No abstract

No abstract

The emergent properties of chiral organic–inorganic hybrid materials offer opportunities in spin-dependent optoelectronic devices. One of the most promising applications where spin, charge, and light are strongly coupled is circularly polarized light (CPL) detection. However, the performance of state-of-the-art CPL detectors using chiral hybrid metal halide semiconductors is still limited by the low anisotropy factor, poor conductivity, and limited photoresponsivity. Here, we synthesize 0D chiral copper chloride hybrids, templated by chiral methylbenzylammonium (R/S-MBA), i.e., (R-/S-MBA)2CuCl4, that display circular dichroism for the ligand-to-metal charge transfer transition with an absorption anisotropy factor (g CD) among the largest reported for chiral metal halide semiconductor hybrids. To circumvent the poor conductivity of the unpercolated inorganic framework of this chiral absorber, we develop a direct CPL detector that utilizes a heterojunction between the chiral (MBA)2CuCl4 absorber layer and a semiconducting single-walled carbon nanotube (s-SWCNT) transport channel. Our chiral heterostructure shows high photoresponsivity of 452 A/W, a competitive anisotropy factor (g res) of up to 0.21, a current response in microamperes, and low working voltage down to 0.01 V. Our results clearly demonstrate a useful strategy toward high-performance chiral optoelectronic devices, where a nanoscale heterostructure enables direct CPL detection even for highly insulating chiral materials.

The replacement of a small amount of organic cations with bulkier organic spacer cations in the perovskite precursor solution to form a 2D perovskite passivation agent (2D‐PPA) in 3D perovskite thin films has recently become a promising strategy for developing perovskite solar cells (PSCs) with long‐term stability and high efficiency. However, the long, bulky organic cations often form a barrier, hindering charge transport. Herein, for the first time, 2D‐PPA engineering based on wide‐bandgap (≈1.68 eV) perovskites are reported. Pentafluorophenethylammonium (F5PEA+) is introduced to partially replace phenylethylammonium (PEA+) as the 2D‐PPA, forming a strong noncovalent interaction between the two bulky cations. The charge transport across and within the planes of pure 2D perovskites, based on mixed ammoniums, increases by a factor of five and three compared with that of mono‐cation 2D perovskites, respectively. The perovskite films based on mixed‐ammonium (F5PEA+‐PEA+) 2D‐PPA exhibit similar surface morphology and crystal structure, but longer carrier lifetime, lower exciton binding energy, less trap density and higher conductivity, in comparison with those using mono‐cation (PEA+) 2D‐PPA. The performance of PSCs based on mixed‐cation 2D‐PPA is enhanced from 19.58% to 21.10% along with improved stability, which is the highest performance for reported wide‐bandgap PSCs.

Doping of semiconductors enables fine control over the excess charge carriers, and thus the overall electronic properties, crucial to many technologies. Controlled doping in lead-halide perovskite semiconductors has thus far proven to be difficult. However, lower dimensional perovskites such as nanocrystals, with their high surface-area-to-volume ratio, are particularly well-suited for doping via ground-state molecular charge transfer. Here, the tunability of the electronic properties of perovskite nanocrystal arrays is detailed using physically adsorbed molecular dopants. Incorporation of the dopant molecules into electronically coupled CsPbI 3 nanocrystal arrays is confirmed via infrared and photoelectron spectroscopies. Untreated CsPbI 3 nanocrystal films are found to be slightly p-type with increasing conductivity achieved by incorporating the electron-accepting dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F 4 TCNQ) and decreasing conductivity for the electron-donating dopant benzyl viologen. Time-resolved spectroscopic measurements reveal the time scales of Auger-mediated recombination in the presence of excess electrons or holes. Microwave conductance and field-effect transistor measurements demonstrate that both the local and long-range hole mobility are improved by F 4 TCNQ doping of the nanocrystal arrays. The improved hole mobility in photoexcited p-type arrays leads to a pronounced enhancement in phototransistors.

The authors investigate how chiral ligands attached to perovskite nanocrystal (PNC) surfaces structurally distort the perovskite lattice. Chiral electro‐optical properties of the resulting PNCs are demonstrated through the fabrication of a circularly polarized light (CPL) detector with a discrimination of up to 14% between left‐ and right‐handed CPL. Both experimental and electronic‐structure‐based simulations are combined to provide insights into the interactions (both structural and electronic) between chiral organic ligands and PNCs. The major finding is a centro‐asymmetric distortion of the surface lattice that penetrates up to five atomic unit cells deep into the PNCs, which is the likely cause of the chiral‐optical properties. Spin‐polarized transport through chiral‐PNCs results from the chiral‐induced spin selectivity effect and amplifies the discrimination between left and right‐handed CPL as is experimentally demonstrated in the detectors.

No abstract

No abstract