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We present results demonstrating a three-stage, high-rate, low-temperature deposition process for Cu(In,Ga)Se2 solar cells including a recrystallization step after the second stage, catalyzed by AgBr. The entire deposition and recrystallization process takes place below 450 °C in less than 15 min. Device results with efficiencies exceeding 16% are shown. We achieve very high levels of grain growth and a greater than a 5% absolute increase in device performance because of the recrystallization step relative to an identical process not involving AgBr.

Solar cell degradation can occur through many pathways and at the different stages of the fabrication process, notably because of the water condensation. In the case of Cu(In,Ga)Se2 (CIGS) solar cells, the impact of water ingress on Mo back contact can be substantial for not only the film itself but also the device performance and reliability. Microstructural modification, change in film morphology, loss in reflectance, and increased resistivity because of the moisture ingress were observed via X-ray diffraction, transmission electron microscopy, spectroscopic ellipsometry, and four-point probe measurements, respectively. Secondary ion mass spectrometry measurements revealed drastic changes in the alkali (Na, K) profiles in both the CIGS and Mo layers, likely because of the modification of their diffusion coefficient through Mo. This, in turn, negatively impacts the solar cell efficiency by decreasing both fill factor and open-circuit voltage. Additional experiments, modifying the substrate and utilizing a NaF postdeposition treatment, highlight the mechanisms of degradation as being due to both a modification of the Mo/CIGS interface and the lack of alkali diffusion after water ingress.

In this paper, we studied the effect of rubidium fluoride (RbF) post-deposition treatment (PDT) on the properties of Cu(In,Ga)Se2 (CIGS) solar cells. Specifically, the recombination mechanisms were analyzed by a series of characterizations including thermal and optical defect spectroscopies, temperature dependent current density-voltage measurements, and time resolved photoluminescence. It was found that the main effect of RbF PDT on the solar cell was an increase of the open circuit-voltage, Voc, by 30 mV due to a decrease of the values of the diode quality factor and reverse saturation current. Recombination mechanisms were identified as being in the CIGS space charge region, likely at the grain boundaries and near the CIGS surface. Breakdown of contributions to the Voc increase showed that part of it is due to an increase of the majority carrier concentration (16 mV) and another to the increase in the minority carrier lifetime (1 mV). The latest is mostly due to a reduction in the EV +0.99 eV deep-level trap density. An additional CIGS surface modification (contributing 13 mV), observed by the secondary ion mass spectrometry, is essential to explain the full change in Voc.

Alkali ions are key to improving the performance of polycrystalline Cu(In,Ga)Se2 (CIGS) solar cells. Typically, a soda–lime glass substrate acts as an intrinsic source for many alkali ions. For these ions to reach the CIGS layer, diffusion through a metallic back contact is necessary. Typically deposited via sputtering, the morphology of this metallic back contact is dependent on multiple deposition parameters, including substrate temperature. By preparing films with varying deposition parameters, and utilizing both, multiple material characterizations (X-ray diffraction, scanning electron microscopy, and secondary ion mass spectrometry) and numerical modeling, we demonstrate here that effective paths of diffusion are just as important as diffusion rate for the alkali ions. As the substrate temperature increases, the mechanism that hinders the ability for alkali ions to diffuse switches effectively from diffusion rate to effective path of diffusion. It is shown that the lack of viable diffusion paths at substrate temperatures above 100 °C becomes the dominant factor for the transport of alkali ions.

The impact of moisture and heat treatment on the microstructural, chemical, and electrical properties of Cu(In,Ga)Se2 films and their collective effect on the solar cell device performance was studied. X-ray photoelectron spectroscopy and secondary ion mass spectroscopy measurements show that water exposure causes surface modification and alters the alkali metal distribution, while no composition or structural effect was observed. Deep level transient and optical spectroscopies revealed that the trap densities (NT) for both the EV + 0.65 eV and EV + 0.98 eV traps increase after water exposure, while the majority carrier concentration (NA) decreases. Time-resolved photoluminescence (PL) and steady-state PL measurements indicated the presence of static, not dynamic, quenching. Reduction of open-circuit voltage (VOC) and fill factor (FF) was observed for the devices but was not associated with a change of recombination mechanism, which remains in the absorber space charge region. A small increase in series resistance and shunt conductance accounts for most of the FF change, while the modification in both NA and NT yield most of the change in VOC. A gradient of majority carrier concentration, related to the alkali profile, also yields a small voltage-dependent current collection after moisture and heat treatment.