Growth of Large Crystalline Grains of Vanadyl‐Phthalocyanine without Epitaxy on Graphene

The performance of organic semiconductor thin films in electronic devices is related to their crystal structure and morphology, with charge transport mobility dependent on the degree of crystallinity and on the crystallographic orientation. Here organic molecular beam deposition of vanadyl phthalocyanine is studied on graphene and it is shown that crystalline grains up to several micrometers across can be formed at substrate temperatures of 155 °C, compared to room temperature grain sizes of ≈30 nm. Transmission electron microscopy confirms the presence of long range order at elevated substrate temperatures and reveals that the molecules are stacked in an edge‐on orientation, but are not epitaxially aligned to the graphene. The crystalline grain sizes are significantly larger on graphene than on disordered substrates such as graphene oxide and silicon oxide. The effect on charge transport is probed by conducting atomic force microscopy, with the high temperature films on graphene showing increased mobility and uniformity and decreased trap density. These results illustrate an important advantage for the integration of graphene electrodes with organic semiconductor devices: the homogeneous surface of graphene results in high diffusion and low nucleation rates for thin film growth, encouraging the formation of highly crystalline films even with nonepitaxial growth.     

Water-Surface-Mediated Precise Patterning of Organic Single-Crystalline Films via Double-Blade Coating for High-Performance Organic Transistors

Application-oriented growth of patterned organic semiconductor (OSC) thin films with a single domain is a nonnegotiable requirement for the manufacturing of high-performance organic electronic devices. However, the prevalent selective-wetting patterning method remains a challenge in controlling the density of nucleation events in microscale spaces, resulting in thin films with high grain boundary density and no preferential orientation spherulites. Herein, a simple double-blade-coating printing technique using a combination of wetting-patterned substrates to produce an array of highly crystalline OSC thin films is developed. Specifically, the approach confines the OSC crystallization on a molecular-flat water surface in specific areas, enabling a significant reduction in the number of nuclei. Consequently, patterned 2,7-dioctyl[1]benzothieno[3,2-b] benzothiophene (C₈-BTBT) thin films comprising single-crystal domains are achieved with an exceptionally high yield of 62.5%. The organic field-effect transistor array developed from such patterns of C₈-BTBT single-crystalline films exhibits an excellent average mobility of 11.5 cm² V⁻¹ s⁻¹ which is 12.5-fold higher compared to that of the reference sample fabricated via conventional single-blade coating. It is believed that this approach can be widely applied to other soluble organic materials, thereby opening up opportunities for fabricating multicomponent integrated electronics.     

The Role of OTS Density on Pentacene and C60 Nucleation,Thin Film Growth,and Transistor Performance

In organic thin film transistors (OTFTs), charge transport occurs in the first few monolayers of the semiconductor near the semiconductor/dielectric interface. Previous work has investigated the roles of dielectric surface energy, roughness, and chemical functionality on performance. However, large discrepancies in performance, even with apparently identical surface treatments, indicate that additional surface parameters must be identified and controlled in order to optimize OTFTs. Here, a crystalline, dense octadecylsilane (OTS) surface modification layer is found that promotes two‐dimensional semiconductor growth. Higher mobility is consistently achieved for films deposited on crystalline OTS compared to on disordered OTS, with mobilities as high as 5.3 and 2.3 cm² V^?1 s^?1 for C₆₀ and pentacene, respectively. This is a significant step toward morphological control of organic semiconductors which is directly linked to their thin film charge carrier transport.     

Hall Effect in Polycrystalline Organic Semiconductors: The Effect of Grain Boundaries

Highly crystalline thin films in organic semiconductors are important for applications in high‐performance organic optoelectronics. Here, the effect of grain boundaries on the Hall effect and charge transport properties of organic transistors based on two exemplary benchmark systems is elucidated: (1) solution‐processed blends of 2,7‐dioctyl[1]benzothieno[3,2‐b][1]benzothiophene (C₈‐BTBT) small molecule and indacenodithiophene‐benzothiadiazole (C₁₆IDT‐BT) conjugated polymer, and (2) large‐area vacuum evaporated polycrystalline thin films of rubrene (C₄₂H₂₈). It is discovered that, despite the high field‐effect mobilities of up to 6 cm² V^?1 s^?1 and the evidence of a delocalized band‐like charge transport, the Hall effect in polycrystalline organic transistors is systematically and significantly underdeveloped, with the carrier coherence factor α < 1 (i.e., yields an underestimated Hall mobility and an overestimated carrier density). A model based on capacitively charged grain boundaries explaining this unusual behavior is described. This work significantly advances the understanding of magneto‐transport properties of organic semiconductor thin films.     

Rational Design of Organic Semiconductors for Texture Control and Self‐Patterning on Halogenated Surfaces

Understanding the interactions at interfaces between the materials constituting consecutive layers within organic thin‐film transistors (OTFTs) is vital for optimizing charge injection and transport, tuning thin‐film microstructure, and designing new materials. Here, the influence of the interactions at the interface between a halogenated organic semiconductor (OSC) thin film and a halogenated self‐assembled monolayer on the formation of the crystalline texture directly affecting the performance of OTFTs is explored. By correlating the results from microbeam grazing incidence wide angle X‐ray scattering (μGIWAXS) measurements of structure and texture with OTFT characteristics, two or more interaction paths between the terminating atoms of the semiconductor and the halogenated surface are found to be vital to templating a highly ordered morphology in the first layer. These interactions are effective when the separating distance is lower than 2.5 d_w, where d_w represents the van der Waals distance. The ability to modulate charge carrier transport by several orders of magnitude by promoting “edge‐on” versus “face‐on” molecular orientation and crystallographic textures in OSCs is demonstrated. It is found that the “edge‐on” self‐assembly of molecules forms uniform, (001) lamellar‐textured crystallites which promote high charge carrier mobility, and that charge transport suffers as the fraction of the “face‐on” oriented crystallites increases.     

2D Organic–Inorganic Hybrid Thin Films for Flexible UV–Visible Photodetectors

Flexible 2D inorganic MoS₂ and organic g‐C₃N₄ hybrid thin film photodetectors with tunable composition and photodetection properties are developed using simple solution processing. The hybrid films fabricated on paper substrate show broadband photodetection suitable for both UV and visible light with good responsivity, detectivity, and reliable and rapid photoswitching characteristics comparable to monolayer devices. This excellent performance is retained even after the films are severely deformed at a bending radius of ≈2 mm for hundreds of cycles. The detailed charge transfer and separation processes at the interface between the 2D materials in the hybrid films are confirmed by femtosecond transient absorption spectroscopy with broadband capability.     

Stretchable Mesh-Patterned Organic Semiconducting Thin Films on Creased Elastomeric Substrates

Recently, many researchers have tried to develop stretchable semiconducting thin films that can maintain their electrical performance under stretching. However, the fabrication processes have not been sufficiently practical and feasible to be used for soft electronics. Here, a stretchable high-performance organic semiconducting thin film is fabricated by exploiting simultaneous patterning and pinning of a polymer semiconductor solution on an elastomeric substrate in which creasing-instability has occurred. As a result, a mesh-like polymer semiconducting thin film having vacant regions in the crease centers and surrounding crystalline regions near them can be fabricated. Due to the mesh-like morphology and the percolated crystalline regions, the polymer semiconducting thin film shows superior stretchability and charge-transport performance compared to the reference flat polymer thin film. When incorporated into organic thin-film transistors, the DPP-DTT polymer semiconducting thin film maintains its high field-effect carrier mobility (0.53 ± 0.03 cm² (V s)⁻¹) under a strain ε of 80% and is highly stable under repeated stretching cycles at an ε of 50%.     

Self‐Assembled,Millimeter‐Sized TIPS‐Pentacene Spherulites Grown on Partially Crosslinked Polymer Gate Dielectric

Here, a highly crystalline and self‐assembled 6,13‐bis(triisopropylsilylethynyl) pentacene (TIPS‐Pentacene) thin films formed by simple spin‐coating for the fabrication of high‐performance solution‐processed organic field‐effect transistors (OFETs) are reported. Rather than using semiconducting organic small‐molecule–insulating polymer blends for an active layer of an organic transistor, TIPS‐Pentacene organic semiconductor is separately self‐assembled on partially crosslinked poly‐4‐vinylphenol:poly(melamine‐co‐formaldehyde) (PVP:PMF) gate dielectric, which results in a vertically segregated semiconductor‐dielectric film with millimeter‐sized spherulite‐crystalline morphology of TIPS‐Pentacene. The structural and electrical properties of TIPS‐Pentacene/PVP:PMF films have been studied using a combination of polarized optical microscopy, atomic force microscopy, 2D‐grazing incidence wide‐angle X‐ray scattering, and secondary ion mass spectrometry. It is finally demonstrated a high‐performance OFETs with a maximum hole mobility of 3.40 cm² V^?1 s^?1 which is, to the best of our knowledge, one of the highest mobility values for TIPS‐Pentacene OFETs fabricated using a conventional solution process. It is expected that this new deposition method would be applicable to other small molecular semiconductor–curable polymer gate dielectric systems for high‐performance organic electronic applications.     

A Highly Sensitive Graphene‐Organic Hybrid Photodetector with a Piezoelectric Substrate

To create a sensitive photodetector, the transparent and conductive properties of graphene and the optical and photovoltaic properties of poly(3‐hexylthiophene) (P3HT) are combined as a hybrid composite. Based on the inherent nature of the band alignment between graphene and P3HT, the photogenerated holes are able to transfer to the graphene layer and improve the photoresponse to be much better than the traditional layer by layer organic system. Additionally, the graphene is deposited on a piezoelectric Pb(Zr_0.2Ti_0.8)O₃ (PZT) substrate, and the photoresponse of such composite photodetectors is found to be ten times larger than on SiO₂ base. It is demonstrated that the electric field of the polarization of piezoelectric substrate helps the spatial separation of photogenerated electrons and holes and promotes the hole doping of graphene to enhance the photoconduction. A detailed investigation of graphene layers, thickness of P3HT and time evolution shows that the composite of graphene and P3HT on PZT can be used as a sensitive photodetector and has potential as an effective solar cell. Moreover, with the replacement of P3HT by a thin layer of bulk heterojunction of polymer and fullerene, the photosensitivity can be further increased by more than one order of magnitude.     

Colossal magnetoresistance in Sol-Gel derived epitaxial thin film of Co-doped La1−xCaxMnOx

Electrical, magnetic, and magnetotransport properties of sol-gel derived epitaxial thin films of Co-doped La_1?xCa_xMnO₃ are reported. The epitaxial thin films, deposited using metal-salt routed sol-gel processing, show excellent quality of epitaxy (FWHM=0.3°). Their surface roughness is about 30Å and average grain size is 500Å. The thin films exhibit the typical behavior of colossal magnetoresistive oxide, manifesting paramagnetic semiconductor to ferromagnetic metal transition near magnetic transition. The doping of Co reduces electrical conductivity, Curie temperature (T_c) and saturation magnetization (M_s). However, the peak magnetoresistance ratio does not show a monotonous change with increasing Co content. These results are interpreted by spin-disorder scattering, magnetic inhomogeneity, and lattice distortion.     

Pr3+掺杂SrTiO3薄膜的聚合物前驱体法制备及发光性能

采用聚合物前驱体法,在LaNiO<,3>/si(100)衬底上低温制备了Pr<,3+>掺杂SrTiO<,3>薄膜.用XRD,AFM、PL手段分析了薄膜的晶体结构、表面形貌与发光性能.结果显示,退火温度决定SrTiO<,3>薄膜的晶粒大小和表面形貌,在600℃退火2 h获得的薄膜表面均匀、无裂痕,晶粒大小约为60 nm,...     

Underlying Mechanism of Inkjet Printing of Uniform Organic Semiconductor Films Through Antisolvent Crystallization

An underlying mechanism is reported for the formation of highly uniform crystalline organic semiconductor films by the double‐shot inkjet printing (IJP) technique utilizing antisolvent crystallization. It is demonstrated that the ability to form uniform films with this technique can be attributed to the unique nature of the initial contact dynamics between the chemically different microdroplets before occurrence of solute crystallization. Experiments are conducted systematically where a single microdroplet is over‐deposited by the IJP technique on a chemically different sessile droplet, for ten kinds of pure and miscible solvent combinations. The subsequent behavior is observed by high speed camera. The initial contact dynamics can be classified into three dramatically different cases that are respectively referred to as wetting, dewetting, and sinking. These phenomena are unique to microdroplets and the conditions for the occurrence of each type of phenomenon can be consistently explained by the fact that the initial contact dynamics are driven by the difference of surface tension of the liquids. Among the three kinds of dynamics, the wetting phenomenon creates a thin solution layer on the antisolvent droplet surface and can be used thus to manufacture uniform semiconductor films, where the coffee ring effect can be eliminated.     

Porous Organic Field‐Effect Transistors for Enhanced Chemical Sensing Performances

The thin‐film structures of chemical sensors based on conventional organic field‐effect transistors (OFETs) can limit the sensitivity of the devices toward chemical vapors, because charge carriers in OFETs are usually concentrated within a few molecular layers at the bottom of the organic semiconductor (OSC) film near the dielectric/semiconductor interface. Chemical vapor molecules have to diffuse through the OSC films before they can interact with charge carriers in the OFET conduction channel. It has been demonstrated that OFET ammonia sensors with porous OSC films can be fabricated by a simple vacuum freeze‐drying template method. The resulted devices can have ammonia sensitivity not only much higher than the pristine OFETs with thin‐film structure but also better than any previously reported OFET sensors, to the best of our knowledge. The porous OFETs show a relative sensitivity as high as 340% ppm^?1 upon exposure to 10 parts per billion (ppb) NH₃. In addition, the devices also exhibit decent selectivity and stability. This general and simple strategy can be applied to a wide range of OFET chemical sensors to improve the device sensitivity.     

High‐Resolution Near‐Field Optical Investigation of Crystalline Domains in Oligomeric PQT‐12 Thin Films

The structure and morphology on different length scales dictate both the electrical and optical properties of organic semiconductor thin films. Using a combination of spectroscopic methods, including scanning near‐field optical microscopy, we study the domain structure and packing quality of highly crystalline thin films of oligomeric PQT‐12 with 100 nanometer spatial resolution. The pronounced optical anisotropy of these layers measured by polarized light microscopy facilitates the identification of regions with uniform molecular orientation. We find that a hierarchical order on three different length scales exists in these layers, made up of distinct well‐ordered dichroic areas at the ten‐micrometer‐scale, which are sub‐divided into domains with different molecular in‐plane orientation. These serve as a template for the formation of smaller needle‐like crystallites at the layer surface. A high degree of crystalline order is believed to be the cause of the rather high field‐effect mobility of these layers of 10^?3 cm² V^?1 s^?1, whereas it is limited by the presence of domain boundaries at macroscopic distances.     

Highly Conductive and Environmentally Stable Organic Transparent Electrodes Laminated with Graphene

Improving the lifetime and the operational and thermal stability of organic thin‐film materials while maintaining high conductivity and mechanical flexibility is critical for flexible electronics applications. Here, it is reported that highly conductive and environmentally stable organic transparent electrodes (TEs) can be fabricated by mechanically laminating poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) films containing dimethylsulfoxide and Zonyl fluorosurfactant (PDZ films) with a monolayer graphene barrier. The proposed lamination process allows graphene to be coated onto the PDZ films uniformly and conformally with tight interfacial binding, free of wrinkles and air gaps. The laminated films exhibit an outstanding room‐temperature hole mobility of ≈85.1 cm² V^?1 s^?1 since the graphene can serve as an effective bypass for charge carriers. The significantly improved stability of the graphene‐laminated TEs against high mechanical/thermal stress, humidity, and ultraviolet irradiation is particularly promising. Furthermore, the incorporation of the graphene barrier increases the expected lifetime of the TEs by more than two orders of magnitude.     

High‐Mobility Air‐Stable Solution‐Shear‐Processed n‐Channel Organic Transistors Based on Core‐Chlorinated Naphthalene Diimides

High charge carrier mobility solution‐processed n‐channel organic thin‐film transistors (OTFTs) based on core‐chlorinated naphthalene tetracarboxylic diimides (NDIs) with fluoroalkyl chains are demonstrated. These OTFTs were prepared through a solution shearing method. Core‐chlorination of NDIs not only increases the electron mobilities of OTFTs, but also enhances their air stability, since the chlorination in the NDI core lowers the lowest unoccupied molecular orbital (LUMO) levels. The air‐stability of dichlorinated NDI was better than that of the tetrachlorinated NDIs, presumably due to the fact that dichlorinated NDIs have a denser packing of the fluoroalkyl chains and less grain boundaries on the surface, reducing the invasion pathway of ambient oxygen and moisture. The devices of dichlorinated NDIs exhibit good OTFT performance, even after storage in air for one and a half months. Charge transport anisotropy is observed from the dichlorinated NDI. A dichlorinated NDI with ?CH₂C₃F₇ side chains reveals high mobilities of up to 0.22 and 0.57 cm² V^?1 s^?1 in parallel and perpendicular direction, respectively, with regard to the shearing direction. This mobility anisotropy is related to the grain morphology. In addition, we find that the solution‐shearing deposition affects the molecular orientation in the crystalline thin films and lowers the d(001)‐spacing (the out‐of‐plane interlayer spacing), compared to the vapor‐deposited thin films. Core‐chlorinated NDI derivatives are found to be highly suitable for n‐channel active materials in low‐cost solution‐processed organic electronics.     

UV-directly patternable organic–inorganic hybrid composite dielectrics for organic thin-film transistors

A research on the design, synthesis, and characterization of novel cross-linked polymer organic–inorganic hybrid materials as gate insulators for organic thin-film transistors (OTFTs) with vanadyl-phthalocyanine as the organic semiconductor is presented. The hybrid films (0.5–1.2 μm thick) can be easily prepared by sol–gel technology and fabricated by spin-coating a mixture of zirconium n-butoxide sol with a side-chain triethoxysilane-capped polyurethane solution in ambient conditions, followed by curing at low temperatures (∼120 °C) and cross-linking under UV light. OTFTs with this film as gate insulator were achieved with good processability, high charge-carrier mobility of 0.56 cm²/Vs, surface roughness of around 0.49–0.59 nm, ultralow threshold of −6 V, and ultralow leakage of 0.24 mA. Hybrid films with various compositions were investigated, and the results showed that the field-effect mobility of the OTFTs was dominated by the high dielectric constant component ZrO₂. The result indicated that these hybrid materials are promising candidates for the exploration of devices using OTFTs.     

Reconfigurable Electronic Physically Unclonable Functions Based on Organic Thin-Film Transistors with Multiscale Polycrystalline Entropy for Highly Secure Cryptography Primitives

In this study, organic thin-film transistors (OTFTs) are investigated as a promising platform for cost-effective, reconfigurable, and strong electronic physically unclonable functions (PUFs) for highly secure cryptography primitives. Simple spin-casting of solution-processable small-molecule organic semiconductors forms unique and unclonable fingerprint thin films with randomly distributed polycrystalline structures ranging from nanoscale molecular orientations to microcrystalline orientations, which provides a stochastic entropy source of device-to-device variations for OTFT arrays. Blending organic semiconductors with polymer materials is a promising strategy to improve the reliability of OTFT-based PUFs. Studies on the relationship between the phase-separated polycrystalline microstructure of organic semiconductor/polymer blend films and PUF characteristics reveal that the 2D mosaic microcrystalline structure of organic semiconductors in the vertically phase-separated trilayered structure enables the implementation of OTFT-based PUFs that simultaneously satisfy the requirements of being unclonable and unpredictable, with reliable cryptographic properties. The inherent multiscale randomness of the crystalline structure allows random distribution in OTFT-based PUFs even with various channel dimensions. The secret bit stream generated from the OTFT-based PUF developed in this study is reconfigurable by simply changing the gate bias, demonstrating the potential to counter evolving security attack threats.     

Ag纳米颗粒有机薄膜受激辐射增强研究

为进一步降低有机半导体材料的激射阈值,文章研究利用银纳米颗粒的表面等离子体共振效应来实现对有机半导体薄膜受激辐射的增强.将制备好的Ag纳米溶液旋涂于玻璃基底上,然后在其上再旋涂PS:Alq3:DCJTB有机薄膜发光层,构成平面波导结构.用355nm波长的YAG激光泵浦样品.实验发现:相比于无Ag纳米颗粒情况,有Ag纳米...     

Scalable,Template Driven Formation of Highly Crystalline Lead-Tin Halide Perovskite Films

Low bandgap lead-tin halide perovskites are predicted to be candidates to maximize the performance of single junction and tandem solar cells based on metal halide perovskites. In spite of the tremendous progress in lab-scale device efficiency, devices fabricated with scalable techniques fail to reach the same efficiencies, which hinder their potential industrialization. Herein, a method is proposed that involves a template of a 2D perovskite deposited with a scalable technique (blade coating), which is then converted in situ to form a highly crystalline 3D lead-tin perovskite. These templated grown films are alloyed with stoichiometric ratio and are highly oriented with the (l00) planes aligning parallel to the substrate. The low surface/volume ratio of the obtained single-crystal-like films contributes to their enhanced stability in different environments. Finally, the converted films are demonstrated as active layer for solar cells, opening up the opportunity to develop this scalable technique for the growth of highly crystalline hybrid halide perovskites for photovoltaic devices.