All existing solar cell materials including hybrid perovskites show rather small absorption coefficient (α) of ≈104 cm−1 in the bandgap (Eg) transition region. The weak band‐edge light absorption is an essential problem, limiting conversion efficiency particularly in a tandem solar cell. Herein, all distorted chalcogenide perovskites (BaZrS3, SrZrS3, BaHfS3, and SrHfS3) are found experimentally to exhibit extraordinary high α exceeding 105 cm−1 near Eg, indicating the highest band‐edge α among all known solar cell materials. The giant absorption in the Eg region, which is consistent with the first principles, arises from the intense p–d interband transition enabled by dense S 3p valence states. For solar cell application, low‐gap BaZrS3 derivatives, Ba(Zr,Ti)S3 and BaZr(S,Se)3, are further synthesized. Among the possible candidates of top‐cell materials, an earth‐abundant and nontoxic Ba(Zr,Ti)S3 alloy shows great potential, reaching a maximum potential efficiency exceeding 38% in a chalcogenide perovskite/crystalline Si tandem architecture.

Tail state formation in solar cell absorbers leads to a detrimental effect on solar cell performance. Nevertheless, the characterization of the band tailing in experimental semiconductor crystals is generally difficult. In this article, to determine the tail state generation in various solar cell materials, we have developed a quite general theoretical scheme in which the experimental Urbach energy is compared with the absorption edge energy derived from density functional theory (DFT) calculation. For this purpose, the absorption spectra of solar cell materials, including CdTe, CuInSe 2 (CISe), CuGaSe 2 (CGSe), Cu 2 ZnSnSe 4 (CZTSe), Cu 2 ZnSnS 4 (CZTS) and hybrid perovskites, have been calculated by DFT particularly using very-high-density k meshes. As a result, we find that the tail state formation is negligible in CdTe, CISe, CGSe and hybrid perovskite polycrystals. However, coevaporated CZTSe and CZTS layers exhibit very large Urbach energies, which are far larger than the theoretical counterparts. Based on DFT analysis results, we conclude that the quite large tail state formation observed in the CZTSe and CZTS originates from extensive cation disordering. In particular, even a slight cation substitution is found to generate unusual band fluctuation in CZTS(Se). In contrast, CH 3 NH 3 PbI 3 hybrid perovskite shows the sharpest absorption edge theoretically, which agrees with experiment.

We find that coevaporated Cu2ZnGeSe4 has an ideal bandgap for solar cells (1.39 ± 0.01 eV) and shows quite reduced tail state absorption with a very low Urbach energy of 28 meV, which is far smaller than those of more studied Cu2ZnSnSe4 and Cu2ZnSnS4. The small tail states in Cu2ZnGeSe4 are found to originate from almost perfect cation ordering, while unusual tail state generation occurs in the Sn-based quaternary compounds by extensive cation substitution. Quite remarkably, the crystal total energy derived from first-principles calculations reveals a unified rule for the cation disordering, confirming that the lighter group-IV element (i.e., Ge) is essential for eliminating the tail state generation induced by cation mixing.

Theoretical material investigation based on density functional theory (DFT) has been a breakthrough in the last century. Nevertheless, the optical properties calculated by DFT generally show poor agreement with experimental results particularly when the absorption-coefficient (α) spectra in logarithmic scale are compared. In this study, we have established an alternative DFT approach (PHS method) that calculates highly accurate α spectra, which show remarkable agreement with experimental spectra even in logarithmic scale. In the developed method, the optical function estimated from generalized gradient approximation (GGA) using very high-density k mesh is blue-shifted by incorporating the energy-scale correction by a hybrid functional and the amplitude correction by sum rule. Our simple approach enables high-precision prediction of the experimental α spectra of all solar-cell materials (GaAs, InP, CdTe, CuInSe 2 and Cu 2 ZnGeSe 4 ) investigated here. The developed method is superior to conventional GGA, hybrid functional and GW methods and has clear advantages in accuracy and computational cost.

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