Lead-free halide double perovskites with the formula of quaternary + + 3+ -
26A B B' X have recently attracted intense interest as alternatives to lead-halide-perovskite-based optoelectronic materials for their non-toxicity and enhanced chemical and thermodynamic stability. However, the understanding of intrinsic defect properties and their effects on carrier transport and Fermi level tuning is still limited. In this paper, we show that, by exploring the phase diagram of a halide double perovskite, one can control the effects of intrinsic defects on carrier trapping and Fermi level pinning. We reveal the ideal growth conditions to grow p-type Cs2AgInCl6 and Cs2AgBiCl6 as well as semi-insulating Cs2AgBiBr6 with low trap density for targeted photovoltaic or visible-light/radiation detection application.Lead (Pb) halide perovskites have been extensively investigated for diverse applications, including photovoltaics [1-10], light-emitting diode [11][12][13], laser [14][15][16], and radiation detection [17][18][19][20], owing to their unique electronic and optical properties. However, the toxicity of Pb and the intrinsic material instability have hindered their development. Recently, inorganic Pb-free halide double perovskites (HDPs), which are a large class of quaternary compounds with a general formula of + + 3+ -26 A B B' X , have attracted great attention as alternatives to Pb halide perovskites [21-31]. In particular, Cs2AgInCl6 and Cs2AgBiX6 (X=Cl, Br), which have been successfully synthesized in experiment and have the bandgap values of 2.0-3.0 eV and good material stability, have shown great potential as useful optoelectronic materials such as photovoltaic (PV) absorbers [32-35], photon and ionizing radiation detectors [36,37]. Cs2AgInCl6 exhibits direct band gap (2.0 eV according to the photoluminescence measure) as well as an ultra-long carrier lifetime (6 μs) [21,38-40], which are suitable for PV applications. However, Meng et al. reported that the optical absorption at the visible range in Cs2AgInCl6 may be significantly reduced due to the parity-forbidden transition at band edges [41]. Nevertheless, the low trap density (towards 10 8 cm -3 ) in single-crystal Cs2AgInCl6 makes it a promising ultraviolet detector material [37], which may find applications in fire and missile flame detection as well as optical communications. Cs2AgInBr6, with a theoretically predicted direct band gap of ~1.50 eV [21], is expected to be a good PV absorber or visible-light detector, although its synthesis is still a challenge. In contrast to the direct band gaps found in Cs2AgInX6, Cs2AgBiCl6 and Cs2AgBiBr6 have indirect band gaps of 2.77 and 2.19 eV, respectively [25,29,42]. Despite their relatively large band gaps for PV applications, it has been reported that the solar cells based on Cs2AgBiBr6 films show power conversion efficiencies up to 2.5% without device optimization [43]. The efficiency might be further improved by narrowing the bandgap of Cs2AgBiBr6 via trivalent metal doping/alloying [31,44]. Moreover, the indirect...