Energy Level Alignment at Metal/Solution‐Processed Organic Semiconductor Interfaces

Energy barriers between the metal Fermi energy and the molecular levels of organic semiconductor devoted to charge transport play a fundamental role in the performance of organic electronic devices. Typically, techniques such as electron photoemission spectroscopy, Kelvin probe measurements, and in‐device hot‐electron spectroscopy have been applied to study these interfacial energy barriers. However, so far there has not been any direct method available for the determination of energy barriers at metal interfaces with n‐type polymeric semiconductors. This study measures and compares metal/solution‐processed electron‐transporting polymer interface energy barriers by in‐device hot‐electron spectroscopy and ultraviolet photoemission spectroscopy. It not only demonstrates in‐device hot‐electron spectroscopy as a direct and reliable technique for these studies but also brings it closer to technological applications by working ex situ under ambient conditions. Moreover, this study determines that the contamination layer coming from air exposure does not play any significant role on the energy barrier alignment for charge transport. The theoretical model developed for this work confirms all the experimental observations.     

Mapping Energy Levels for Organic Heterojunctions

An organic semiconductor thin film is a solid‐state matter comprising one or more molecules. For applications in electronics and photonics, several distinct functional organic thin films are stacked together to create a variety of devices such as organic light‐emitting diodes and organic solar cells. The energy levels at these thin‐film junctions dictate various electronic processes such as the charge transport across these junctions, the exciton dissociation rates at donor–acceptor molecular interfaces, and the charge trapping during exciton formation in a host–dopant system. These electronic processes are vital to a device's performance and functionality. To uncover a general scientific principle in governing the interface energy levels, highest occupied molecular orbitals, and vacuum level dipoles, herein a comprehensive experimental research is conducted on several dozens of organic–organic heterojunctions representative of various device applications. It is found that the experimental data map on interface energy levels, after correcting variables such as molecular orientation‐dependent ionization energies, consists of three distinct regions depending on interface fundamental physical parameters such as Fermi energy, work function, highest occupied molecular orbitals, and lowest unoccupied molecular orbitals. This general energy map provides a master guide in selection of new materials for fabricating future generations of organic semiconductor devices.     

Role of Thick‐Lithium Fluoride Layer in Energy Level Alignment at Organic/Metal Interface: Unifying Effect on High Metallic Work Functions

The function of ≈3‐nm thick lithium fluoride (LiF) buffer layers in combination with high work function metal contacts such as coinage metals and ferromagnetic metals for use in organic electronics and spintronics is investigated. The energy level alignment at the organic/LiF/metal interface is systematically studied using photoelectron spectroscopy and the integer charge transfer model. The thick‐LiF buffer layer is found to pin the Fermi level to ≈3.8 eV, regardless of the work function of the initial metal due to energy level bending in the LiF layer caused by depletion of defect states. At 3‐nm thickness, the LiF buffer layer provides full coverage, and the organic semiconductor adlayers are found to physisorb with the consequence that the energy level alignment at the organic/LiF interface follows the integer charge transfer model's predictions.     

Rational Tuning of Molecular Interaction and Energy Level Alignment Enables High‐Performance Organic Photovoltaics

The performance of organic photovoltaics (OPVs) has rapidly improved over the past years. Recent work in material design has primarily focused on developing near‐infrared nonfullerene acceptors with broadening absorption that pair with commercialized donor polymers; in the meanwhile, the influence of the morphology of the blend film and the energy level alignment on the efficiency of charge separation needs to be synthetically considered. Herein, the selection rule of the donor/acceptor blend is demonstrated by rationally considering the molecular interaction and energy level alignment, and highly efficient OPV devices using both‐fluorinated or both‐nonfluorinated donor/acceptor blends are realized. With the enlarged absorption, ideal morphology, and efficient charge transfer, the devices based on the PBDB‐T‐F/Y1‐4F blend and PBDB‐T‐F/Y6 exhibit champion power conversion efficiencies as high as 14.8% and 15.9%, respectively.     

Highly Sensitive and Broadband Organic Photodetectors with Fast Speed Gain and Large Linear Dynamic Range at Low Forward Bias

Photodetectors with high photoelectronic gain generally require a high negative working voltage and a very low environment temperature. They also exhibit low response speed and narrow linear dynamic range (LDR). Here, an organic photodiode is demonstrated, which shows a large amount of photon to electron multiplication at room temperature with highest external quantum efficiency (EQE) from ultraviolet (UV) to near‐infrared region of 5.02 × 10³% (29.55 A W^?1) under a very low positive voltage of 1.0 V, accompanied with a fast response speed and a high LDR from 10^?7 to 10¹ mW cm^?2. At a relatively high positive bias of 10 V, the EQE is up to 1.59 × 10⁵% (936.05 A W^?1). Inversely, no gain is found at negative bias. The gain behavior is exactly similar to a bipolar phototransistor, which is attributed to the photoinduced release of accumulated carriers. The devices at a low voltage exhibit a normalized detectivity (D *) over 10¹⁴ Jones by actual measurements, which is about two or three order of magnitudes higher than that of the highest existing photodetectors. These pave a new way for realization of high sensitive detectors with fast response toward the single photon detection.     

结构抗震消能控制的试验与应用研究

为了改善高层剪力墙结构的抗震性能,根据结构控制的原理提出了一种新型剪力墙—沿竖向消能的带竖缝剪力墙。首先,进行了竖缝处消能装置的剪切—摩擦试验,研究了这种消能装置的受力机理和消能机理,给出了荷载—位移骨架曲线的理论计算方法。其次,进行了带有此消能装置的一层带竖缝剪力墙和普通实体墙的低周反复荷载试验,对比研究了这两类剪力墙的破坏机理和滞回特性,试验表明这种新型消能剪力墙具有良好的抗震性能。接着,讨论了这种剪力墙的消能计算方法。最后,介绍了消能剪力墙的一个工程应用实例。     

Engineering the Au-Cu2O Crystalline Interfaces for Structural and Catalytic Integration

Precise structural control has attracted tremendous interest in pursuit of the tailoring of physical properties. Here, this work shows that through strong ligand-mediated interfacial energy control, Au-Cu₂O dumbbell structures where both the Au nanorod (AuNR) and the partially encapsulating Cu₂O domains are highly crystalline. The synthetic advance allows physical separation of the Au and Cu₂O domains, in addition to the use of long nanorods with tunable absorption wavelength, and the crystalline Cu₂O domain with well-defined facets. The interplay of plasmon and Schottky effects boosts the photocatalytic performance in the model photodegradation of methyl orange, showing superior catalytic efficiency than the AuNR@Cu₂O core–shell structures. In addition, compared to the typical core–shell structures, the AuNR-Cu₂O dumbbells can effectively electrochemically catalyze the CO₂ to C₂₊ products (ethanol and ethylene) via a cascade reaction pathway. The excellent dual function of both photo- and electrocatalysis can be attributed to the fine physical separation of the crystalline Au and Cu₂O domains.     

Unique Energy Alignments of a Ternary Material System toward High‐Performance Organic Photovoltaics

Incorporating narrow‐bandgap near‐infrared absorbers as the third component in a donor/acceptor binary blend is a new strategy to improve the power conversion efficiency (PCE) of organic photovoltaics (OPV). However, there are two main restrictions: potential charge recombination in the narrow‐gap material and miscompatibility between each component. The optimized design is to employ a third component (structurally similar to the donor or acceptor) with a lowest unoccupied molecular orbital (LUMO) energy level similar to the acceptor and a highest occupied molecular orbital (HOMO) energy level similar to the donor. In this design, enhanced absorption of the active layer and enhanced charge transfer can be realized without breaking the optimized morphology of the active layer. Herein, in order to realize this design, two new narrow‐bandgap nonfullerene acceptors with suitable energy levels and chemical structures are designed, synthesized, and employed as the third component in the donor/acceptor binary blend, which boosts the PCE of OPV to 11.6%.