An optimization of band alignment at the p-n junction interface is realized on alcohol-based solution-processed Cu(In,Ga)(S,Se) (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 CuSe-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.

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)S (CIGS) or Cu(In,Ga)(S,Se) (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 (V) 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.

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.

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.

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.

As CuInGa-based chalcopyrite photocathodes suffer from poor hydrogen evolution activity, n-type overlayers and hydrogen evolution catalysts (HECs) need to be deposited on the film surface to drive surface band bending and reduce the overpotential for the hydrogen evolution reaction (HER). Here, we present a Cu­(In,Ga)­(S,Se)2 (CIGSSe) photocathode with grown-in Cu x S HECs enabling solar water splitting without the deposition of additional n-type overlayers and HECs. The controlled two-step chalcogenization using a Cu-rich CuInGa precursor film resulted in the natural formation of the Cu x S phase at the CIGSSe film surface and an increase in S content by substituting Se. Electrochemical water reduction tests elucidated that the naturally formed Cu x S alters the surface state of CIGSSe and reduces the overpotential for HER. Also, the S incorporation allows fine-tuning to make the CIGSSe band gap favorable for solar water splitting. Consequently, the CIGSSe photocathode showed −25.7 mA·cm–2 photocurrent density and 3 h photostability for photoelectrochemical hydrogen evolution.

Ultrathin solar cells (UTSCs) have attracted much research attention because of their superior potential for low‐cost production and diverse applications. For UTSCs to achieve high efficiency, rear‐interface passivation is critical because it has greater influence on thinner absorbers. Conventional passivation layers (e.g., Al2O3 and SiO2) inevitably require patterned contact openings for electrical conduction, the complex processing of which severely impedes the scale‐up production of UTSCs. Herein, this study reports that amorphous TiO2 layers can act as a passivating contact, which not only passivates defective rear‐interfaces but also provides excellent electrical conduction, for solution‐processed Cu(In,Ga)(S,Se)2 UTSCs. The amorphous nature of TiO2 layers is found to play a key role in achieving desirable ohmic conduction over the entire area without any contact openings. Holes in absorbers easily move into amorphous TiO2 layers, even in the presence of large valence band offset (2.6 eV), proving that the defect states within these TiO2 layers act as hole conduction pathways. While control devices experience huge open‐circuit voltage (VOC) losses (−303 mV) after reduction of absorber thickness from 750 to 300 nm, devices with amorphous TiO2 layers exhibit VOC gains (+8 mV), encouraging the realization of high‐efficiency UTSCs with a simple, easily scalable, and highly reproducible process.

Easily processed, low cost, and highly efficient solar cells are desirable for photovoltaic conversion of solar energy to electricity. We present the fabrication of precursor solution processed CuInGaS 2 (CIGS) thin film solar cells on transparent indium tin oxide (ITO) substrates. The CIGS absorber film was prepared by a spin-coating method, followed by two successive heat treatment processes. The first annealing process was on a hot plate at 300 o C for 30 min in air to remove carbon impurities in the film; this was followed by a sulfurization process at 500 o C in an H 2 S(1%)/Ar environment to form a polycrystalline CIGS film. The absorber film with an optical band-gap of 1.52 eV and a thickness of about 1.1 µm was successfully synthesized. Because of the usage of a transparent glass substrate, a bifacial CIGS thin film device could be achieved; its power conversion efficiency was measured to be 6.64% and 0.96% for front and rear illumination, respectively, under standard irradiation conditions.