Optical, Electronic, and Magnetic Engineering of ⟨111⟩ Layered Halide Perovskites

Abstract

Antimony and bismuth ⟨111⟩ layered perovskites have recently attracted significant attention as possible, nontoxic alternatives to lead halide perovskites. Unlike lead halide perovskites, however, ⟨111⟩ halide perovskites have shown limited ability to tune their optical and electronic properties. Herein, we report on the metal alloying of manganese and copper into the family of materials with formula Cs 4 Mn 1−x Cu x Sb 2 Cl 12 (x = 0−1). By changing the concentration of manganese and copper, we show the ability to modulate the bandgap of this family of compounds over the span of 2 electron volts, from 3.0 to 1.0 eV. Furthermore, we show that in doing so, we can also adjust other relevant properties such as their magnetic behavior and their electronic structure.

Two‐Dimensional Halide Perovskites in Solar Cells: 2D or not 2D?

“…Despite some disadvantages, <111>‐layered perovskites offer excellent thermal stability and tolerance to humidity, likely because of their inorganic nature (they have no organic cations). Moreover, this family of materials provides the possibility to use three‐valent metal ions and even to combine 2+ and 3+ metals, akin to lead‐free double perovskites, making them an interesting for research.…”

“…[112][113][114][115] All these materials have shown bandgaps that make them attractive as solar cell absorbers;h owever,t hey show also excitonic behavior, [8] which is likely the main culprit for the limited PCEs obtained for the solar cells made using these materials so far.D espite some disadvantages, < 111 >layered perovskiteso ffer excellent thermal stability and tolerance to humidity, likely because of their inorganic nature (they have no organic cations). Moreover,t his family of materials provides the possibility to use three-valent metal ions and even to combine 2 + and 3 + metals, [116,117] akin to lead-free double perovskites, [102][103][104] making them an interesting for research.…”

Reversible Thermochromism and Strong Ferromagnetism in Two‐Dimensional Hybrid Perovskites

“…The MQW electronic structure enables 2D halide perovskite particularly interesting for optoelectronic applications and magnetic studies . Magnetic susceptibility was investigated in Cs 4 Mn 1− x Cu x Sb 2 Cl 12 ( x =0–1), which were dependent on the concentration of manganese and copper . Investigations on the spin‐reorientation and spin‐control in 2D hybrid perovskite may help to design new materials for future spintronics .…”

“…[30] Magnetic susceptibility was investigated in Cs 4 Mn 1Àx Cu x Sb 2 Cl 12 (x = 0-1), which were dependent on the concentration of manganese and copper. [31] Investigations on the spin-reorientation and spin-control in 2D hybrid perovskite may help to design new materials for future spintronics. [32,33] Despite extensive investigations on perovskites, ferromagnets coupled with thermochromism has not been reported to date.…”

Prediction of room-temperature half-metallicity in layered halide double perovskites

“…[9][10][11][12][13][14][15][16][17][18][19][20][21][22] Very recently, a new type of 〈111〉-oriented layered halide double perovskite (LHDP), e.g., Cs 4 CuSb 2 Cl 12 and Cs 4 MnSb 2 Cl 12 , have been synthesized successfully in experiments with good tolerance towards humidity, heat and light. [23][24][25][26] Interestingly, it is found that Cs 4 MnSb 2 Cl 12 exhibits weak antiferromagnetic (AFM) ordering between the first nearestneighboring (NN) Mn ions. The observation of AFM ground-state in Cs 4 MnSb 2 Cl 12 opens up new possibilities in discovering ferromagnetic (FM) ordering, even half-metallicity, in LHDPs.…”