Project description:GeSe monolayer (ML) has recently attracted much interest due to its unique structure and excellent physical properties that can be effectively tuned through single doping of various elements. However, the co-doping effects on GeSe ML are rarely studied. In this study, the structures and physical properties of Mn-X (X = F, Cl, Br, I) co-doped GeSe MLs are investigated by using first-principle calculations. The formation energy and phonon disspersion analyses reveal the stability of Mn-Cl and Mn-Br co-doped GeSe MLs and instability of Mn-F and Mn-I co-doped GeSe MLs. The stable Mn-X (X = Cl, Br) co-doped GeSe MLs exhibit complex bonding structures with respect to Mn-doped GeSe ML. More importantly, Mn-Cl and Mn-Br co-doping can not only tune magnetic properties, but also change the electronic properties of GeSe MLs, which makes Mn-X co-doped GeSe MLs indirect band semiconductors with anisotropic large carrier mobility and asymmetric spin-dependent band structures. Furthermore, Mn-X (X = Cl, Br) co-doped GeSe MLs show weakened in-plane optical absorption and reflection in the visible band. Our results may be useful for electronic, spintronic and optical applications based on Mn-X co-doped GeSe MLs.
Project description:Lead halide perovskites have generated considerable interest in solar cell, sensor, and electronics applications. While great focus has been placed on (CH3NH3)PbI3, an organic-inorganic hybrid perovskite, comparatively little work has been done to understand some of its existing crystal phases and analogous materials after substituting with Sn and/or other halogens in the framework. Here, first-principles density functional theory calculations are performed to comprehensively evaluate the electronic and optical properties of (CH3NH3)BX3 (B = Sn, Pb; X = F, Cl, Br, I) in a low-temperature orthorhombic phase. Bulk modulus, electronic structures, and several optical properties of these perovskite systems are further calculated. The obtained results are first confirmed by comparing with existing perovskite systems in literature. The shifting trends on those physical properties when extending to other barely studied systems of (CH3NH3)BX3 is further revealed. The band gap of these perovskites is found to decrease when varying halogen anion in "X" sites from F to I, and/or substituting Pb cations with Sn in "B" sites. Notably, the less toxic Sn-containing perovskites, (CH3NH3)SnI3 in particular, display higher absorption coefficients in the visible light range than their Pb-containing counterparts. An orthorhombic (CH3NH3)PbF3 is predicted to exist at low temperature, and adsorb strongly UV energy. Our systematical examination efforts on the two groups of perovskites provide valuable physical insights in these materials, and the accompanied new findings warrant further investigation on such subjects.
Project description:Six BiOX1-xYx (X, Y?=?F, Cl, Br, and I) solid solutions have been systematically investigated by density functional theory calculations. BiOCl1-xBrx, BiOBr1-xIx, and BiOCl1-xIx solid solutions have very small bowing parameters; as such, some of their properties increase almost linearly with increasing x. For BiOF1-xYx solid solutions, the bowing parameters are very large and it is extremely difficult to fit the related calculated data by a single equation. Consequently, BiOX1-xYx (X, Y?=?Cl, Br, and I) solid solutions are highly miscible, while BiOF1-xYx (Y?=?Cl, Br, and I) solid solutions are partially miscible. In other words, BiOF1-xYx solid solutions have miscibility gaps or high miscibility temperature, resulting in phase separation and F/Y inhomogeneity. Comparison and analysis of the calculated results and the related physical-chemical properties with different halogen compositions indicates that the parameters of BiOX1-xYx solid solutions are determined by the differences of the physical-chemical properties of the two halogen compositions. In this way, the large deviation of some BiOX1-xYx solid solutions from Vegard's law observed in experiments can be explained. Moreover, the composition ratio of BiOX1-xYx solid solutions can be measured or monitored using optical measurements.
Project description:The highly successful PBE functional and the modified Becke-Johnson exchange potential were used to calculate the structural, electronic, and optical properties of the vacancy-ordered double perovskites A2BX6 (A = Rb, Cs; B = Sn, Pd, Pt; X = Cl, Br, and I) using the density functional theory, a first principles approach. The convex hull approach was used to check the thermodynamic stability of the compounds. The calculated parameters (lattice constants, band gap, and bond lengths) are in tune with the available experimental and theoretical results. The compounds, Rb2PdBr6 and Cs2PtI6, exhibit band gaps within the optimal range of 0.9-1.6 eV, required for the single-junction photovoltaic applications. The photovoltaic efficiency of the studied materials was assessed using the spectroscopic-limited-maximum-efficiency (SLME) metric as well as the optical properties. The ideal band gap, high dielectric constants, and optimum light absorption of these perovskites make them suitable for high performance single and multi-junction perovskite solar cells.
Project description:Lead-free perovskites of Cs3Sb2X9 (X = Cl, Br, or I) have attracted wide attention owing to their low toxicity. High pressure is an effective and reversible method to tune bandgap without changing the chemical composition. Here, the structural and photoelectric properties of Cs3Sb2X9 under high pressure were theoretically studied by using the density functional theory. The results showed that the ideal bandgap for Cs3Sb2X9 can be achieved by applying high pressure. Moreover, it was found that the change of the bandgap is caused by the shrinkage of the Sb-X long bond in the [Sb2X9]3- polyhedra. Partial density of states indicated that Sb-5s and X-p orbitals contribute to the top of the valence band, while Sb-5p and X-p orbitals dominate the bottom of the conduction band. Moreover, the band structure and density of states showed significant metallicity at 38.75, 24.05 GPa for Cs3Sb2Br9 and Cs3Sb2I9, respectively. Moreover, the absorption spectra showed the absorption edge redshifted, and the absorption coefficient of the Cs3Sb2X9 increased under high pressure. According to our calculated results, the narrow bandgap and enhanced absorption ability under high pressure provide a new idea for the design of the photovoltaic and photoelectric devices.
Project description:In hybrid perovskite materials like CH3NH3PbI3, methylammonium (MA) lead iodide (MAPI), the orientation of the MA+ cations and their ordering can significantly affect the structure of the inorganic framework. Although the states near the band edges are known to be primarily derived from the Pb and halogen orbitals rather than from the organic ion, the latter may have an indirect effect through their impact on the structural relaxation. In this work, we investigate both the structural relaxation effects of the inorganic framework in response to the MA+ orientation and their impact on the electronic structure near the band edges. Calculations are performed for MA(Pb,Sn)X 3 with (X = I, Br, and Cl) materials for both Pb- and Sn-based compounds. The work focuses on the high-temperature α-phase, which is nominally cubic if averaged over all possible MA orientations and in which no alternating rotations of the octahedral occur, so that the unit cell is the smallest possible. The effects of van der Waals (vdW) corrections to density functional theory on the structural relaxation are investigated. Our results reveal that the vdW interactions between the MA+ cation and the inorganic framework can strongly affect the optimized orientation and position of the molecule and the resulting distortion of the inorganic framework. Consequently, it also affects the electronic properties of the materials and specifically can change the band structure from direct to indirect band gaps. The robustness of this result is studied by comparing hybrid functional calculations and quasiparticle self-consistent GW calculations as well as spin-orbit coupling.
Project description:The multiple anion superlattice Bi4O4SeCl2 has been reported to exhibit extremely low thermal conductivity along the stacking c-axis, making it a promising material for thermoelectric applications. In this study, we investigate the thermoelectric properties of Bi4O4SeX2 (X = Cl, Br) polycrystalline ceramics with different electron concentrations by adjusting the stoichiometry. Despite optimizing the electric transport, the thermal conductivity remained ultra-low and approached the Ioffe-Regel limit at high temperatures. Notably, our findings demonstrate that non-stoichiometric tuning is a promising approach for enhancing the thermoelectric performance of Bi4O4SeX2 by refining its electric transport, resulting in a figure of merit of up to 0.16 at 770 K.
Project description:We report a correlation between the structural phase transition of CsPbX3 (X=Cl, Br, I) nanocrystals (NCs) and their temperature dependent steady-state photoluminescence (PL) and time-resolved PL (TRPL). In constrast to CsPbBr3 and CsPbI3 NCs which exhibited a continuous blue shift in their bandgap with increasing temperature, the CsPbCl3 exhibited a blue shift until ~193 K, followed by a red shift until room temperature. We attribute this change from a blue to a red shift to a structural phase transtion in CsPbCl3, which also manifested in the temperature dependent TRPL. Notably, the exciton recombination lifetimes showed a similar reverse trend due to the phase transition in CsPbCl3, which has not been reported previously.
Project description:The ionic liquid (IL) trihalogen monoanions [N2221 ][X3 ]- and [N2221 ][XY2 ]- ([N2221 ]+ =triethylmethylammonium, X=Cl, Br, I, Y=Cl, Br) were investigated electrochemically via temperature dependent conductance and cyclic voltammetry (CV) measurements. The polyhalogen monoanions were measured both as neat salts and as double salts in 1-butyl-1-methyl-pyrrolidinium trifluoromethane-sulfonate ([BMP][OTf], [X3 ]- /[XY2 ]- 0.5 M). Lighter IL trihalogen monoanions displayed higher conductivities than their heavier homologues, with [Cl3 ]- being 1.1 and 3.7 times greater than [Br3 ]- and [I3 ]- , respectively. The addition of [BMP][OTf] reduced the conductivity significantly. Within the group of polyhalogen monoanions, the oxidation potential develops in the series [Cl3 ]- >[BrCl2 ]- >[Br3 ]- >[IBr2 ]- >[ICl2 ]- >[I3 ]- . The redox potential of the interhalogen monoanions was found to be primarily determined by the central halogen, I in [ICl2 ]- and [IBr2 ]- , and Br in [BrCl2 ]- . Additionally, tetrafluorobromate(III) ([N2221 ]+ [BrF4 ]- ) was analyzed via CV in MeCN at 0 °C, yielding a single reversible redox process ([BrF2 ]- /[BrF4 ]- ).
Project description:Chiral organic compounds are excellent second-order nonlinear optical (NLO) materials due to their inherent non-symmetric electronic structures combined with the advantages of organic compounds. At present, density functional theory (DFT) has become a powerful tool for predicting the properties of novel materials. In this paper, based on chiral lemniscular [16]cycloparaphenylene, three novel compounds are designed by introduction of donor/acceptor units and their combinations. The geometrical/electronic structure, electronic absorption, and the second-order NLO properties of these compounds have been systematically investigated by DFT/TDDFT theory. The simulated UV-Vis/CD spectra of compound 1 are in good agreement with the experimental ones, enabling us to assign their electronic transition characteristics and absolute configuration with high confidence. The investigations show that energy gaps, absorption wavelength and second-order NLO response may be effectively tuned by the introduction of the donor or acceptor units or their combinations. For instance, the second-order NLO value of compound 4 is about 207 times as large as the average second-order polarizability of the organic molecule urea. Thus, the studied compounds are expected to be potential large second-order NLO materials.