Precise Control of Quantum Confinement in Cesium Lead Halide Perovskite Quantum Dots via Thermodynamic Equilibrium

Cesium lead halide (CsPbX₃) nanocrystals have emerged as a new family of materials that can outperform the existing semiconductor nanocrystals due to their superb optical and charge-transport properties. However, the lack of a robust method for producing quantum dots with controlled size and high ensemble uniformity has been one of the major obstacles in exploring the useful properties of excitons in zero-dimensional nanostructures of CsPbX₃. Here, we report a new synthesis approach that enables the precise control of the size based on the equilibrium rather than kinetics, producing CsPbX₃ quantum dots nearly free of heterogeneous broadening in their exciton luminescence. The high level of size control and ensemble uniformity achieved here will open the door to harnessing the benefits of excitons in CsPbX₃ quantum dots for photonic and energy-harvesting applications

Effects of Direct Solvent-Quantum Dot Interaction on the Optical Properties of Colloidal Monolayer WS₂ Quantum Dots

Because of the absence of native dangling bonds on the surface of the layered transition metal dichalcogenides (TMDCs), the surface of colloidal quantum dots (QDs) of TMDCs is exposed directly to the solvent environment. Therefore, the optical and electronic properties of TMDCS QDs are expected to have stronger influence from the solvent than usual surface-passivated QDs due to more direct solvent-QD interaction. Study of such solvent effect has been difficult in colloidal QDs of TMDC due to the large spectroscopic heterogeneity resulting from the heterogeneity of the lateral size or (and) thickness in ensemble. Here, we developed a new synthesis procedure producing the highly uniform colloidal monolayer WS₂ QDs exhibiting well-defined photoluminescence (PL) spectrum free from ensemble heterogeneity. Using these newly synthesized monolayer WS₂ QDs, we observed the strong influence of the aromatic solvents on the PL energy and intensity of monolayer WS₂ QD beyond the simple dielectric screening effect, which is considered to result from the direct electronic interaction between the valence band of the QDs and molecular orbital of the solvent. We also observed the large effect of stacking/separation equilibrium on the PL spectrum dictated by the balance between inter QD and QD-solvent interactions. The new capability to probe the effect of the solvent molecules on the optical properties of colloidal TMDC QDs will be valuable for their applications in various liquid surrounding environments

Synthesis and Optical Properties of One Year Air-Stable Chiral Sb(III) Halide Semiconductors

Chiral hybrid metal-halide semiconductors (MHS) pose as ideal candidates for spintronic applications owing to their strong spin–orbit coupling (SOC), and long spin relaxation times. Shedding light on the underlying structure–property relationships is of paramount importance for the targeted synthesis of materials with an optimum performance. Herein, we report the synthesis and optical properties of 1D chiral (R-/S-THBTD)SbBr5 (THBTD = 4,5,6,7-tetrahydro-benzothiazole-2,6-diamine) semiconductors using a multifunctional ligand as a countercation and a structure directing agent. (R-/S-THBTD)SbBr5 feature direct and indirect band gap characteristics, exhibiting photoluminescence (PL) light emission at RT that is accompanied by a lifetime of a few ns. Circular dichroism (CD), second harmonic generation (SHG), and piezoresponse force microscopy (PFM) studies validate the chiral nature of the synthesized materials. Density functional theory (DFT) calculations revealed a Rashba/Dresselhaus (R/D) spin splitting, supported by an energy splitting (ER) of 23 and 25 meV, and a Rashba parameter (αR) of 0.23 and 0.32 eV·Å for the R and S analogs, respectively. These values are comparable to those of the 3D and 2D perovskite materials. Notably, (S-THBTD)SbBr5 has been air-stable for a year, a record performance among chiral lead-free MHS. This work demonstrates that low-dimensional, lead-free, chiral semiconductors with exceptional air stability can be acquired, without compromising spin splitting and manipulation performance