Mono- and Co-Doped Mn-Doped CsPbCl3 Perovskites with Enhanced Doping Efficiency and Photoluminescent Performance.

To investigate the effect of Mn and other metal dopants on the photoelectronic performance of CsPbCl3 perovskites, we conducted a series of theoretical analyses. Our findings showed that after Mn mono-doping, the CsPbCl3 lattice contracted and the bonding strength increased, resulting in a more compact structure of the metal octahedral cage. The relaxation of the metal octahedral cage, along with the Jahn-Teller effect, results in a decrease in lattice strain between the octahedra and a reduction in the energy of the entire lattice due to the deformation of the metal octahedron. These three factors work together to reduce intrinsic defects and enhance the stability and electronic properties of CsPbCl3 perovskites. The solubility of the Mn dopant is significantly increased when co-doped with Ni, Fe, and Co dopants, as it compensates for the lattice strain induced by Mn. Doping CsPbCl3 perovskites reduces the band gap due to the decreased contributions of 3d orbitals from the dopants. Our analyses have revealed that strengthening the CsPbCl3 lattice and reducing intrinsic defects can result in improved stability and PL properties. Moreover, increasing Mn solubility and decreasing the bandgap can enhance the PLQY of orange luminescence in CsPbCl3 perovskites. These findings offer valuable insights for the development of effective strategies to enhance the photoelectronic properties of these materials.

Studies on the Light-Induced Phase Transition of CsPbBr3 Metal Halide Perovskite Materials.

We investigate the internal mechanism of the light-induced phase transition of CsPbBr3 perovskite materials via density functional theory simulations. Although CsPbBr3 tends to appear in the orthorhombic structure, it can be changed easily by external stimulus. We find that the transition of photogenerated carriers plays the decisive role in this process. When the photogenerated carriers transit from the valence band maximum to conduction band minimum in the reciprocal space, they actually transit from Br ions to Pb ions in the real space, which are taken away by the Br atoms with higher electronegativity from Pb atoms during the initial formation of the CsPbBr3 lattice. The reverse transition of valence electrons leads to the weakening of bond strength, which is proved by our calculated Bader charge, electron localization function, and integral value of COHP results. This charge transition releases the distortion of the Pb-Br octahedral framework and expands the CsPbBr3 lattice, providing possibilities to the phase transition from the orthorhombic structure to tetragonal structure. This phase transition is a self-accelerating positive feedback process, increasing the light absorption efficiency of the CsPbBr3 material, which is of great significance for the widespread promotion and application of the photostriction effect. Our results are helpful to understand the performance of CsPbBr3 perovskite under a light irradiation environment.

Studies on the photoelectronic properties of a manganese (Mn)-doped lead-free double perovskite.

Taking Cs2NaBiCl6, Cs2AgInCl6 and Cs2AgBiCl6 as examples of lead-free double perovskites (DPs), we study the photoluminescence (PL) properties of Mn-doped DPs. The electron localization function (ELF) reveals the more ionic nature of the Na-Cl bond in Cs2NaBiCl6 than that of the Ag-Cl bond in Cs2AgBiCl6. Bader charge calculations confirm the nominal +2 valence state of Mn ions in both DPs. Mn2+ ions introduce two defect levels in the band gap of the Cs2NaBiCl6 host, accounting for the d-d transition (4T1-6A1 transition) of Mn2+ and thus the subsequent orange PL. The changes of the crystal field and their influences on the emission energy of Mn2+ ions in different DPs are evaluated by calculating the Racah parameters (B and C) and the crystal field strength (Dq) obtained from energies of the terms of d5 in the Cs2NaBiCl6:Mn2+ and Cs2AgInCl6:Mn2+ systems. The results show that Dq in Cs2AgInCl6:Mn2+ is stronger than that in Cs2NaBiCl6:Mn2+. The analyses on bonding interactions of the Mn-Cl bond via ELF and the integrated projected pCOHP also confirm the stronger ionic bonding interactions and thus the boost of the crystal field strength in the Cs2AgInCl6:Mn2+ system, which results in the blue-shift of the Mn2+ introduced PL peak from Cs2AgInCl6 to Cs2NaBiCl6. Our results provide a new strategy to modulate the emission wavelengths, i.e., tuning the crystal field.

Investigations of modulation effect of co-metal ions on the optical properties of the hybrid double perovskites (MA)2AgBi1-xSbxBr6.

Composition engineering plays an important role in generating novel properties and decreasing the lead (Pb) toxicity for halide perovskite materials. To find out the modulation effect introduced by the composition engineering, namely,B'-site co-metal ions, in (MA)2AgBi1-xSbxBr6systems with various Bi/Sb ratios ofx= 0, 0.25, 0.75, 1.00, series of theoretical simulations and analyses are carried out. For the (MA)2AgBi1-xSbxBr6systems, the Goldschmidt tolerance factortand the octahedral factorµindicate that all samples are in a standard double perovskite structure with alternating AgBr6and Bi/SbBr6octahedra. The calculated electronic structures show that the band gap of (MA)2AgBi1-xSbxBr6decreases with the increase of Sb content, but the indirect band gaps are maintained for all samples. By analyses of the imaginary partɛ2(ω) of dielectric function and the absorption spectra, we find that all (MA)2AgBi1-xSbxBr6systems show absorption in the visible-light region. All these results indicate that the composition engineering adopted in this paper is an effective strategy to modulate the optical properties of (MA)2AgBi1-xSbxBr6systems and may open a new way to put it into applications in the fields of solar cells and other optoelectronic devices.

Modulation Effect Generated by A Cations in Hybrid A2BB'X6 Double Halogen Perovskite Materials.

Double perovskite A2BB'X6, including all-inorganic and hybrid organic-inorganic composition, show great potential applications. The role of A cations (organic molecules or inorganic ions) in the double perovskite is distinct from that in the standard perovskite. Therefore, we carried out systematic analyses of the geometric and electronic structures of Cs2AgBiBr6 and (MA)2AgBiBr6 (MA = CH3NH3) double perovskites. Cs2AgBiBr6 maintains the standard cubic double perovskite lattice. While MA molecules prefer to align in the [110] direction in (MA)2AgBiBr6 and give rise to obvious lattice distortion. The band gap of (MA)2AgBiBr6 is slightly less than that of Cs2AgBiBr6. Because of the spherical or quasi-spherical wave functions of the s/d orbitals, the lattice distortion and the transverse shift between Ag/Bi and Br induced by MA molecules do not change the composition of the band edges. But the complex bonding interactions between MA and the inorganic frameworks make the Ag-Br or Bi-Br bond lengths no longer identical values, so the bond strength and the energy level of each bonding state are dispersed and the band is expanded, which reduces the band gap of the hybrid organic-inorganic double perovskite (MA)2AgBiBr6. Making the role of A cations in the A2BB'X6 double perovskite clear, we could find an excellent double perovskite to put forward their applications.

Investigation of the Mn dopant-enhanced photoluminescence performance of lead-free Cs2AgInCl6 double perovskite crystals.

The lead-free double perovskite Cs2AgInCl6 is a potential candidate for LEDs, the photoluminescence performance of which is reinforced greatly by Mn doping. Here, we analyzed the geometric, electronic and photoluminescence properties of Mn-doped Cs2AgInCl6 by means of first-principle calculations. We found that in the interior of Cs2AgInCl6, the Mn dopant formed defect complexes by substituting an Ag atom and generating an Ag vacancy (MnAgVAg) owing to the charge balance and the weak distortion of the metal octahedra. The MnAgVAg defect introduced two defect bands in the forbidden gap, which was contributed predominantly by the 3d orbitals of the Mn2+ ions. The electron transition of the Mn2+ ions from the first excited state to the ground state, i.e., from 4T1 to 6A1 states, gives rise to the PL spectrum that is lower than the bandgap. Therefore, we show that the Mn dopant indeed reinforces the PL performance of Cs2AgInCl6 greatly and is beneficial for its use as an LED material.

Magnetism tuned by the charge states of defects in bulk C-doped SnO2 materials.

To analyze the controversial conclusions on the magnetism of C-doped SnO2 (SnO2:C) bulk materials between theoretical calculations and experimental observations, we propose the critical role of the charge states of defects in the geometric structures and magnetism, and carry out a series of first principle calculations. By changing the charge states, we can influence Bader charge distributions and atomic orbital occupancies in bulk SnO2:C systems, which consequently conduct magnetism. In all charged SnO2:C supercells, C-2px/py/pz electron occupancies are significantly changed by the charge self-regulation, and thus they make the C-2p orbitals spin polarized, which contribute to the dominant magnetic moment of the system. When the concentration of C dopant in the SnO2 supercell increases, the charge redistribution assigns extra electrons averagely to each dopant, and thus effectively modulates the magnetism. These findings provide an experimentally viable way for controlling the magnetism in these systems.