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.     

A flexible and scalable component-based system architecture for video surveillance as a service,running on infrastructure as a service

There are many proposals for moving traditional video surveillance systems into the cloud, commonly known as Video Surveillance as a Service (VSaaS). Most systems use Hadoop technology for storing video records and distributing video analysis tasks. However, Hadoop is more appropriate for video retrieval services than real time video analysis. Also, existing systems offer neither flexible deployment plans, nor are they capable of automatically minimizing the number of required servers (whether they are physical or virtual machines). Our proposal involves the design and implementation of a component-based VSaaS running on Infrastructure as a Service (IaaS). This paper focuses on the design concepts and component functions that provide solutions for the availability and scalability of VSaaS. Our system can easily scale from one server up to a more complex cluster to support the varying requirements of users. It accesses cloud services via Amazon EC2 for computing services and Amazon S3 API for object storage services, since they are supported by many cloud computing IaaS providers. We also present a components deployment that is suitable for any size and type of system, which combines both physical and virtual machines. Experiments show that the system performs well, and can tolerate difficult scenarios.     

PAHs in Sediments: Unmixing and CMB Modeling of Sources

A chemical mass balance (CMB) model, applied to polycyclic aromatic hydrocarbon (PAH) compounds, is used to apportion PAH sources in a group of seven sediment cores in the Milwaukee Basin of the central Lake Michigan area. PAH apportionment results indicate the dominance of coke oven emissions from 1925–1976, and of highway inputs from 1983–1992 for most of the seven cores. This is consistent with results of carbon particle analysis from the same basin. Milwaukee and Port Washington appear to be primary contributors of point source inputs of PAHs from coke ovens and highway dust. Wood burning is a minor source (<13%). These findings are supported by an independent factor analysis study. Historical PAH records are also determined for the seven sediment cores. The records are unmixed and averaged over the basin. The resulting average record is then used as measured profile in a CMB model to determine PAH sources. Source profiles are historical records of the consumption of coal, petroleum, and wood, including coal used for coke production. A cubic spline technique is developed and applied for the curve fitting of original data points for all of the cores. Unmixed profiles reveal a number of features that are not seen in the original data. Wood burning, coke oven emissions, and highway dust profiles are found to resemble the national consumption records. Coal burning is a very small PAH source (<1%).     

Metal‐Halide Perovskite Transistors for Printed Electronics: Challenges and Opportunities

Following the unprecedented rise in photovoltaic power conversion efficiencies during the past five years, metal‐halide perovskites (MHPs) have emerged as a new and highly promising class of solar‐energy materials. Their extraordinary electrical and optical properties combined with the abundance of the raw materials, the simplicity of synthetic routes, and processing versatility make MHPs ideal for cost‐efficient, large‐volume manufacturing of a plethora of optoelectronic devices that span far beyond photovoltaics. Herein looks beyond current applications in the field of energy, to the area of large‐area electronics using MHPs as the semiconductor material. A comprehensive overview of the relevant fundamental material properties of MHPs, including crystal structure, electronic states, and charge transport, is provided first. Thereafter, recent demonstrations of MHP‐based thin‐film transistors and their application in logic circuits, as well as bi‐functional devices such as light‐sensing and light‐emitting transistors, are discussed. Finally, the challenges and opportunities in the area of MHPs‐based electronics, with particular emphasis on manufacturing, stability, and health and environmental concerns, are highlighted.