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.     

C8 BTBT薄膜结晶形貌及OTFT器件性能研究

以p型共轭有机小分子2,7二辛基[1]苯并噻吩并[3,2‐b]苯并噻吩(C8‐BTBT)作为底栅顶接触有机薄膜晶体管(OTFT)的有源层,采用浸渍提拉法、喷墨打印法和真空蒸镀法三种制备工艺,探究半导体薄膜载流子迁移率与结晶形貌的关系,发现不同工艺下有机小分子呈现出不同的生长行为和结晶情况,在很大程度上决定了OTFT器件性能的优劣;此外,通过XRD分析研究了退火处理对C8‐BTBT结晶的影响。结果表明,真空蒸镀制备的薄膜具有更高的结晶度、衬底覆盖率高,并且呈现出SK(Stranski‐Krastanov)模式的结晶生长特征,相应器件中陷阱密度最低,迁移率高达5.44 cm^2·V^-1·s^-1,开关比超过106;且退火处理会严重破坏C8‐BTBT薄膜的结晶。因此,控制半导体层的生长行为,提升半导体层的覆盖率和结晶度是制备高性能共轭小分子OTFT器件的有效途径。     

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.     

Enhancement of n‐Type Organic Field‐Effect Transistor Performances through Surface Doping with Aminosilanes

Dopants, i.e., electronically active impurities, are added to organic semiconductor materials to control the material's Fermi level and conductivity, to improve injection at the device contacts, or to fill trap states in the active device layers and interfaces. In contrast to bulk doping as achieved by blending or co‐deposition of dopant and semiconductor, surface doping has a lower propensity to introduce additional traps or scattering centers or to even alter the layer morphology relative to the undoped active material layers. In this study, the electrical effects of a very simple, post‐device‐fabrication surface doping process involving various amine group–containing alkoxysilanes on the performance of organic field‐effect transistors (OFETs) made from the well‐known n‐type materials PTCDI‐C8 and N2200 are researched. It is demonstrated that OFETs doped in such a way generally show enhanced characteristics (up to 10 times mobility increase and a significant reduction in threshold voltage) without any adverse effects on the devices' on/off ratio. It is also shown that the efficiency of the doping process is linked to the number of amine groups.     

“Layer‐Filter Threshold” Technique for Near‐Infrared Laser Ablation in Organic Semiconductor Device Processing

Although conventional laser ablation (CLA) method has widely been used in patterning of organic semiconductor thin films, its quality control still remains unsatisfied due to the ambiguous photochemical and photothermal processes. Based on industrial available near‐infrared laser source, herein, a novel “layer‐filter threshold” (LFT) technique is proposed, which involves the decomposition of targeted “layer‐filter” and subsequent explosive evaporation process to purge away the upper layers instead of layer‐by‐layer ablation. For photovoltaic device with structure of metal/blend/PEDOT:PSS/ITO/glass, the PEDOT:PSS layer as the “layer‐filter” is first demonstrated to be effective, and then the merged P1–P2 line and metal electrode layer are readily patterned through the “self‐aligned” effect and regulation of ablation direction, respectively. The correlation between laser fluence and explosive ablation efficacy is also investigated. Finally, photovoltaic modules based on classical P3HT:PC₆₁BM and low‐bandgap PBDT‐TFQ:PC₇₁BM systems are separately fabricated following the LFT technique. It is found that over 90% of geometric fill factor is achieved while device performances maintain in a limited change with increased number of series cells. In comparison to conventional laser ablation methods, the LFT technique does not require sophisticated instruments but reaches comparable processing accuracy, which shows promising potential in the fabrication and commercialization of organic semiconductor thin‐film devices.     

Understanding the Composition of Layer-by-Layer Deposited Active Layer at Buried Bottom Surface

Layer-by-layer (LbL) coating is becoming a widely used method to fabricate nonfullerene active layer films for organic solar cells. However, the vertical compositional distribution of the LbL-coated active layer, particularly at the buried bottom surface, is not clear yet. In common sense, it is believed that the LbL-coating yields a donor–mixture–acceptor (D–m–A) vertical distribution in the active layer, i.e., a thin polymer donor layer at the bottom surface, a thin acceptor layer at the top surface and a donor-acceptor mixture in the middle. In this study, it is shown that the LbL active layer vertically is an entire donor:acceptor mixture. A pure layer of polymer donor doesn't exist at the bottom surface. The LbL active layer delivers high performance in both conventional and inverted device structures. A thin polymer layer with different thicknesses (2, 6, 12 nm) is inserted at the bottom surface to study their effects on the device performance. Those inserted layers substantially deteriorate the device's performance. Furthermore, the assumption is further confirmed by X-ray photoelectron spectroscopy measurement on the exposed “originally buried” surface. This study sheds light on understanding the vertical compositional distribution of active layer via layer-by-layer solution processing.     

Organozinc Compounds as Effective Dielectric Modification Layers for Polymer Field‐Effect Transistors

The interface between the organic semiconductor and dielectric plays an important role in determining the device performance of organic field‐effect transistors (OFETs). Although self‐assembled monolayers (SAMs) made from organosilanes have been widely used for dielectric modification to improve the device performance of OFETs, they suffer from incontinuous and lack uniform coverage of the dielectric layer. Here, it is reported that by introduction of a solution‐processed organozinc compound as a dielectric modification layer between the dielectric and the silane SAM, improved surface morphology and reduced surface polarity can be achieved. The organozinc compound originates from the reaction between diethylzinc and the cyclohexanone solvent, which leads to formation of zinc carboxylates. Being annealed at different temperatures, organozinc compound exists in various forms in the solid films. With organozinc modification, p‐type polymer FETs show a high charge carrier mobility that is about two‐fold larger than a control device that does not contain the organozinc compound, both for devices with a positive threshold voltage and for those with a negative one. After organozinc compound modification, the threshold voltage of polymer FETs can either be altered to approach zero or remain unchanged depending on positive or negative threshold voltage they have.     

Facile and solvent-free fabrication of highly oriented ferroelectric copolymer thin films and its application in ferroelectric field effect transistors

An environmentally friendly and solvent-free method was reported for fabrication of ferroelectric copolymer P(VDF-TrFE) thin films directly from their molten mass. Friction-transferred poly(tetrafluoroethylene) (PTFE) templates were used for epitaxy during solidification process. The obtained films showed highly-oriented crystallite structure and improved degree of crystallinity. Electrical measurement indicated that these films presented good ferroelectric property with remnant polarization comparable to those solution deposited and epitaxially processed films. A ferroelectric field effect transistor (FeFET) was constructed with one oxide semiconductor as an active layer and P(VDF-TrFE) as a ferroelectric layer. The memory device showed an ON/OFF ratio as high as 10⁵ and good retention performance during the whole experimental duration. This work developed a new route for environmentally friendly fabrication of organic ferroelectric devices.     

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.     

Inkjet‐Printed Single‐Droplet Organic Transistors Based on Semiconductor Nanowires Embedded in Insulating Polymers

Fabrication of organic field‐effect transistors (OFETs) using a high‐throughput printing process has garnered tremendous interest for realizing low‐cost and large‐area flexible electronic devices. Printing of organic semiconductors for active layer of transistor is one of the most critical steps for achieving this goal. The charge carrier transport behavior in this layer, dictated by the crystalline microstructure and molecular orientations of the organic semiconductor, determines the transistor performance. Here, it is demonstrated that an inkjet‐printed single‐droplet of a semiconducting/insulating polymer blend holds substantial promise as a means for implementing direct‐write fabrication of organic transistors. Control of the solubility of the semiconducting component in a blend solution can yield an inkjet‐printed single‐droplet blend film characterized by a semiconductor nanowire network embedded in an insulating polymer matrix. The inkjet‐printed blend films having this unique structure provide effective pathways for charge carrier transport through semiconductor nanowires, as well as significantly improve the on‐off current ratio and the environmental stability of the printed transistors.     

Channel Protection Layer Effect on the Performance of Oxide TFTs

We have investigated the channel protection layer (PL) effect on the performance of an oxide thin film transistor (TFT) with a staggered top gate ZnO TFT and Al‐doped zinc tin oxide (AZTO) TFT. Deposition of an ultra‐thin PL on oxide semiconductor films enables TFTs to behave well by protecting the channel from a photo‐resist (PR) stripper which removes the depleted surface of the active layer and increases the carrier amount in the channel. In addition, adopting a PL prevents channel contamination from the organic PR and results in high mobility and small subthreshold swings. The PL process plays a critical role in the performance of oxide TFTs. When a plasma process is introduced on the surface of an active layer during the PL process, and as the plasma power is increased, the TFT characteristics degrade, resulting in lower mobility and higher threshold voltage. Therefore, it is very important to form an interface using a minimized plasma process.     

Tailoring Morphology and Structure of Inkjet‐Printed Liquid‐Crystalline Semiconductor/Insulating Polymer Blends for High‐Stability Organic Transistors

Inkjet printing of semiconducting polymers is desirable for realizing low‐cost, large‐area printed electronics. However, sequential inkjet printing methods often suffer from nozzle clogging because the solubility of semiconducting polymers in organic solvents is limited. Here, it is demonstrated that the addition of an insulating polymer to a semiconducting polymer ink greatly enhances the solubility and stability of the ink, leading to the stable ejection of ink droplets. This bicomponent blend comprising a liquid‐crystalline semiconducting copolymer, poly(didodecylquaterthiophene‐alt‐didodecylbithiazole) (PQTBTz‐C12), and an insulating commodity polymer, polystyrene, is extremely useful as a semiconducting layer in organic field‐effect transistors (OFETs), providing fine control over the phase‐separated morphology and structure of the inkjet‐printed film. Tailoring the solubility‐induced phase separation of the two components leads to a bilayer structure consisting of a polystyrene layer on the top and a highly crystalline PQTBTz‐C12 layer on the bottom. The blend film is used as the semiconducting layer in OFETs, reducing the semiconductor content to several tens of pictograms in a single device without degrading the device performance. Furthermore, OFETs based on the PQTBTz‐C12/polystyrene film exhibit much greater environmental and electrical stabilities compared to the films prepared from homo PQTBTz‐C12, mainly due to the self‐encapsulated structure of the blend film.     

Azeotropic Binary Solvent Mixtures for Preparation of Organic Single Crystals

Here, a new approach is introduced to prepare large single crystals of π‐conjugated organic molecules from solution. Utilizing the concept of azeotropism, single crystals of tri‐isopropylsilylethynyl pentacene (TIPS‐PEN) with dimensions up to millimeters are facilely self‐assembled from homogeneous solutions comprising two solvents with opposing polarities and a positive azeotropic point. At solvent compositions close to the azeotropic point, an abrupt transition of morphology from polycrystalline thin‐films to large single crystals is found. How to adjust the initial ratio of the binary solvents so that the change in solvent composition during evaporation favors the specific H‐aggregation and promotes an efficient self‐assembly of TIPS‐PEN is explained. The charge‐carrier (hole) mobilities are substantially enhanced by a factor of 4 from the morphology of thin‐films to large single crystals used as active layer in field‐effect transistors. Additionally, this approach is extended to other π–π stacked organic molecules to elucidate its broad applicability.     

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.     

The Influence of Solubilizing Chain Stereochemistry on Small Molecule Photovoltaics

Three stereochemically pure isomers and two isomeric mixtures of a solution‐processable diketopyrrolopyrrole‐containing oligothiophene ( SMDPPEH ) have been used to study the effect of 2‐ethylhexyl solubilizing group stereochemistry on the film morphology and bulk heterojunction (BHJ) solar cell characteristics of small molecule organic photovoltaics. The different SMDPPEH stereoisomer compositions exhibit nearly identical optoelectronic properties in the molecularly dissolved state, as well as in amorphous films blended with PCBM. However, for films in which SMDPPEH crystallization is induced by thermal annealing, significant differences in molecular packing between the different stereoisomer formulations are observed. These differences are borne out in photovoltaic device characteristics for which unannealed devices show very similar behavior, while after annealing the RR‐ and SS‐SMDPPEH enantiomers show blue‐shifted peak EQE relative to the SMDPPEH isomer mixtures. Unannealed devices made from the most crystalline stereoisomer, meso RS‐SMDPPEH , are not completely amorphous, and show improved photocurrent generation as a result. Unlike the other compounds, after thermal annealing the RS‐SMDPPEH devices show reduced device performance. The results reveal that the chirality of commonly used 2‐ethylhexyl solubilizing chains can have a significant effect on the morphology, absorption, and optimum processing conditions of small molecule organic thin films used as photovoltaic device active layers.     

Impact of Materials versus Geometric Parameters on the Contact Resistance in Organic Thin‐Film Transistors

The contact resistance is known to severely hamper the performance of organic thin‐film transistors, especially when dealing with large injection barriers, high mobility organic semiconductors, or short channel lengths. Here, the relative significance of how it is affected by materials‐parameters (mobility and interfacial level‐offsets) and geometric factors (bottom‐contact vs top‐contact geometries) is assessed. This is done using drift‐diffusion‐based simulations on idealized device structures aiming at a characterization of the “intrinsic” situation in the absence of traps, differences in the film morphology, or metal‐atoms diffusing into the organic semiconductor. It is found that, in contrast to common wisdom, in such a situation the top‐contact devices do not always outperform the bottom‐contact ones. In fact, the observed ratio between the contact resistances of the two device structures changes by up to two orders of magnitude depending on the assumed materials parameters. The contact resistance is also shown to be strongly dependent on the hole mobility in the organic semiconductor and influenced by the chosen point of operation of the device.     

Monitoring the Channel Formation in Organic Field‐Effect Transistors via Photoinduced Charge Transfer

Conducting channel formation in organic field‐effect transistors (OFETs) is considered to happen in the organic semiconductor layer very close to the interface with the gate dielectric. In the gradual channel approximation, the local density of accumulated charge carriers varies as a result of applied gate bias, with the majority of the charge carriers being localized in the first few semiconductor monolayers close to the dielectric interface. In this report, a new concept is employed which enables the accumulation of charge carriers in the channel by photoinduced charge transfer. An OFET employing C₆₀ as a semiconductor and divinyltetramethyldisiloxane‐bis(benzocyclobutene) as the gate dielectric is modified by a very thin noncontinuous layer of zinc‐phthalocyanine (ZnPc) at the semiconductor/dielectric interface. With this device geometry, it is possible to excite the phthalocyanine selectively and photogenerate charges directly at the semiconductor/dielectric interface via photoinduced electron transfer from ZnPc onto C₆₀. Thus the formation of a gate induced and a photoinduced channel in the same device can be correlated.     

Perfluorinated Ionomer‐Modified Hole‐Injection Layers: Ultrahigh‐Workfunction but Nonohmic Contacts

Recently it has been reported that Nafion oligomers, i.e., 2‐(2‐sulfonatotetrafluoroethoxy)‐2‐trifluoromethyltrifluoroethoxyfunctionalized oligotetrafluoroethylenes, also called perfluorinated ionomers (PFIs), can be blended into poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDT:PSSH) films to increase their workfunctions beyond 5.2 eV. These PFI‐modified films are useful for energy‐level alignment studies, and have been proposed as hole‐injection layers (HILs). It is shown here however that these HILs do not provide sufficiently fast hole transfer into adjacent polymer semiconductor layers with ionization potentials deeper than ≈5.2 eV. X‐ray and ultraviolet photoemission spectroscopies reveal that these HILs exhibit a molecularly‐thin PFI overlayer that sets up a surface dipole that provides the ultrahigh workfunction. This dipolar layer persists even when the subsequent organic semiconductor layer is deposited, as evidenced by measurements of the diode built‐in potentials. As a consequence, the PFI‐modified HILs produce a higher contact resistance, and a lower equilibrium density of holes at the semiconductor contact than might have been expected from simple thermodynamic considerations of the reduction in hole‐injection barrier. Thus the use of insulating dipolar surface layers at the charge‐injection contact to tune its workfunction to match the relevant transport level of the semiconductor is of limited utility to achieve ohmic contact in these devices.     

Controlled Crystallization of Conjugated Polymer Films from Solution and Solvent Vapor for Polymer Electronics

Over the years, solution‐processable conjugated oligomers and polymers have proven to be very promising for application in organic electronic devices. In addition to tuning the chemical structure of the materials, the role of morphology has been identified as a key parameter in determining device performance. Conjugated polymers are typically semicrystalline in nature consisting of both crystalline and amorphous domains giving rise to a wealth of superstructures. In comparison to classical non‐conjugated semicrystalline polymers, they bear the additional advantage of absorbing light. This makes UV‐vis absorption spectroscopy an excellent tool to monitor polymer aggregation and crystallization in‐situ both in solution and in films. With this feature article we point out the delicate interplay between solution processing and the obtained morphology in polythiophenes and low bandgap copolymers. Subtle changes in the preparation protocol lead to significant changes in textures and also give rise to polymorphism. Solvent vapor annealing and solution crystallization are highlighted as tools to control the nucleation and growth processes in semicrystalline polymer films. Structure‐function relationships between morphological, optical and electronic properties are demonstrated.     

Surface Directed Phase Separation of Semiconductor Ferroelectric Polymer Blends and their Use in Non‐Volatile Memories

The polymer phase separation of P(VDF‐TrFE):F8BT blends is studied in detail. Its morphology is key to the operation and performance of memory diodes. In this study, it is demonstrated that it is possible to direct the semiconducting domains of a phase‐separating mixture of P(VDF‐TrFE) and F8BT in a thin film into a highly ordered 2D lattice by means of surface directed phase separation. Numerical simulation of the surface‐controlled de‐mixing process provides insight in the ability of the substrate pattern to direct the phase separation, and hence the regularity of the domain pattern in the final dry blend layer. By optimizing the ratio of the blend components, the number of electrically active semiconductor domains is maximized. Pattern replication on a cm‐scale is achieved, and improved functional device performance is demonstrated in the form of a 10‐fold increase of the ON‐current and a sixfold increase in current modulation. This approach therefore provides a simple and scalable means to higher density integration, the ultimate target being a single semiconducting domain per memory cell.