Organic-on-organic semiconductor heterojunctions: building blockfor the next generation of optoelectronic devices

A novel class of optoelectronic devices utilizing thin films of stable crystalline organic semiconductors layered onto inorganic semiconductor substrates is described. The electrical properties of these devices are determined by the energy barrier at the heterojunction contact between the organic and inorganic materials, and in many ways are similar to those of ideal diffused-junction inorganic semiconductor devices. The organic materials can be layered onto semiconductor substrates without inducing large strains in either material, hence allowing a wide range of material combinations with a similarly broad range of optoelectronic functions to be realized. As examples, high-bandwidth photodetectors and field-effect transistors made using organic/inorganic semiconductor heterojunctions are discussed. Modification of the optical and electronic properties of the organic films by irradiation with energetic electron and ion beams is considered     

Electronic properties of irradiated semiconductors. A model of the fermi level pinning

A theoretical model of a defect state with highest localization in a semiconductor crystal is suggested. This model can be used to calculate the steady-state position of the Fermi level in radiation-modified semiconductors and to estimate the barrier height in metal-semiconductor contacts and the energy-band offsets in semiconductor heterojunctions. It is shown that the deepest level in the band gap of each semiconductor corresponds to the above state. This level plays a role similar to that of the level of electronic chemical potential in a bulk imperfect semiconductor and at the interphase boundary. Numerical calculations of the energy position of the level under consideration in the band gaps of Group IV and III-V compound semiconductors were performed.     

A charge-separated interfacial hole transport semiconductor for efficient and stable perovskite solar cells

Perovskite solar cells (PSCs) with high efficiency and high stability are still a challenge to produce although remarkable successes have been achieved since they were first reported in 2009. One strategy to effectively improve both the performance as well as the stability is to introduce an interfacial layer between perovskite and hole transport material. Herein, we report a charge-separated (CS) organic semiconductor as the interfacial layer that forms cascaded energy levels between perovskite and hole transportation material. This CS semiconductor displays high hole and electron mobilities by converting long-lived CS states in solution into permanent polarons (charged carriers) in films. Doping with iodinehydride is able to improve the surface morphology of the CS semiconductor layer. Our devices with an iodinehydride-doped CS semiconductor layer exhibit an efficiency of 17.87%, which is increased by ~25% in comparison with 14.24% of the reference devices that have no interfacial layer. This additional CS semiconductor layer also enhances the unsealed device stability by maintaining 90% of initial PCE, while the reference devices degraded by 35% at a relative humidity of 20–30%, temperature of 25 °C and ambient light for 240 h. This result reveals that the utilization of CS states is an alternative approach to construct high charge transport organic semiconductors. An interfacial semiconductor with proper energy level and a matching hole transport mobility can improve the hole extraction, speed up hole transport and suppress charge recombination of PSCs, and thus may be an effective strategy to improve their efficiency and stability.     

Optoelectronic Synapses and Photodetectors Based on Organic Semiconductor/Halide Perovskite Heterojunctions: Materials,Devices, and Applications

Both photodetectors (PDs) and optoelectronic synaptic devices (OSDs) are optoelectronic devices converting light signals into electrical responses. Optoelectronic devices based on organic semiconductors and halide perovskites have aroused tremendous research interest owing to their exceptional optical/electrical characteristics and low-cost processability. The heterojunction formed between organic semiconductors and halide perovskites can modify the exciton dissociation/recombination efficiency and modulate the charge-trapping effect. Consequently, organic semiconductor/halide perovskite heterojunctions can endow PDs and OSDs with high photo responsivity and the ability to simulate synaptic functions respectively, making them appropriate for the development of energy-efficient artificial visual systems with sensory and recognition functions. This article summarizes the recent advances in this research field. The physical/chemical properties and preparation methods of organic semiconductor/halide perovskite heterojunctions are briefly introduced. Then the development of PDs and OSDs based on organic semiconductor/halide perovskite heterojunctions, as well as their innovative applications, are systematically presented. Finally, some prospective challenges and probable strategies for the future development of optoelectronic devices based on organic semiconductor/halide perovskite heterojunctions are discussed.     

Dynamic Photoswitching of Electron Energy Levels at Hybrid ZnO/Organic Photochromic Molecule Junctions

The functionality of interfaces in hybrid inorganic/organic (opto)electronic devices is determined by the alignment of the respective frontier energy levels at both sides of the heterojunctions. Controlling the interface electronic landscape is a key element for achieving favourable level alignment for energy and charge transfer processes. Here, it is shown that the electronic properties of polar ZnO surfaces can be reversibly modified using organic photochromic switches. By employing a range of surface characterization techniques combined with density functional theory calculations, it is demonstrated that self‐assembled monolayers (SAMs) of photochromic phosphonic acid diarylethenes (PA‐DAEs) can be employed to reversibly change the electronic properties of polar ZnO/SAM structures by light stimuli. The highest occupied molecular orbital level of PA‐DAE is raised by 0.7 eV and the lowest unoccupied one lowered by 0.9 eV, respectively, upon illumination by ultraviolet light and the levels shift back to their original position upon illumination by green light. The results thus provide a pathway to tailor hybrid interface electronic properties in a dynamic manner upon simple light illumination, which can be exploited to reversibly tune the electrical properties of photoswitchable (opto)electronic devices.     

Probing Local Electronic Transitions in Organic Semiconductors through Energy‐Loss Spectrum Imaging in the Transmission Electron Microscope

Improving the performance of organic electronic devices depends on exploiting the complex nanostructures formed in the active layer. Current imaging methods based on transmission electron microscopy provide limited chemical sensitivity, and thus the application to materials with compositionally similar phases or complicated multicomponent systems is challenging. Here, it is demonstrated that monochromated transmission electron microscopes can generate contrast in organic thin films based on differences in the valence electronic structure at energy losses below 10 eV. In this energy range, electronic fingerprints corresponding to interband excitations in organic semiconductors can be utilized to generate significant spectral contrast between phases. Based on differences in chemical bonding of organic materials, high‐contrast images are thus obtained revealing the phase separation in polymer/fullerene mixtures. By applying principal component analysis to the spectroscopic image series, further details about phase compositions and local electronic transitions in the active layer of organic semiconductor mixtures can be explored.     

Micro‐/Nanostructured Highly Crystalline Organic Semiconductor Films for Surface‐Enhanced Raman Spectroscopy Applications

The utilization of inorganic semiconductors for surface‐enhanced Raman spectroscopy (SERS) has attracted enormous interest. However, despite the technological relevance of organic semiconductors for enabling inexpensive, large‐area, and flexible devices via solution processing techniques, these π‐conjugated systems have never been investigated for SERS applications. Here for the first time, a simple and versatile approach is demonstrated for the fabrication of novel SERS platforms based on micro‐/nanostructured 2,7‐dioctyl[1]benzothieno[3,2‐b][1]benzothiophene (C8‐BTBT) thin films via an oblique‐angle vapor deposition. The morphology of C8‐BTBT thin films is manipulated by varying the deposition angle, thus achieving highly favorable 3D vertically aligned ribbon‐like micro‐/nanostructures for a 90° deposition angle. By combining C8‐BTBT semiconductor films with a nanoscopic thin Au layer, remarkable SERS responses are achieved in terms of enhancement (≈10⁸), stability (>90 d), and reproducibility (RSD < 0.14), indicating the great promise of Au/C8‐BTBT films as SERS platforms. Our results demonstrate the first example of an organic semiconductor‐based SERS platform with excellent detection characteristics, indicating that π‐conjugated organic semiconductors have a great potential for SERS applications.     

A Novel Approach for the Evaluation of Band Gap Energy in Semiconductors

On the basis of absorption nature of semiconductors, we present a novel and simple method to determine the band gap energies of semiconductors directly from their absorption spectra at any temperatures, without any fitting processes and restrictions of sample thickness. The key point of the approach is the different dependence of the absorption coefficient derivative on the photon energy at different absorption regions in semiconductors. We first demonstrate and verify the approach by detailed temperature-dependent absorption measurements, combined with photoluminescence measurements and empirical band gap equations for the direct band gap of uniform InAs films, and then extend successfully to the indirect band gap of elemental Ge and to the ternary HgCdTe alloys with composition gradient. Furthermore, we have also shown that our approach can not only evaluate the average band gap energy for ternary semiconductor alloys, but also estimate their composition uniformity to monitor the material quality.     

Proposed new heterojunction device for infrared detection

A novel heterojunction diode structure is proposed in which a thin metal layer, inserted between two dissimilar semiconductors, pins the surface potential of each semiconductor with respect to a common reference level (the metal Fermi energy). The resultant structure will, in principle, permit the control of interface potential in heterojunctions.     

Interface Engineering for Solid‐State Dye‐Sensitized Nanocrystalline Solar Cells: The Use of Ion‐Solvating Hole‐Transporting Polymers

The control of interfacial charge transfer is central to the design of photovoltaic devices. This charge transfer is strongly dependent upon the local chemical environment at each interface. In this paper we report a methodology for the fabrication of a novel nanostructured multicomponent film, employing a dual‐function supramolecular organic semiconductor to allow molecular‐level control of the local chemical composition at a nanostructured inorganic/organic semiconductor heterojunction. The multicomponent film comprises a lithium ion doped dual‐functional hole‐transporting material (Li⁺–DFHTM), sandwiched between a dye‐sensitized nanocrystalline TiO₂ film and a mono‐functional organic hole‐transporting material (MFHTM). The DFHTM consists of a conjugated organic semiconductor with ion supporting side chains, designed to allow both electronic and ionic charge transport properties. The Li⁺–DFHTM layers provide a new and versatile way to control the interface electrostatics, and consequently the charge transfer, at a nanostructured dye‐sensitized inorganic/organic semiconductor heterojunction.     

Fabrication and electrical characteristics of Perylene-3,4,9,10-tetracarboxylic dianhydride/p-GaAs diode structure

This study aims to experimentally investigate whether Perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) organic layer at p-GaAs/Ag interface affects electrical transport across this interface or not. The electronic properties of metal–organic semiconductor–inorganic semiconductor structure between p type GaAs and PTCDA organic film have been investigated via current–voltage (I–V) and capacitance–voltage (C–V) methods. The Ag/PTCDA/p-GaAs contact exhibits a rectification behavior with the barrier height of 0.74 eV and ideality factor value of 3.42. Modification of the potential barrier of Ag/p-GaAs diode was achieved by using thin interlayer of the PTCDA organic material. This was attributed to the fact that the PTCDA organic interlayer increased the effective barrier height by influencing the space charge region of GaAs. The low and high frequency capacitance–voltage plots were used to determine the interface state density of the diode.     

GaAs/Si/AlAs异质结的DLTS实验研究

利用深能级瞬态谱(DLTS)技术研究了Si夹层和GaAs层不同生长温度对GaAs/AlAs异质结晶体品质的影响.发现Si夹层的引入并没有引起明显深能级缺陷,而不同温度下生长的GaAs/Si/AlAs异质结随着温度的降低,深能级缺陷明显增加,并进行了分析,得到深能级是由Ga空位引起的,在600℃时生长的晶体质量最佳.     

Doped Organic Semiconductors: Trap‐Filling,Impurity Saturation,and Reserve Regimes

A typical human being carries billions of silicon‐based field‐effect transistors in his/her pockets. What makes these transistors work is Fermi level control, both by doping and field effect. Organic semiconductors are the core of a novel flexible electronics age, but the key effect of doping is still little understood. Here, precise handling is demonstrated for molar doping ratios as low as 10^?5 in p‐ and n‐doped organic thin‐films by vacuum co‐sublimation, allowing comprehensive studying of the Fermi level control over the whole electronic gap of an organic semiconductor. In particular, dopant saturation and reserve regimes are observed for the first time in organic semiconductors. These results will allow for completely new design rules of organic transistors with improved long term stability and precise parameter control.     

The Effects of Electronic Impurities and Electron–Hole Recombination Dynamics on Large‐Grain Organic–Inorganic Perovskite Photovoltaic Efficiencies

Hybrid organic‐inorganic perovskites have attracted considerable attention after promising developments in energy harvesting and other optoelectronic applications. However, further optimization will require a deeper understanding of the intrinsic photophysics of materials with relevant structural characteristics. Here, the dynamics of photoexcited charge carriers in large‐area grain organic‐inorganic perovskite thin films is investigated via confocal time‐resolved photoluminescence spectroscopy. It is found that the bimolecular recombination of free charges is the dominant decay mechanism at excitation densities relevant for photovoltaic applications. Bimolecular coefficients are found to be on the order of 10^?9 cm³ s^?1, comparable to typical direct‐gap semiconductors, yet significantly smaller than theoretically expected. It is also demonstrated that there is no degradation in carrier transport in these thin films due to electronic impurities. Suppressed electron–hole recombination and transport that is not limited by deep level defects provide a microscopic model for the superior performance of large‐area grain hybrid perovskites for photovoltaic applications.     

Electronic Structure and Geminate Pair Energetics at Organic–Organic Interfaces: The Case of Pentacene/C60 Heterojunctions

Organic semiconductors are characterized by localized states whose energies are predominantly determined by electrostatic interactions with their immediate molecular environment. As a result, the details of the energy landscape at heterojunctions between different organic semiconductors cannot simply be deduced from those of the individual semiconductors, and they have so far remained largely unexplored. Here, microelectrostatic computations are performed to clarify the nature of the electronic structure and geminate pair energetics at the pentacene/C₆₀ interface, as archetype for an interface between a donor molecule and a fullerene electron acceptor. The size and orientation of the molecular quadrupole moments, determined by material choice, crystal orientation, and thermodynamic growth parameters of the semiconductors, dominate the interface energetics. Not only do quadrupoles produce direct electrostatic interactions with charge carriers, but, in addition, the discontinuity of the quadrupole field at the interface induces permanent interface dipoles. That discontinuity is particularly striking for an interface with C₆₀ molecules, which by virtue of their symmetry possess no quadrupole. Consequently, at a pentacene/C₆₀ interface, both the vacuum‐level shift and geminate pair dissociation critically depend on the orientation of the pentacene π‐system relative to the adjacent C₆₀.     

Mechanism for Efficient Photoinduced Charge Separation at Disordered Organic Heterointerfaces

Despite the poor screening of the Coulomb potential in organic semiconductors, excitons can dissociate efficiently into free charges at a donor–acceptor heterojunction, leading to application in organic solar cells. A kinetic Monte Carlo model that explains this high efficiency as a two‐step process is presented. Driven by the band offset between donor and acceptor, one of the carriers first hops across the interface, forming a charge transfer (CT) complex. Since the electron and hole forming the CT complex have typically not relaxed within the disorder‐broadened density of states (DOS), their remaining binding energy can be overcome by further relaxation in the DOS. The model only contains parameters that are determined from independent measurements and predicts dissociation yields in excess of 90% for a prototypical heterojunction. Field, temperature, and band offset dependencies are investigated and found to be in agreement with earlier experiments. Whereas the investigated heterojunctions have substantial energy losses associated with the dissociation process, these results suggest that it is possible to reach high dissociation yields at low energy loss.     

Flexible and Ultrasoft Inorganic 1D Semiconductor and Heterostructure Systems Based on SnIP

Low dimensionality and high flexibility are key demands for flexible electronic semiconductor devices. SnIP, the first atomic‐scale double helical semiconductor combines structural anisotropy and robustness with exceptional electronic properties. The benefit of the double helix, combined with a diverse structure on the nanoscale, ranging from strong covalent bonding to weak van der Waals interactions, and the large structure and property anisotropy offer substantial potential for applications in energy conversion and water splitting. It represents the next logical step in downscaling the inorganic semiconductors from classical 3D systems, via 2D semiconductors like MXenes or transition metal dichalcogenides, to the first downsizeable, polymer‐like atomic‐scale 1D semiconductor SnIP. SnIP shows intriguing mechanical properties featuring a bulk modulus three times lower than any IV, III‐V, or II‐VI semiconductor. In situ bending tests substantiate that pure SnIP fibers can be bent without an effect on their bonding properties. Organic and inorganic hybrids are prepared illustrating that SnIP is a candidate to fabricate flexible 1D composites for energy conversion and water splitting applications. SnIP@C₃N₄ hybrid forms an unusual soft material core–shell topology with graphenic carbon nitride wrapping around SnIP. A 1D van der Waals heterostructure is formed capable of performing effective water splitting.     

Highly Efficient Hybrid Solar Cells Based on an Octithiophene–GaAs Heterojunction

We report a new type of hybrid heterojunction solar cell based on rod‐like octithiophene (8T) as the organic p‐type semiconductor and GaAs(111) as the inorganic n‐type semiconductor. By using a semitransparent gold layer as the front contact deposited onto the 8T films, solar‐energy conversion efficiencies of up to 4.2 % could be obtained. The reduction in the contact resistance at the Au/8T interface induced by iodine doping is found to be a very crucial factor for the high efficiency. Furthermore, we demonstrate that hybrid solar cells can be successfully used to investigate the photovoltaic properties of organic semiconductors in detail. By means of external quantum efficiency (EQE) measurements, the influence of film morphology on the photocurrent collection length in 8T films is studied. The results show that, in hybrid solar cells using highly ordered microcrystalline 8T films, an active contribution of the organic‐layer semiconductor to the total photocurrent exists. A very large photocurrent collection length of up to 100 nm has been estimated from EQE measurements, indicating that exciton diffusion is very efficient in microcrystalline 8T. On the other hand, the use of nanocrystalline 8T leads to high photocurrent losses in the organic part of the hybrid solar cell. The strong influence of the film morphology on the photocurrent collection in 8T is attributed to a reduction in the exciton diffusion length due to a high trap density in nanocrystalline 8T films. Thus, our results reveal the importance of high crystalline order for obtaining efficient photocurrent collection in 8T films.     

Magneto-optical behaviors at a 2-D ferromagnetic/organic semiconductor interface for singlet fission

This article reports the magneto-optical effects on the singlet fission of the p-type organic semiconductor, tetracene, from a ferromagnetic/semiconductor interface between thin films of cobalt and tetracene. We experimentally show that this interface has two effects on the thin films of tetracene: spin interactions and electrical polarization. The experimental tools used to study the interface include magnetic field effect photoluminescence (MFE_PL), photoluminescence and absorption. Spin interaction effects are shown by MFE_PL data, where we observe a large increase in the maximum MFE_PL when cobalt is introduced, as well as changes in the hyperfine interactions at low magnetic fields. Electrical polarization is analyzed with photoluminescence and absorption measurements, showing small changes in the energy difference between the HOMO and LUMO levels of tetracene, as well as an increase in the electron-phonon coupling in tetracene. Also, electrical polarization is shown to increase electrical interactions between tetracene molecules. Therefore, we conclude that using spin interactions and electrical polarization from the ferromagnetic/organic semiconductor interface can tune the properties of tetracene, ultimately enhancing singlet fission. This work gives new insight to understand the singlet fission process using a ferromagnetic interface. These changes can be further utilized in photovoltaic applications based on this singlet fission material and be applied to other similar types of singlet fission organic semiconductors.