Origin of Hole-Trapping States in Solution-Processed Copper(I) Thiocyanate and Defect-Healing by I2 Doping

Solution-processed copper(I) thiocyanate (CuSCN) typically exhibits low crystallinity with short-range order; the defects result in a high density of trap states that limit the device's performance. Despite the extensive electronic applications of CuSCN, its defect properties are not understood in detail. Through X-ray absorption spectroscopy, pristine CuSCN prepared from the standard diethyl sulfide-based recipe is found to contain under-coordinated Cu atoms, pointing to the presence of SCN⁻ vacancies. A defect passivation strategy is introduced by adding solid I₂ to the processing solution. At small concentrations, the iodine is found to exist as I⁻ which can substitute for the missing SCN⁻ ligand, effectively healing the defective sites and restoring the coordination around Cu. Computational study results also verify this point. Applying I₂-doped CuSCN as a p-channel in thin-film transistors shows that the hole mobility increases by more than five times at the optimal doping concentration of 0.5 mol.%. Importantly, the on/off current ratio and the subthreshold characteristics also improve as the I₂ doping method leads to the defect-healing effect while avoiding the creation of detrimental impurity states. An analysis of the capacitance-voltage characteristics corroborates that the trap state density is reduced upon I₂ addition.     

Copper(I) Thiocyanate (CuSCN) Hole‐Transport Layers Processed from Aqueous Precursor Solutions and Their Application in Thin‐Film Transistors and Highly Efficient Organic and Organometal Halide Perovskite Solar Cells

This study reports the development of copper(I) thiocyanate (CuSCN) hole‐transport layers (HTLs) processed from aqueous ammonia as a novel alternative to conventional n‐alkyl sulfide solvents. Wide bandgap (3.4–3.9 eV) and ultrathin (3–5 nm) layers of CuSCN are formed when the aqueous CuSCN–ammine complex solution is spin‐cast in air and annealed at 100 °C. X‐ray photoelectron spectroscopy confirms the high compositional purity of the formed CuSCN layers, while the high‐resolution valence band spectra agree with first‐principles calculations. Study of the hole‐transport properties using field‐effect transistor measurements reveals that the aqueous‐processed CuSCN layers exhibit a fivefold higher hole mobility than films processed from diethyl sulfide solutions with the maximum values approaching 0.1 cm² V^?1 s^?1. A further interesting characteristic is the low surface roughness of the resulting CuSCN layers, which in the case of solar cells helps to planarize the indium tin oxide anode. Organic bulk heterojunction and planar organometal halide perovskite solar cells based on aqueous‐processed CuSCN HTLs yield power conversion efficiency of 10.7% and 17.5%, respectively. Importantly, aqueous‐processed CuSCN‐based cells consistently outperform devices based on poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate HTLs. This is the first report on CuSCN films and devices processed via an aqueous‐based synthetic route that is compatible with high‐throughput manufacturing and paves the way for further developments.     

Study of the Hole Transport Processes in Solution‐Processed Layers of the Wide Bandgap Semiconductor Copper(I) Thiocyanate (CuSCN)

Wide bandgap hole‐transporting semiconductor copper(I) thiocyanate (CuSCN) has recently shown promise both as a transparent p‐type channel material for thin‐film transistors and as a hole‐transporting layer in organic light‐emitting diodes and organic photovoltaics. Herein, the hole‐transport properties of solution‐processed CuSCN layers are investigated. Metal–insulator–semiconductor capacitors are employed to determine key material parameters including: dielectric constant [5.1 (±1.0)], flat‐band voltage [?0.7 (±0.1) V], and unintentional hole doping concentration [7.2 (±1.4) × 10¹⁷ cm^?3]. The density of localized hole states in the mobility gap is analyzed using electrical field‐effect measurements; the distribution can be approximated invoking an exponential function with a characteristic energy of 42.4 (±0.1) meV. Further investigation using temperature‐dependent mobility measurements in the range 78–318 K reveals the existence of three transport regimes. The first two regimes observed at high (303–228 K) and intermediate (228–123 K) temperatures are described with multiple trapping and release and variable range hopping processes, respectively. The third regime observed at low temperatures (123–78 K) exhibits weak temperature dependence and is attributed to a field‐assisted hopping process. The transitions between the mechanisms are discussed based on the temperature dependence of the transport energy.     

Influence of the Electron Deficient Co‐Monomer on the Optoelectronic Properties and Photovoltaic Performance of Dithienogermole‐based Co‐Polymers

A series of donor–acceptor (D–A) conjugated polymers utilizing 4,4‐bis(2‐ethylhexyl)‐4H‐germolo[3,2‐b:4,5‐b′]dithiophene ( DTG ) as the electron rich unit and three electron withdrawing units of varying strength, namely 2‐octyl‐2H‐benzo[d][1,2,3]triazole ( BTz ), 5,6‐difluorobenzo[c][1,2,5]thiadiazole ( DFBT ) and [1,2,5]thiadiazolo[3,4‐c]pyridine ( PT ) are reported. It is demonstrated how the choice of the acceptor unit ( BTz , DFBT , PT ) influences the relative positions of the energy levels, the intramolecular transition energy (ICT), the optical band gap (E_g^opt), and the structural conformation of the DTG ‐based co‐polymers. Moreover, the photovoltaic performance of poly[(4,4‐bis(2‐ethylhexyl)‐4H‐germolo[3,2‐b:4,5‐b′]dithiophen‐2‐yl)‐([1,2,5]thiadiazolo[3,4‐c]pyridine)] ( PDTG‐PT ), poly[(4,4‐bis(2‐ethylhexyl)‐4H‐germolo[3,2‐b:4,5‐b′]dithiophen‐2‐yl)‐(2‐octyl‐2H‐benzo[d][1,2,3]triazole)] ( PDTG‐BTz ), and poly[(4,4‐bis(2‐ethylhexyl)‐4H‐germolo[3,2‐b:4,5‐b′]dithiophen‐2‐yl)‐(5,6‐difluorobenzo[c][1,2,5]thiadiazole)] ( PDTG‐DFBT ) is studied in blends with [6,6]‐phenyl‐C₇₀‐butyric acid methyl ester ( PC₇₀BM ). The highest power conversion efficiency (PCE) is obtained by PDTG‐PT (5.2%) in normal architecture. The PCE of PDTG‐PT is further improved to 6.6% when the device architecture is modified from normal to inverted. Therefore, PDTG‐PT is an ideal candidate for application in tandem solar cells configuration due to its high efficiency at very low band gaps (E_g^opt = 1.32 eV). Finally, the 6.6% PCE is the highest reported for all the co‐polymers containing bridged bithiophenes with 5‐member fused rings in the central core and possessing an E_g^opt below 1.4 eV.     

Elucidating the Coordination of Diethyl Sulfide Molecules in Copper(I) Thiocyanate (CuSCN) Thin Films and Improving Hole Transport by Antisolvent Treatment

Copper(I) thiocyanate (CuSCN) is rising to prominence as a hole‐transporting semiconductor in various opto/electronic applications. Its unique combination of good hole mobility, high optical transparency, and solution‐processability renders it a promising hole‐transport layer for solar cells and p‐type channel in thin‐film transistors. CuSCN is typically deposited from sulfide‐based solutions with diethyl sulfide (DES) being the most widely used. However, little is known regarding the effects of DES on CuSCN films despite the fact that DES can coordinate with Cu(I) and result in a different coordination polymer having a distinct crystal structure when fully coordinated. Herein, the coordination of DES in CuSCN films is thoroughly investigated with a suite of characterization techniques as well as density functional theory. This study reveals that DES directly affects the microstructure of CuSCN by stabilizing the polar crystalline surfaces via the formation of strong coordination bonds. Furthermore, a simple antisolvent treatment is demonstrated to be effective at modifying the microstructure and morphology of CuSCN films. The treatment with tetrahydrofuran or acetone leads to uniform films consisting of CuSCN crystallites with high crystallinity and their surfaces passivated by DES molecules, resulting in an increase in the hole mobility from 0.01 to 0.05 cm² V^?1 s^?1.