (AM 1.5, total area). Copyright © 2003 John Wiley & Sons, Ltd.     

Fabrication of Cu(In,Ga)Se2 thin films by sputtering from a single quaternary chalcogenide target

Single‐layered Cu‐In‐Ga‐Se precursors were fabricated by one‐step sputtering of a single quaternary Cu(In,Ga)Se₂ (CIGS) chalcogenide target at room temperature, followed by post selenization using Se vapor obtained from elemental Se pellets. The morphological and structural properties of both as‐deposited and selenized films were characterized by X‐ray diffraction (XRD), Raman spectroscope and scanning electron microscope (SEM). The precursor films exhibited a chalcopyrite structure with a preferential orientation in the (112) direction. The post‐selenization process at high‐temperature significantly improved the quality of the chalcopyrite CIGS. The CIGS layers after post‐selenization were used to fabricate solar cells. The solar cell had an open‐circuit voltage Voc of 0.422 V, a short‐circuit current density J = 24.75 mA, a fill factor of 53.29%, and an efficiency of 7.95%. Copyright © 2010 John Wiley & Sons, Ltd.     

8.2% pure selenide kesterite thin‐film solar cells from large‐area electrodeposited precursors

Cu₂ZnSnSe₄ solar cell absorbers are synthesized by large‐area electrodeposition of metal stack precursors followed by selenization. A champion solar cell exhibits 8.2% power conversion efficiency, a new record for Cu₂ZnSnSe₄ solar cells prepared from electrodeposited metallic precursors. Significant improvements of device performance are achieved by the application of two etching procedures and buffer layer optimization. These results validate electrodeposition as a credible alternative to vacuum processes (sputtering, co‐evaporation) for earth‐abundant thin‐film solar cell fabrication at low cost. Copyright © 2015 John Wiley & Sons, Ltd.     

Preparation of CuInxGa1−xSe2 solar cells by electron beam evaporation of powdered evaporants

Cu(In,Ga)Se₂ (CIGS) thin films were deposited by electron beam evaporation of ball-milled powders containing various amounts of gallium. The effects of the gallium concentration in the Cu(In,Ga)Se₂ on the structure, surface morphology and optical properties of the films were investigated using X-ray diffraction, energy-dispersive X-ray analysis, atomic force microscopy and optical spectroscopy. All of the films, which were deposited at 450 °C, were polycrystalline and exhibited a chalcopyrite structure with a (112) preferred orientation. The optical constants of the films were calculated. The grain size, the roughness and the band gap increased with increasing amounts of gallium in the films. A glass/TCO/CdS/CIGS/Au solar cell with 12.87% efficiency was prepared directly from the powdered material.     

Growth of Cu(In,Ga)Se2 thin films by a novel single‐stage route based on pulsed electron deposition

We report a novel route for growing Cu(In,Ga)Se₂ (CIGS) thin films, based upon the Pulsed Electron Deposition (PED) technique. Unlike other well‐known deposition techniques, PED process allows the stoichiometric deposition of CIGS layers in a single stage, without requiring any further treatments for Cu/(In + Ga) ratio adjustment nor selenization. The structural properties of polycrystalline CIGS films strongly depend on the growth temperature, whereas post‐deposition annealing enhances the grain size and the <112> out‐of‐plane preferred orientation of the chalcopyrite structure, without affecting the film composition. Preliminary measurements of the performances of solar cells based on these films confirm the great potentiality of PED‐grown CIGS as absorber layers. Copyright © 2011 John Wiley & Sons, Ltd.     

Fabrication and characterization of thin-film Cu (In,Ga) Se2 solar cells on a PET plastic substrate using screen printing

Chalcopyrite copper indium gallium diselenide (CIGS) ink was prepared by dissolving copper, indium, gallium acetylacetonate and Se powder in oleylamine using the hot injection methods. CIGS films were deposited on a PET plastic substrate by a screen-printing technique using CIGS ink with a Ga content ranging from 0.3 to 0.6. X-ray diffraction patterns reveal that the films exhibit a chalcopyrite-type structure. The crystalline grain sizes of the films decrease with increasing Ga content. AFM data shows that the root mean square (RMS) surface roughness of the CIGS film decreases with increasing Ga content. The effects of the Ga content in the CIGS absorber layer on the optical properties of the corresponding thin films and solar cells were studied. The band-gap energies of the CIGS thin films increased with an increasing Ga/(In+Ga) ratio. The short-circuit current (I_SC) of the solar cell decreased linearly with the Ga/(In+Ga) ratio, while the open-circuit voltage (V_OC) increased with this ratio. The solar cell exhibited its highest efficiency of 4.122% at a Ga/(In+Ga) ratio of 0.3.     

Influence of the Cu(In,Ga)Se2 thickness and Ga grading on solar cell performance

Thin‐film solar cells with Cu(In,Ga)Se₂ (CIGS) absorber layers ranging from 1.8 to 0.15 μm in thickness were fabricated by co‐evaporation, with both homogeneous and Ga/(Ga + In) graded composition. The absorption of the CIGS layers was determined and compared with corresponding QE measurements in order to obtain the optical related losses. The material characterization included XRD as well as cross‐sectional SEM analysis. Devices with CIGS layers of all thicknesses were fabricated, and down to 0.8–1 μm they showed a maintained high performance (η ∼ 15%). When the CIGS layer was further reduced in thickness the loss in performance increased. The main loss was observed for the short‐circuit current, although the loss was not only due to a reduced absorbance. The open‐circuit voltage was essentially not affected by the reduction of the CIGS thickness, while the fill factor showed a slight decrease. The fill factor loss was eliminated by introducing a Ga/(Ga+In) graded CIGS, which also resulted in an increased open‐circuit voltage of 20–30 mV for all CIGS thicknesses. Device results of 16.1% efficiency at 1.8 μm CIGS thickness, 15.0% at 1.0 μm and 12.1% at 0.6 μm (total area without anti‐reflective coating) were achieved. Copyright © 2002 John Wiley & Sons, Ltd.     

Impact of compositional grading and overall Cu deficiency on the near‐infrared response in Cu(In,Ga)Se2 solar cells

Highly efficient thin film solar cells based on co‐evaporated Cu(In,Ga)Se₂ (CIGS) absorbers are typically grown with a [Ga]/([Ga] + [In]) (GGI) gradient across the thickness and a Cu‐poor composition. Upon increasing the Cu content towards the CIGS stoichiometry, lower defect density is expected, which should lead to increased absorption in the near‐infrared (NIR), diffusion length and carrier collection. Further, optimization of the GGI grading is expected to increase the NIR response. In this contribution [Cu]/([In] + [Ga]) (CGI) values are increased by shortening the deposition stage after the first stoichiometric point. In order to obtain comparable Ga contents at the interface for proper band alignment, the front GGI gradings were actively modified. With a relative CGI increase of 7%, we observe an increased photocurrent, originating from an improved NIR external quantum efficiency response. By characterizing the modified absorber properties by reflection‐transmission spectroscopy, we attribute the observed behavior to changes in the optical properties rather than to improved carrier collection. Cu‐dependent modifications of the NIR‐absorption coefficients are likely to be responsible for the variations in the optical properties, which is supported by device simulations. Adequate re‐adjustments of the co‐evaporation process and of the alkali‐fluorides post‐deposition treatments allow maintaining V_oc and FF values, yielding an overall increase of efficiency as compared to a reference baseline. © 2016 The Authors. Progress in Photovoltaics : Research and Applications published by John Wiley & Sons Ltd.     

Non‐destructive optical analysis of band gap profile,crystalline phase,and grain size for Cu(In,Ga)Se2 solar cells deposited by 1‐stage, 2‐stage,and 3‐stage co‐evaporation

Cu(In,Ga)Se₂ (CIGS) thin films co‐evaporated by 1‐stage, 2‐stage, and 3‐stage processes have been studied by spectroscopic ellipsometry (SE). The disappearance of a Cu_2‐xSe optical signature, detected by real time SE during multistage CIGS, has enabled precise endpoint control. Band gap energies determined by SE as depth averages show little process variation for fixed [Ga]/([In] + [Ga]) atomic ratio, whereas their broadening parameters decrease with increasing number of stages, identifying successive grain size enhancements. Refined SE analysis has revealed band gap profiling only for 3‐stage CIGS. Solar cells incorporating these absorbers have yielded increased efficiencies in correlation with phase control, grain size, and band gap profiling. Copyright © 2013 John Wiley & Sons, Ltd.     

Controllable Formation of Ordered Vacancy Compound for High Efficiency Solution Processed Cu(In,Ga)Se2 Solar Cells

Solution processing of Cu(In,Ga)Se₂ (CIGS) absorber makes it cost-competitive in the photovoltaic market. It is reported that copper-poor ordered vacancy compound (OVC) is crucial for high performance CIGS solar cells. However, in solution process method, controllable formation of OVC is unavailable and limited research has been carried out. In this work, the controllable formation of the OVC phase on the CIGS surface is successful by controlling the selenization temperature and intentional variation of Cu/(In+Ga) stoichiometry in precursors for top layers and bulk layers deposition. The effects of OVC contents on the device performance are investigated. The CIGS thin film with OVC phase exhibits a lower valence band position. Meanwhile, the CIGS devices with optimized OVC content show decreased interface defects density and better carrier collection ability. The above advantages translate into a champion PCE of 16.39% for CIGS device with OVC phase, which is the champion performance among non-hydrazine solution-processed CIGS solar cells. The results demonstrate that the controllable formation of OVC phase approach should make a significant contribution to the efficiency promoting of solution processed CIGS solar cells.     

Record 1.0 V open‐circuit voltage in wide band gap chalcopyrite solar cells

Tandem solar cell structures require a high‐performance wide band gap absorber as top cell. A possible candidate is CuGaSe₂, with a fundamental band gap of 1.7 eV. However, a significant open‐circuit voltage deficit is often reported for wide band gap chalcopyrite solar cells like CuGaSe₂. In this paper, we show that the open‐circuit voltage can be drastically improved in wide band gap p‐Cu(In,Ga)Se₂ and p‐CuGaSe₂ devices by improving the conduction band alignment to the n‐type buffer layer. This is accomplished by using Zn_1−x Sn_x O_y , grown by atomic layer deposition, as a buffer layer. In this case, the conduction band level can be adapted to an almost perfect fit to the wide band gap Cu(In,Ga)Se₂ and CuGaSe₂ materials. With an improved buffer band alignment for CuGaSe₂ absorbers, evaporated in a 3‐stage type process, we show devices exhibiting open‐circuit voltages up to 1017 mV, and efficiencies up to 11.9%. This is to the best of our knowledge the highest reported open‐circuit voltage and efficiency for a CuGaSe₂ device. Temperature‐dependent current‐voltage measurements show that the high open‐circuit voltage is explained by reduced interface recombination, which makes it possible to separate the influence of absorber quality from interface recombination in future studies.     

Development of an intelligent design tool for non-stoichiometric compound devices: an example

In this paper, we discuss the idea of intelligent design of thin film CIGS solar cell, and we focus on the methodology of material design. We first introduce the calculation of the neutral defect concentrations of non-stoichiometric CuInSe₂, CuGaSe₂ and ZnO under specific atomic chemical potential conditions, and predict the formation of the order defect compound using the concept of minimization of total free energy, which includes the configurational entropy. This calculation is the main procedure in the material design and the key to the device design and process design. We then calculate the carrier concentrations using multi-level defect statistics and mobilities of these materials of different constitutions. The functions of the intelligent design tool are demonstrated.     

Texture and morphology variations in (In,Ga)2Se3 and Cu(In,Ga)Se2 thin films grown with various Se source conditions

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 (V_oc) 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.     

Effects of Sb-doping on the grain growth of CIGS thin films fabricated by electrodeposition

Cu(InGa)Se2 (CIGS) solar cells become one of the most important thin film photovoltaic devices thus far. The doping of Sb has improved the grain size of CIGS thin film and therefore led to the enhancement of solar cell efficiency. Various approaches have been used for the Sb doping. Not many reports of electrodeposition of In, Ga and Sb alloy have been reported. In this work, the Sb thin film was coated over Cu film surface prior to the In and Ga deposition in order to form a Cu/Sb/In/Ga metal precursor. After selenization, the Sb doped CIGS film was prepared. The structure and morphology of Sb doped CIGS films were investigated compared with the undoped CIGS reference samples. A modified selenization method was proposed, which improved the grain size. Finally, the conversion efficiency of Sb doped CIGS based solar cells has been improved by 1.02%.     

Bandgap optimization of submicron‐thick Cu(In,Ga)Se2 solar cells

Reducing Cu(In,Ga)Se₂ (CIGS) absorber thickness into submicron regime provides an opportunity for reducing CIGS solar cell manufacturing time and cost. However, CIGS with submicron‐thick absorber would suffer strong absorption loss in the long‐wavelength region. In this paper, we report a new fabrication route for CIGS solar cells on soda‐lime glass substrates with different Ga content (0.3 < [Ga]/([Ga] + [In]) < 0.6), all with absorber thicknesses around 0.9 µm. Efficiency of 17.52% has been achieved for cells with high Ga content of [Ga]/([Ga] + [In]) = 41%, which is currently the best reported efficiency for submicron‐thick CIGS solar cells. Unlike the normal‐thickness absorber (2–3 µm) that has an optimal [Ga]/([Ga] + [In]) of ~32%, the increased value of optimal [Ga]/([Ga] + [In]) in submicron‐thick absorber greatly enhances the open‐circuit voltage, by nearly 15% compared with that of samples with Ga content optimized at normal absorber thickness. This large gain in V_OC well compensates the absorption loss in the long‐wavelength region and contributes to the enhancement of final solar cell efficiency. Copyright © 2014 John Wiley & Sons, Ltd.     

The formation of large-grain CulnSe2 films by selenization by high-rate Se transport under moderate vacuum conditions

A novel method for forming large-grain CuInSe₂ thin films by the reaction of In and Cu with Se inside a sealed ampoule is presented. A Se source and a selenization precursor consisting of a co-evaporated In+Cu film deposited onto an alumina substrate were placed at opposite ends of a closed quartz crucible sealed at 100 Torr. By establishing a small thermal gradient between the ends of the ampoule, Se was transported to the precursor where selenization of the In-Cu layer occurred. The maximum substrate temperature used was 475°C. Resulting film microstructures were extremely well formed, consisting of 3 to 5 μm grains of densely packed CuInSe₂ crystallites. It is suggested that such enhanced grain growth may be the result of the preferential formation of the Serich liquid, L3, under conditions of high Se flux. Such a mechanism may be exploited for fabricating large-grain CuInSe₂ films at temperatures compatible with substrates-of-choice in solar cell manufacturing.     

Cu2ZnSnSe4 thin film solar cells produced via co‐evaporation and annealing including a SnSe2 capping layer

Cu₂ZnSnSe₄ (CZTSe) thin film solar cells have been produced via co‐evaporation followed by a high‐temperature annealing. In order to reduce the decomposition of the CZTSe, a SnSe₂ capping layer has been evaporated onto the absorber prior to the high‐temperature treatment. This eliminates the Sn losses due to SnSe evaporation. A solar cell efficiency of 5.1% could be achieved with this method. Moreover, the device does not suffer from high series resistance, and the dominant recombination pathway is situated in the absorber bulk. Finally, different illumination conditions (white light, red light, and yellow light) reveal a strong loss in fill factor if no carriers are generated in the CdS buffer layer. This effect, known as red‐kink effect, has also been observed in the closely related Cu(In,Ga)Se₂ thin film solar cells. Copyright © 2013 John Wiley & Sons, Ltd.     

Combinatorial study of NaF addition in CIGSe films for high efficiency solar cells

We report on a sodium fluoride (NaF) thickness variation study for the H₂Se batch furnace selenization of sputtered Cu(In,Ga) films in a wide range of Cu(In,Ga) film compositions to form Cu(In,Ga)Se₂ (CIGSe) films and solar cells. Literature review indicates lack of consensus on the mechanisms involved in Na altering CIGSe film properties. In this work, for sputtered and batch‐selenized CIGSe, NaF addition results in reduced gallium content and an increase in grain size for the top portion of the CIGSe film, as observed by scanning electron microscopy and secondary ion mass spectrometry. The addition of up to 20 nm of NaF resulted in an improvement in all relevant device parameters: open‐circuit voltage, short‐circuit current, and fill factor. The best results were found for 15 nm NaF addition, resulting in solar cells with 16.0% active‐area efficiency (without anti‐reflective coating) at open‐circuit voltage (V_OC) of 674 mV. Copyright © 2013 John Wiley & Sons, Ltd.     

Investigation of Cu(In,Ga)Se2 thin‐film formation during the multi‐stage co‐evaporation process

In order to transfer the potential for the high efficiencies seen for Cu(In,Ga)Se₂ (CIGSe) thin films from co‐evaporation processes to cheaper large‐scale deposition techniques, a more intricate understanding of the CIGSe growth process for high‐quality material is required. Hence, the growth mechanism for chalcopyrite‐type thin films when varying the Cu content during a multi‐stage deposition process is studied. Break‐off experiments help to understand the intermediate growth stages of the thin‐film formation. The film structure and morphology are studied by X‐ray diffraction and scanning electron microscopy. The different phases at the film surface are identified by Raman spectroscopy. Depth‐resolved compositional analysis is carried out via glow discharge optical emission spectrometry. The experimental results imply an affinity of Na for material phases with a Cu‐poor composition, affirming a possible interaction of sodium with Cu vacancies mainly via In(Ga)_Cu antisite defects. An efficiency of 12.7% for vacancy compound‐based devices is obtained. Copyright © 2011 John Wiley & Sons, Ltd.