Singly and Doubly Occupied Higher Quantum States in Nanocrystals

Filling the lowest quantum state of the conduction band of colloidal nanocrystals with a single electron, which is analogous to the filling the lowest unoccupied molecular orbital in a molecule with a single electron, has attracted much attention due to the possibility of harnessing the electron spin for potential spin-based applications. The quantized energy levels of the artificial atom, in principle, make it possible for a nanocrystal to be filled with an electron if the Fermi-energy level is optimally tuned during the nanocrystal growth. Here, we report the singly occupied quantum state (SOQS) and doubly occupied quantum state (DOQS) of a colloidal nanocrystal in steady state under ambient conditions. The number of electrons occupying the lowest quantum state can be controlled to be zero, one (unpaired), and two (paired) depending on the nanocrystal growth time via changing the stoichiometry of the nanocrystal. Electron paramagnetic resonance spectroscopy proved the nanocrystals with single electron to show superparamagnetic behavior, which is a direct evidence of the SOQS, whereas the DOQS of the two- or zero-electron occupied nanocrystals in the 1S_e exhibit diamagnetic behavior. In combination with the superconducting quantum interference device measurement, it turns out that the SOQS of the HgSe colloidal quantum dots has superparamagnetic property. The appearance and change of the steady-state mid-IR intraband absorption spectrum reflect the sequential occupation of the 1S_e state with electrons. The magnetic property of the colloidal quantum dot, initially determined by the chemical synthesis, can be tuned from diamagnetic to superparamagnetic and vice versa by varying the number of electrons through postchemical treatment. The switchable magnetic property will be very useful for further applications such as colloidal nanocrystal based spintronics, nonvolatile memory, infrared optoelectronics, catalyst, imaging, and quantum computing

Enhanced Efficiency and Long-Term Stability of Perovskite Solar Cells by Synergistic Effect of Nonhygroscopic Doping in Conjugated Polymer-Based Hole-Transporting Layer

A face-on oriented and p-doped semicrystalline conjugated polymer, poly­[(2,5-bis­(2-hexyldecyloxy)­phenylene)-<i>alt</i>-(5,6-difluoro-4,7-di­(thiophen-2-yl)­benzo­[<i>c</i>]­[1,2,5]-thiadiazole)] (PPDT2FBT), was studied as a hole-transport layer (HTL) in methylammonium lead triiodide-based perovskite solar cells (PVSCs). PPDT2FBT exhibits a mid-band gap (1.7 eV), high vertical hole mobility (7.3 × 10^–3 cm²/V·s), and well-aligned frontier energy levels with a perovskite layer for efficient charge transfer/transport, showing a maximum power conversion efficiency (PCE) of 16.8%. Upon doping the PPDT2FBT HTL with a nonhygroscopic Lewis acid, tris­(pentafluorophenyl)­borane (BCF, 2–6 wt %), the vertical conductivity was improved by a factor of approximately 2, and the resulting PCE was further improved up to 17.7%, which is higher than that of standard PVSCs with 2,2′,7,7′-tetrakis­(<i>N,N</i>-di-<i>p</i>-methoxyphenylamine)-9,9′-spirobifluorene (spiro-OMeTAD) as an HTL. After BCF doping, the clearly enhanced carrier diffusion coefficient, diffusion length, and lifetime were measured using intensity-modulated photocurrent and photovoltage spectroscopy. Furthermore, compared to the standard PVSCs with spiro-OMeTAD, the temporal device stability was remarkably improved, preserving the ∼60% of the original PCE for 500 h without encapsulation under light-soaking condition (1 sun AM 1.5G) at 85 °C and 85% humidity, which is mainly due to the highly crystalline conjugated backbone of PPDT2FBT and nonhygroscopic nature of BCF. In addition, formamidinium lead iodide/bromide (FAPbI_3–<i>x</i>Br<i>_x</i>)-based PVSCs with the BCF-doped PPDT2FBT as an HTL was also prepared to show 18.8% PCE, suggesting a wide applicability of PPDT2FBT HTL for different types of PVSCs

A Planar Cyclopentadithiophene–Benzothiadiazole-Based Copolymer with sp²‑Hybridized Bis(alkylsulfanyl)methylene Substituents for Organic Thermoelectric Devices

A semicrystalline p-type thermoelectric conjugated polymer based on a polymer backbone of cyclopentadithiophene and benzothiadiazole, poly­[(4,4′-(bis­(hexyldecyl­sulfanyl)­methylene)­cyclopenta­[2,1-<i>b</i>:3,4-<i>b</i>′]­dithiophene)-<i>alt</i>-(benzo­[<i>c</i>]­[1,2,5]­thiadiazole)] (PCPDTSBT), is designed and synthesized by replacing normal alkyl side-chains with bis­(alkylsulfanyl)­methylene substituents. The sp²-hybridized olefinic bis­(alkylsulfanyl)­methylene side-chains and the sulfur–sulfur (S–S) chalcogen interactions extend a chain planarity with strong interchain packing, which is confirmed by density functional calculations and morphological studies, i.e., grazing incidence X-ray scattering measurement. The doping, electrical, morphological, and thermoelectric characteristics of PCPDTSBT are investigated by comparison with those of poly­[(4,4′-bis­(2-ethylhexyl)­cyclopenta­[2,1-<i>b</i>:3,4-<i>b</i>′]­dithiophene)-<i>alt</i>-(benzo­[<i>c</i>]­[1,2,5]­thiadiazole)] (PCPDTBT) with ethylhexyl side-chains. Upon doping with a Lewis acid, B­(C₆F₅)₃, the maximum electrical conductivity (7.47 S cm^–1) of PCPDTSBT is ∼1 order higher than that (0.65 S cm^–1) of PCPDTBT, and the best power factor is measured to be 7.73 μW m^–1 K^–2 for PCPDTSBT with doping 9 mol % of B­(C₆F₅)₃. The Seebeck coefficient–electrical conductivity relation is analyzed by using a charge transport model for polymers, suggesting that the doped PCPDTSBT film has superb charge transport property based on a high crystallinity with olefinic side-chains. This study emphasizes the importance of side-chain engineering by using the sp²-hybridized olefinic substituents to modulate interchain packing, crystalline morphology, and the resulting electrical properties