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Wide-gap, high-Ga (Ag,Cu)(In,Ga)Se₂ thin-film solar cells with a wide range of Ag contents are fabricated and characterized before and after dark storage, dark annealing at 85 degrees C, and light soaking. A 1:4 ratio of Ag to Cu enhances initial device performance significantly, with excess Ag enhancing carrier collection at the expense of open-circuit voltage and fill factor for close-stoichiometric devices. For off-stoichiometric devices, increased open-circuit voltages are offset by losses in carrier collection. Efficiency degradation after treatments is typically increased with additional Ag alloying. A second observation is a behavior threshold identified slightly below an Ag to Cu ratio of 1:1. For compositions below the threshold, the doping response to light soaking and dark annealing is similar to that exhibited by low-Ga Cu(In,Ga)Se₂. Above the threshold, light soaking reduces net doping and that dark annealing can even increase net doping. Furthermore, devices above the threshold exhibit a far greater doping responsivity than those below and display a strong dependence of initial performance and stability on group-I/group-III stoichiometry. A third observation is that all devices lose approximate to 1-2% (absolute) in efficiency after a 3 h light soak, indicating that this loss originates from the high-Ga content (1:3 In:Ga), rather than the Ag alloying.

This study evaluates In2O3:W as a transparent back contact material in wide-gap (bandgap range = 1.44–1.52 eV) (Ag,Cu)(In,Ga)Se2 (ACIGS) solar cells for potential application as a top cell in a tandem device. High silver concentrations and close-stoichiometric absorber compositions result in a complete depletion of free charge carriers, allowing for decent electron collection, despite the low diffusion length. Remarkable efficiencies of 13.6% and 7.5% are reached using 1 μm- and 400 nm-thick absorbers, respectively. At rear illumination (i.e., superstrate backwall), the best cell shows an efficiency of 8.7%. For each of the four analyzed samples, the short-circuit current at rear illumination reaches at least 60% of the value at front illumination. Losses arise from recombination at the back contact and a too low drift/diffusion length. The parasitic absorption by the transparent electrodes for photon energies close to the bandgap of a potential Si bottom cell (1.1 eV) is close to 15%. Strategies to reduce this value and to further increase the efficiency are discussed.

This contribution studies the effect of ordered vacancy compounds (OVCs) on the minority carrier collection in wide-gap (Ag,Cu)(In,Ga)Se2 (ACIGS) solar cells. For this purpose, three samples with different ([Ag]+[Cu])/([In]+[Ga]) (I/III) values were processed: 1) a very off-stoichiometric absorber (I/III = 0.31), consisting of isolated chalcopyrite patches embedded in a major OVC bulk phase, 2) a moderately off-stoichiometric absorber (I/III = 0.77) with OVC patches at the front and back interfaces and 3) a close-stoichiometric absorber (I/III = 0.94) with only very few, isolated OVC patches. For each of these samples, synchrotron-based X-ray fluorescence (XRF) was measured on a nanoscale (55 nm resolution), while simultaneously recording the X-ray beam induced current (XBIC). The results, complemented by transmission electron microscopy and electron-beam induced current analyses, clearly indicate that the presence of the OVC phase reduces the carrier collection and thus the short-circuit current density of off-stoichiometric wide-gap ACIGS solar cells.

Chalcopyrite-based solar cells have reached an efficiency of 23.35%, yet further improvements have been challenging. Here we present a 23.64% certified efficiency for a (Ag,Cu)(In,Ga)Se2 solar cell, achieved through the implementation of a series of strategies. We introduce a relatively high amount of silver ([Ag]/([Ag] + [Cu]) = 0.19) into the absorber and implement a ‘hockey stick’-like gallium profile with a high concentration of Ga close to the molybdenum back contact and a lower, constant concentration in the region closer to the CdS buffer layer. This kind of elemental profile minimizes lateral and in-depth bandgap fluctuations, reducing losses in open-circuit voltage. In addition, the resulting bandgap energy is close to the local optimum of 1.15 eV. We apply a RbF post-deposition treatment that leads to the formation of a Rb–In–Se phase, probably RbInSe2, passivating the absorber surface. Finally, we discuss future research directions to reach 25% efficiency.

The stability of thin-film solar cells spanning a wide range of compositions within the (Ag,Cu)(In,Ga)Se-2 material system is evaluated over time, after dry-heat annealing and after light soaking, and the role of Ag and Ga content is explored. Ag-free CuInSe2 is relatively stable to annealing and storage, while Cu(In,Ga)Se-2 suffers a degradation of fill factor and carrier collection. High-Ga (Ag,Cu)(In,Ga)Se-2 suffers degradation of carrier collection after prolonged annealing, reducing the short-circuit current by approximate to 12%. Ga-free (Ag,Cu)InSe2 loses up to a third of open-circuit voltage and a quarter of fill factor after all treatments are applied. All samples suffer voltage losses after light soaking, with the Ga-free devices losing up to 50 mV and those containing Ga losing up to 90 mV. Ag incorporation leads to a significant reduction in doping, and a significant increase in the response of doping to treatments, with the depletion width of (Ag,Cu)(In,Ga)Se-2 samples expanding from approximate to 0.1 mu m as-grown to beyond 1.0 mu m after all treatments, compared to the Cu(In,Ga)Se-2 sample variation of approximate to 0.1-0.3 mu m. Connections between Ag content, doping instability, and performance degradation are discussed.

This study evaluates the effect of silver alloying, stoichiometry, and deposition temperature of wide-gap (Ag,Cu)GaSe2 (ACGS) absorber films for solar cell applications. Devices using a standard CdS buffer exhibit a strong anticorrelation between the open-circuit voltage (V-OC) and short-circuit current density (J(SC)), with V-OC decreasing and J(SC) increasing toward stoichiometric absorber composition. Increasing the ACGS deposition temperature leads to larger grains and improved J(SC), while V-OC is not affected. By adding more silver to the absorber (maximum tested [Ag]/([Ag]+[Cu]) [AAC] = 0.4), the widening of the space charge region (SCR) significantly enhances carrier collection. Experimental quantum efficiency spectra can be accurately simulated when assuming a very low diffusion length and perfect collection in the SCR. The highest efficiency of 8.3% (without antireflection coating [ARC]) is reached for an absorber with AAC = 0.4 grown at 600 degrees C. Replacing CdS by a (Zn,Sn)O buffer with lower electron affinity strongly mitigates interface recombination. Moreover, the V-OC-J(SC) anticorrelation is not evident anymore and the highest efficiency of 11.2% (11.6% w/ARC, V-OC = 985 mV, J(SC) = 18.6 mA cm(-2), fill factor = 61.0%) is reached for a close-stoichiometric ACGS solar cell with AAC = 0.4 processed at 650 degrees C.

This contribution studies the potential of an RbF postdeposition treatment (RbF-PDT) of wide-gap (Ag,Cu)(In,Ga)Se-2 (ACIGS) absorbers to improve the corresponding solar cell performance. While a higher open-circuit voltage (V-OC) and short-circuit current density are achieved, a lower fill factor (FF) is observed for most of the devices subjected to an RbF-PDT. However, the drop in FF can be avoided for some close-stoichiometric samples, leading to maximum efficiencies beyond 16% (without antireflection coating) at a bandgap energy (E-g) of 1.43 eV. For off-stoichiometric ACIGS, a record V-OC value of 926 mV at E-g = 1.44 eV is reached. Lower V-OC deficits likely require enhanced bulk quality of wide-gap chalcopyrite absorbers. Extensive material analysis shows that the heavy alkali PDT of ACIGS with high Ag and Ga contents leads to similar absorber modifications as commonly observed for low-gap Cu(In,Ga)Se-2 (CIGS). Rubidium is continuously distributed at "internal" (grain boundaries) and "external" (buffer and back contact) absorber interfaces. The results indicate that Rb diffusion into the absorber bulk (including 1:1:2 and 1:3:5 compounds) is restricted. Furthermore, the formation of a very thin RbInSe2 surface layer is suggested. It remains open, which effects alter the device characteristics after RbF-PDT.

(Ag,Cu)(In,Ga)Se₂ solar cells with bandgaps of ≈1.45 eV with a large spread in absorber stoichiometry are characterized with the intention of assessing the effect of composition on the stability of the devices. This material is observed to have a poor diffusion length, leading to very strong dependence upon the depletion region width for charge carrier collection. The depletion width is observed to depend strongly upon the stoichiometry value and shrinks significantly after an initial period of dark storage. It is also seen that the depletion width can be varied strongly through light-soaking and dry-heat treatments, with prolonged annealing leading to detrimental contraction and light soaking leading to expansion which increases current collection. The extent of depletion width variation in response to the treatments is also clearly linked to absorber stoichiometry. Consequently, the device performance, particularly the current output, exhibits a stoichiometry dependence and is considerably affected after each round of treatment. Possible causes of this behavior are discussed.

Herein, the performance of wide-gap Cu(In,Ga)Se-2 (CIGS) and (Ag,Cu)(In,Ga)Se-2 (ACIGS) solar cells with In2O3:Sn (ITO) and In2O3:H (IOH) as transparent back contact (TBC) materials is evaluated. Since both TBCs restrict sodium in-diffusion from the glass substrate, fine-tuning of a NaF precursor layer is crucial. It is found that the optimum Na supply is lower for ACIGS than for CIGS samples. An excessive sodium amount deteriorates the solar cell performance, presumably by facilitating GaOx growth at the TBC/absorber interface. The efficiency (eta) further depends on the absorber stoichiometry, with highest fill factors (and eta) reached for close-stoichiometric compositions. An ACIGS solar cell with eta = 12% at a bandgap of 1.44 eV is processed, using IOH as a TBC. The best CIGS device reaches eta = 11.2% on ITO. Due to its very high infrared transparency, IOH is judged superior to ITO for implementation in a top cell of a tandem device. However, while ITO layers maintain their conductivity, IOH films show an increased sheet resistance after absorber deposition. Chemical investigations indicate that incorporation of Se during the initial stage of absorber processing may be responsible for the deteriorated conductivity of the IOH back contact in the final device.

Direct solar hydrogen generation via a combination of photovoltaics (PV) and water electrolysis can potentially ensure a sustainable energy supply while minimizing greenhouse emissions. The PECSYS project aims at demonstrating asolar-driven electrochemical hydrogen generation system with an area >10 m2 with high efficiency and at reasonable cost. Thermally integrated PV electrolyzers(ECs) using thin-film silicon, undoped, and silver-doped Cu(In,Ga)Se2 and silicon heterojunction PV combined with alkaline electrolysis to form one unit are developed on a prototype level with solar collection areas in the range from 64 to2600 cm2 with the solar-to-hydrogen (StH) efficiency ranging from 4 to 13%. Electrical direct coupling of PV modules to a proton exchange membrane EC test the effects of bifacially (730 cm2 solar collection area) and to study the long-term operation under outdoor conditions (10 m2 collection area) is also investigated. In both cases, StH efficiencies exceeding 10% can be maintained over the test periods used. All the StH efficiencies reported are based on measured gas outflow using mass flow meters.