Achieving over 15% Efficiency in Solution-Processed Cu(In,Ga)(S,Se)2 Thin-Film Solar Cells via a Heterogeneous-Formation-Induced Benign p-n Junction Interface.

Cu(In,Ga)(S,Se)2 (CIGS) thin-film solar cells have attracted considerable interest in the field of photovoltaic devices due to their high efficiency and great potential for diverse applications. While CdS has been the most favorable n-type semiconductor because of its excellent lattice-match and electronic band alignment with p-type CIGS, its narrow optical band gap (∼2.4 eV) has limited light absorption in underlying CIGS absorber films. Reducing the thickness of CdS films to increase the short-circuit current-density has been less effective due to the following decrease in the open-circuit voltage. To overcome this trade-off between the main parameters, we controlled the formation mechanism of CdS films in chemical bath deposition and established its direct correlation with the properties of p-n junctions. Interestingly, a heterogeneous CdS film formation was found to have a synergetic effect with its ammonia bath solution, effectively reducing charge carrier loss from the shunt paths and interface recombination of CIGS/CdS junctions. With these electrical benefits, the trade-off was successfully alleviated and our best device achieved a power conversion efficiency of 15.6%, which is one of the state-of-the-art CIGS thin-film solar cells prepared using solution-processing techniques.

Morphological-Electrical Property Relation in Cu(In,Ga)(S,Se)2 Solar Cells: Significance of Crystal Grain Growth and Band Grading by Potassium Treatment.

Solution-processed Cu(In,Ga)(S,Se)2  (CIGS) has a great potential for the production of large-area photovoltaic devices at low cost. However, CIGS solar cells processed from solution exhibit relatively lower performance compared to vacuum-processed devices because of a lack of proper composition distribution, which is mainly instigated by the limited Se uptake during chalcogenization. In this work, a unique potassium treatment method is utilized to improve the selenium uptake judiciously, enhancing grain sizes and forming a wider bandgap minimum region. Careful engineering of the bandgap grading structure also results in an enlarged space charge region, which is favorable for electron-hole separation and efficient charge carrier collection. Besides, this device processing approach has led to a linearly increasing electron diffusion length and carrier lifetime with increasing the grain size of the CIGS film, which is a critical achievement for enhancing photocurrent yield. Overall, 15% of power conversion efficiency is achieved in solar cells processed from environmentally benign solutions. This approach offers critical insights for precise device design and processing rules for solution-processed CIGS solar cells.

Boosting Solar Cell Performance via Centrally Localized Ag in Solution-Processed Cu(In,Ga)(S,Se)2 Thin Film Solar Cells.

Fabrication of Cu(In,Ga)(S,Se)2 (CIGSSe) absorber films from environmentally friendly solutions under ambient air conditions for use in solar cells has shown promise for the low-cost mass production of CIGSSe solar cells. However, the limited power conversion efficiency (PCE) of these solar cells compared with their vacuum-processed counterparts has been a critical setback to their practical applications. This study aims to fabricate solution-processed CIGSSe solar cells with high PCEs by incorporation of Ag into the precursor layer of the CIGSSe absorber films. The results showed that Ag doping promoted grain growth by accelerating Se uptake, irrespective of the location within the CIGSSe film. Nevertheless, uniform Ag doping formed crevices that lowered the PCE of the cells, while centrally localizing the doped Ag prevented the formation of crevices, resulting in high PCEs up to 15.3%. Our results demonstrate that carefully doping Ag into a selected area of the precursor layer of the CIGSSe films can realize solution-processed chalcopyrite solar cells with high PCE.

Defect Analysis of Solution-Based Process CIGS Thin-Film Solar Cells Using Technology Computer-Aided Design.

Copper indium gallium sulfur selenide (Cu(In1-xGax)SeS, CIGS) thin film solar cells are fabricated using a solution-based process, and their defect models are studied through a computer-aided design method. Cu(In1-xGax)SeS is structured with a graded bandgap by controlling the ambient gas and precursor composition, during the fabrication process. The defects in the CIGS are modeled as two donor-like defects, which are differently distributed as per the CIGS grain size (large and small grains at upper and bottom layers, respectively), whereas those in the cadmium sulfide (CdS)/CIGS interface are modeled as a complex model of both donor- and acceptor-like defects in the CdS, near the interface. By measuring the external quantum efficiency and current density-voltage characteristics, the best-fitting match of the simulated values with the measured values are obtained. The simulation results demonstrate that the defects (defect density of ~7 × 1018) in the CdS interface are more serious, compared to the CIGS defects (defect density of ~2 × 1015 in the bottom), which were initially expected to be more severe because of grain nonuniformity. For increasing the cell efficiency, we establish that the process and material quality need to be further improved not only during CIGS formation using a multistep spin-coated precursor but also during the initial deposition of the CdS buffer. This numerical approach can enable better understanding of the defect behavior in solar cells, and indicate directions for improvement in the fabrication process and device structure, for developing high-efficiency solution-based CIGS solar cells.

Achieving 14.4% Alcohol-Based Solution-Processed Cu(In,Ga)(S,Se)2 Thin Film Solar Cell through Interface Engineering.

An optimization of band alignment at the p-n junction interface is realized on alcohol-based solution-processed Cu(In,Ga)(S,Se)2 (CIGS) thin film solar cells, achieving a power-conversion-efficiency (PCE) of 14.4%. To obtain a CIGS thin film suitable for interface engineering, we designed a novel "3-step chalcogenization process" for Cu2- xSe-derived grain growth and a double band gap grading structure. Considering S-rich surface of the CIGS thin film, an alternative ternary (Cd,Zn)S buffer layer is adopted to build favorable "spike" type conduction band alignment instead of "cliff" type. Suppression of interface recombination is elucidated by comparing recombination activation energies using a dark J- V- T analysis.

A highly efficient Cu(In,Ga)(S,Se)2 photocathode without a hetero-materials overlayer for solar-hydrogen production.

Surface modification of a Cu(In,Ga)(S,Se)2 (CIGSSe) absorber layer is commonly required to obtain high performance CIGSSe photocathodes. However, surface modifications can cause disadvantages such as optical loss, low stability, the use of toxic substances and an increase in complexity. In this work, we demonstrate that a double-graded bandgap structure (top-high, middle-low and bottom-high bandgaps) can achieve high performance in bare CIGSSe photocathodes without any surface modifications via a hetero-materials overlayer that have been fabricated in a cost-effective solution process. We used two kinds of CIGSSe film produced by different precursor solutions consisting of different solvents and binder materials, and both revealed a double-graded bandgap structure composed of an S-rich top layer, Ga- and S-poor middle layer and S- and Ga-rich bottom layer. The bare CIGSSe photocathode without surface modification exhibited a high photoelectrochemical activity of ~6 mA·cm-2 at 0 V vs. RHE and ~22 mA·cm-2 at -0.27 V vs. RHE, depending on the solution properties used in the CIGSSe film preparation. The incorporation of a Pt catalyst was found to further increase their PEC activity to ~26 mA·cm-2 at -0.16 V vs. RHE.

Multiple-Color-Generating Cu(In,Ga)(S,Se)2 Thin-Film Solar Cells via Dichroic Film Incorporation for Power-Generating Window Applications.

There are four prerequisites when applying all types of thin-film solar cells to power-generating window photovoltaics (PVs): high power-generation efficiency, longevity and high durability, semitransparency or partial-light transmittance, and colorful and aesthetic value. Solid-type thin-film Cu(In,Ga)S2 (CIGS) or Cu(In,Ga)(S,Se)2 (CIGSSe) PVs nearly meet the first two criteria, making them promising candidates for power-generating window applications if they can transmit light to some degree and generate color with good aesthetic value. In this study, the mechanical scribing process removes 10% of the window CIGSSe thin-film solar cell with vacant line patterns to provide a partial-light-transmitting CIGSSe PV module to meet the third requirement. The last concept of creating distinct colors could be met by the addition of reflectance colors of one-dimensional (1D) photonic crystal (PC) dichroic film on the black part of a partial-light-transmitting CIGSSe PV module. Beautiful violets and blues were created on the cover glass of a black CIGSSe PV module via the addition of 1D PC blue-mirror-yellow-pass dichroic film to improve the aesthetic value of the outside appearance. As a general result from the low external quantum efficiency (EQE) and absorption of CIGSSe PVs below a wavelength of 400 nm, the harvesting efficiency and short-circuit photocurrent of CIGSSe PVs were reduced by only ∼10% without reducing the open-circuit voltage (VOC) because of the reduced overlap between the absorption spectrum of CIGSSe PV and the reflectance spectrum of the 1D PC blue-mirror-yellow-pass dichroic film. The combined technology of partial-vacancy-scribed CIGSSe PV modules and blue 1D PC dichroic film can provide a simple strategy to be applied to violet/blue power-generating window applications, as such a strategy can improve the transparency and aesthetic value without significantly sacrificing the harvesting efficiency of the CIGSSe PV modules.