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(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.

It is attractive to alloy Cu(In,Ga)Se2 solar-cell absorbers with Ag (ACIGSe), since they lead to similar device performances as the Ag-free absorber layers, while they can be synthesized at much lower deposition temperatures. However, a KF post-deposition treatment (PDT) of the ACIGSe absorber surface is necessary to achieve higher open-circuit voltages (Voc). The present work provides microscopic insights to the effects of this KF PDT, employing correlative scanning-electron microscope techniques on identical positions of cross-sectional specimens of the cell stacks. We found that the increase in Voc after the KF PDT can be explained by the removal of Cu-poor, Ag-poor, and Ga-rich regions near the ACIGSe/CdS interface. The KF PDT leads, when optimally doped, to a very thin K-Ag-Cu-Ga-In-Se layer between ACIGSe and CdS. If the KF dose is too large, we find that Cu-poor and K-rich regions form near the ACIGSe/CdS interface with enhanced nonradiative recombination which explains a decrease in the Voc. This effect occurs in addition to the presence of a (K,Ag,Cu)InSe2 intermediate layer, that might be responsible for limiting the short-current density of the solar cells due to a current blocking behavior. Title in Web of Science: Microscopic insight into the impact of the KF post-deposition treatment on optoelectronic properties of (Ag,Cu)(In,Ga)Se-2 solar cells

Herein, a new route of sulfur grading in CuInSe2 (CISe) thin-film solar absorbers by introducing an ultrathin (

Chalcopyrite Cu(In,Ga)Se-2 (CIGSe) solar absorbers are renowned for delivering high solar power conversion efficiency despite containing high concentration of lattice defects amounting to copper deficiencies of several atomic percent. The unique ability to incorporate this deficiency without triggering decomposition (i.e. "tolerance to off-stoichiometry") is viewed by many as the key feature of CIGSe. In principle, this property could benefit any solar absorber, but remarkably little attention has been paid to it so far. In this study, we assess the tolerance to off-stoichiometry of thin-film photovoltaic materials by carrying out ab initio analysis of group-I-poor ordered defect compounds (ODCs) in the extended family of I-III-VI systems (where I = Cu, Ag, III = Al, Ga, In, and VI = S, Se, Te). We analyze convex hulls and structural evolution with respect to group-I content, link them with experimental phase diagrams, and determine two empirical principles for the future identification of solar energy materials with high tolerance to off-stoichiometry. Practical implications for the deposition of I-III-VI absorbers are also discussed in light of our computational results and recent experimental findings.

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.

High-end organic–inorganic lead halide perovskite semitransparent p–i–n solar cells for tandem applications use a phenyl-C61-butyric acid methyl ester (PCBM)/atomic layer deposition (ALD)-SnOx electron transport layer stack. Omitting the PCBM would be preferred for manufacturing, but has in previous studies on (FA,MA)Pb(Br,I)3 and (Cs,FA)Pb(Br,I)3 and in this study on Cs0.05FA0.79MA0.16PbBr0.51I2.49 (perovskite) led to poor solar cell performance because of a bias-dependent light-generated current. A direct ALD-SnOx exposure was therefore suggested to form a nonideal perovskite/SnOx interface that acts as a transport barrier for the light-generated current. To further investigate the interface formation during the initial ALD SnOx growth on the perovskite, the mass dynamics of monitor crystals coated by partial p–i–n solar cell stacks were recorded in situ prior to and during the ALD using a quartz crystal microbalance. Two major finds were made. A mass loss was observed prior to ALD for growth temperatures above 60 °C, suggesting the decomposition of the perovskite. In addition, a mostly irreversible mass gain was observed during the first exposure to the Sn precursor tetrakis(dimethylamino)tin(IV) that is independent of growth temperature and that disrupts the mass gain of the following 20–50 ALD cycles. The chemical environments of the buried interface were analyzed by soft and hard X-ray photoelectron spectroscopy for a sample with 50 ALD cycles of SnOx on the perovskite. Although measurements on the perovskite bulk below and the SnOx film above did not show chemical changes, additional chemical states for Pb, Br, and N as well as a decrease in the amount of I were observed in the interfacial region. From the analysis, these states and not the heating of the perovskite were concluded to be the cause of the barrier. This strongly suggests that the detrimental effects can be avoided by controlling the interfacial design.

Silver alloying of Cu(In,Ga)Se-2 absorbers for thin film photovoltaics offers improvements in open-circuit voltage, especially when combined with optimal alkali-treatments and certain Ga concentrations. The relationship between alkali distribution in the absorber and Ag alloying is investigated here, combining experimental and theoretical studies. Atom probe tomography analysis is implemented to quantify the local composition in grain interiors and at grain boundaries. The Na concentration in the bulk increases up to similar to 60 ppm for [Ag]/([Ag] + [Cu]) = 0.2 compared to similar to 20 ppm for films without Ag and up to similar to 200 ppm for [Ag]/([Ag] + [Cu]) = 1.0. First-principles calculations were employed to evaluate the formation energies of alkali-on-group-I defects (where group-I refers to Ag and Cu) in (Ag,Cu)(In,Ga)Se-2 as a function of the Ag and Ga contents. The computational results demonstrate strong agreement with the nanoscale analysis results, revealing a clear trend of increased alkali bulk solubility with the Ag concentration. The present study, therefore, provides a more nuanced understanding of the role of Ag in the enhanced performance of the respective photovoltaic devices.

Amorphous tin-gallium oxide (a-SGO) grown with atomic layer deposition was evaluated as a buffer layer in (Ag,Cu)(In,Ga)Se2 thin-film solar cells in search for a new material that is compatible with a variety of absorber band gaps. Hard and soft X-ray photoelectron spectroscopy on absorber/a-SGO stacks combined with J–V characterization of solar cells that were fabricated, showed that the conduction band alignment at the absorber/a-SGO interface can be tuned by varying the cation composition and/or growth temperature. Here, the surface band gap was 1.1 eV for the absorber. However, optical band gap data for a-SGO indicate that a suitable conduction band alignment can most likely be achieved even for wider absorber band gaps relevant for tandem top cells. A best efficiency of 17.0% was achieved for (Ag,Cu)(In,Ga)Se2/a-SGO devices, compared to η = 18.6% for the best corresponding CdS reference. Lower fill factor and open-circuit voltage values were responsible for lower cell efficiencies. The reduced fill factor is explained by a larger series resistance, seemingly related to interface properties, which are yet to be optimized. Some layer constellations resulted in degradation in fill factor during light soaking as well. This may partly be explained by light-induced changes in the electrical properties of a-SGO, according to analysis of Al/SGO/n-Si metal-oxide-semiconductor capacitors that were fabricated and characterized with J–V and C–V. Moreover, the introduction of a 1 nm thick Ga2O3 interlayer between the absorber and a-SGO improved the open-circuit voltage, which further indicates that the absorber/a-SGO interface can be improved.

Herein, sulfurization of CuInSe(2)and CuGaSe2(CGSe) absorber layers is compared to improve the understanding of sulfur incorporation into Cu(In,Ga)Se(2)films by annealing in a sulfur atmosphere. It is found for Cu-poor CuInSe(2)that for an annealing temperature of 430 degrees C, sulfur is incorporated into the surface of the absorber and forms an inhomogeneous CuIn(S,Se)(2)layer. In addition, at 530 degrees C, a surface layer of CuInS(2)is formed. In contrast, for Cu-poor CuGaSe(2)samples, S can only be introduced at 530 degrees C, mainly forming an alloy of CuGa(S,Se)(2), where no closed CuGaS(2)layer is found. In Cu-rich CuGaSe(2)samples, however, selenium is substituted by S already at 330 degrees C, which can be explained by a rapid phase transformation of Cu2 - xSe into Cu2 - x(S,Se). This transformation facilitates S in-diffusion and catalyzes CuGa(S,Se)(2)formation, likewise that previously reported to occur in CuInSe2. Finally, the Cu-poor CuInSe(2)solar cell performance is improved by the sulfurization step at 430 degrees C, whereas for the 530 degrees C sample, a decreasing fill factor and short-circuit current density are observed, indicating lower diffusion length accompanied by possible formation of an electron transport barrier. In contrast, the electrical characteristics deteriorate for all sulfurized Cu-poor CuGaSe(2)cells.

This contribution evaluates the effect of absorber off‐stoichiometry in wide‐gap (Ag,Cu)(In,Ga)Se2 (ACIGS) solar cells. It is found that ACIGS films show an increased tendency to form ordered vacancy compounds (OVCs) with increasing Ga and Ag contents. Very little tolerance to off‐stoichiometry is detected for absorber compositions giving the desired properties of 1) an optimum bandgap (EG) for a top cell in tandem devices (EG = 1.6–1.7 eV) and at the same time 2) a favorable band alignment with a CdS buffer layer. Herein, massive formation of either In‐ or Ga‐enriched OVC patches is found for group I‐poor ACIGS. As a consequence, carrier transport and charge collection are significantly impeded in corresponding solar cells. The transport barrier appears to be increasing with storage time, questioning the long‐term stability of wide‐gap ACIGS solar cells. Furthermore, the efficiency of samples with very high Ga and Ag contents depends on the voltage sweep direction. It is proposed that the hysteresis behavior is caused by a redistribution of mobile Na ions in the 1:1:2 absorber lattice upon voltage bias. Finally, a broader perspective on OVC formation in the ACIGS system is provided and fundamental limitations for wide‐gap ACIGS solar cells are discussed.