High-performance Organic Thin-film Transistors Research Articles

High-Performance Pentacene Organic Thin-Film Transistor Based on Room-Temperature- Processed Hf0.13La0.87O as Gate Dielectric

High-performance pentace organic thin-film transistors (OTFTs) with room-temperature-processed Hf0.13 La0.87O as gate dielectric and Pd as gate electrode have been fabricated on both rigid Si and flexible polymide (PI) substrates. The OTFT on PI (Si) can achieve a high carrier mobility of 10.3 cm2V−1s−1 (12.5 cm2V−1s−1), and has a negligible hysteresis of −0.17 V (−0.08 V), small sub-threshold swing of 0.12 V/dec (0.11 V/dec) and low threshold voltage of −0.65 V (−0.86 V). After the devices have been exposed to the air for 30 days without encapsulation, their carrier mobilities degrade by less than 10%, indicating that the devices have good stability in the air.

Nanocluster-Based Ultralow-Temperature Driven Oxide Gate Dielectrics for High-Performance Organic Electronic Devices.

The development of novel dielectric materials with reliable dielectric properties and low-temperature processibility is crucial to manufacturing flexible and high-performance organic thin-film transistors (OTFTs) for next-generation roll-to-roll organic electronics. Here, we investigate the solution-based fabrication of high-k aluminum oxide (Al2O3) thin films for high-performance OTFTs. Nanocluster-based Al2O3 films fabricated by highly energetic photochemical activation, which allows low-temperature processing, are compared to the conventional nitrate-based Al2O3 films. A wide array of spectroscopic and surface analyses show that ultralow-temperature photochemical activation (<60 °C) induces the decomposition of chemical impurities and causes the densification of the metal-oxide film, resulting in a highly dense high-k Al2O3 dielectric layer from Al-13 nanocluster-based solutions. The fabricated nanocluster-based Al2O3 films exhibit a low leakage current density (<10−7 A/cm2) at 2 MV/cm and high dielectric breakdown strength (>6 MV/cm). Using this dielectric layer, precisely aligned microrod-shaped 2,7-dioctyl[1]benzothieno [3,2-b][1] benzothiophene (C8-BTBT) single-crystal OTFTs were fabricated via solvent vapor annealing and photochemical patterning of the sacrificial layer.

Direct fabrication of high-resolution and high-performance flexible electronics via surface-activation-localized electroless plating

Patterning high-resolution multi-metal layers without using subtractive lithography poses a substantial challenge but is indispensable for the development of the modern electronics industry, especially flexible electronics. Herein, the general and feasible additive manufacturing approach is reported to selectively deposit high-resolution multi-metal patterns via surface-activation-localized electroless plating (SALEP) and enable the fabrication of 3-dimensional (3D) interconnections and high-performance organic thin-film transistor (OTFT) arrays for flexible electronics. The SALEP approach comprises the direct layer-by-layer deposition of multi-metal patterns interconnected by via holes, which are defined by the selective adsorption of palladium catalysts and a metallization process. The localized adsorption of the catalyst is guided by the difference in surface wettability and adsorbability caused by vacuum ultraviolet (VUV)-induced photochemical modification. The low-temperature and 3D approach enables miniaturization of flexible electrical circuits down to 1 µm in width; it also enables integration of an OTFT array on a flexible substrate. The fabricated OTFT array with multi-metal Cu/Ni/Au as contact electrodes exhibits a high hole mobility exceeding 10 cm2 V−1 s−1, demonstrating the adaptability of the SALEP approach for the low-cost, high-efficiency, and scalable fabrication of high-performance flexible electronic devices.

Ultranarrow Bandgap Naphthalenediimide-Dialkylbifuran-Based Copolymers with High-Performance Organic Thin-Film Transistors and All-Polymer Solar Cells.

A new polymer acceptor poly{(N,N'-bis(2-ethylhexyl)-1,4,5,8-naphthalenedicarboximide-2,6-diyl)-alt-5,5-(3,3'-didodecyl-2,2'-bifuran)} (NDI-BFR) made from naphthalenediimide (NDI) and furan-derived head-to-head-linked 3,3'-dialkyl-2,2'-bifuran (BFR) units is reported in this study. Compared to the benchmark polymer poly(naphthalenediimide-alt-bithiophene) (N2200), NDI-BFR exhibits a larger bathochromic shift of absorption maxima (842 nm) with a much higher absorption coefficient (7.2 × 104 m-1 cm-1 ), leading to an ultranarrow optical bandgap of 1.26 eV. Such properties ensure good harvesting of solar light from visible to the near-infrared region in solar cells. Density functional theory calculation reveals that the polymer acceptor NDI-BFR possesses a higher degree of backbone planarity versus the polymer N2200. The polymer NDI-BFR exhibits a decent electron mobility of 0.45 cm2 V-1 s-1 in organic thin-film transistors (OTFTs), and NDI-BFR-based all-polymer solar cells (all-PSCs) achieve a power conversion efficiency (PCE) of 4.39% with a very small energy loss of 0.45 eV by using the environmentally friendly solvent 1,2,4-trimethylbenzene. These results demonstrate that incorporating head-to-head-linked BFR units in the polymer backbone can lead to increased planarity of the polymer backbone, reduced optical bandgap, and improved light absorbing. The study offers useful guidelines for constructing n-type polymers with narrow optical bandgaps.

Wettability Control of Interfaces for High-Performance Organic Thin-Film Transistors by Soluble Insulating Polymer Films.

Organic small-molecule semiconductors have higher carrier mobility compared to polymer semiconductors, while the actual performances of these materials are susceptible to morphological defects and misalignment of crystalline grains. Here, a new strategy is explored to control the crystallization and morphologies of a solution-processed organic small-molecule semiconductor 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) using soluble polymer films to control the wettability of substrates. Different from the traditional surface modification method, the polymer layer as a modification layer is soluble in the semiconductor solution during the fabrication of organic thin-film transistors (OTFTs). The dissolved polymer alters the state of the semiconductor solution, which in turn, changes the crystallographic morphologies of the semiconductor films. By controlling the solubility and thickness of the polymer modification layers, it is possible to regulate the grain boundary and domain size of C8-BTBT films, which determine the performances of OTFTs. The bottom-gate transistors modified by a thick PS layer exhibit a mobility of >7 cm2/V·s and an on/off ratio of >107. It is expected that this new modification method will be applicable to high-performance OTFTs based on other small molecular semiconductors and dielectrics.

Interface Engineering With Polystyrene for High-Performance, Low-Voltage Driven Organic Thin Film Transistor

We report a solution-processed, high-performance organic thin-film transistor (OTFT), using polystyrene (PS) as interlayer with the semiconducting material P2TDPP2TFT4 as an active layer. We achieved a significant improvement employing the PS as an interlayer between the P2TDPP2TFT4 and ${{{\text {AlO}}}}_{X}$ gate insulator. The filed-effect mobility ( $\mu _{{{\text {FE}}}}$ ) and ON/OFF current ratio ${(}{I}_{{ \mathrm{\scriptscriptstyle ON}}}/{I}_{{ \mathrm{\scriptscriptstyle OFF}}}{)}$ reached to $0.82\,\,{{{\text {cm}}}}^{{{{2}}}}{\cdot } {{\text {V}}}^{{{-{1}}}}{\cdot } {{\text {s}}}^{{{-{1}}}}$ and ~105, respectively, which is higher than the devices fabricated with commonly used self-assembled monolayer (SAM) octadecyltrimethoxysilane (OTS) modified substrate under similar experimental conditions. Further analysis of the modified gate insulator utilizing atomic force microscopy, X-ray diffraction, and contact angle measurement revealed that smoother surface and lower surface energy were achieved by employing PS interlayer, which leads to more compatible surface energy with the semiconductor and interfacial trap passivation. Passivation of interfacial traps and lower surface energy using PS interlayer leads to the highly stable device performance, suggesting its application as a new interlayer with ${{{\text {AlO}}}}_{X}$ gate insulator to improve device performance.

Polymer mask-weakening grain-boundary effect: towards high-performance organic thin-film transistors with mobility closing to 20 cm2 V−1 s−1

Polystyrene-based masks are fabricated to produce top-contact high-resolution (5 μm) electrodes. With this mask, the mobility of DPA-based thin-film transistors could reach 19.22 cm2 V−1 s−1, which is a new breakthrough for DPA thin-film transistors.

Narrow bandgap difluorobenzochalcogenadiazole-based polymers for high-performance organic thin-film transistors and polymer solar cells

A series of difluorobenzochalcogenadiazole-bithiophene copolymers are developed for high-performance organic semiconductors.

Architecting layered molecular packing in substituted benzobisbenzothiophene (BBBT) semiconductor crystals

The construction of layered molecular packing structures in a non-layered crystalline material, benzobisbenzothiophene (BBBT), was achieved by employing long-alkyl and phenyl substituents, leading to high-performance organic thin-film transistors.

A comparison of computational equations for understanding the effect of adhesion energy on mobility of DNTT thin-film transistors

In organic thin-film transistors (OTFTs), adhesion energy plays an important role in the morphology of the vacuum-deposited organic semiconductor film and hence affects the field-effect mobility. Currently, two equations have been reported to calculate the adhesion energy between semiconductor and dielectric. However, the differences of the two equations remain unexplored. Here, we reflect the differences by simulation, experiment and theoretical derivation methods. Results show that the change of mobility is consistent with the change of adhesion energy calculated by Eq. (1), which is ascribed to the good availability of Eq. (1) for both polar and non-polar dielectrics. Our results provide an exact guideline for calculation of adhesion energy and help the selection of dielectrics to obtain high-performance OTFTs.

Fused Bithiophene Imide Oligomer and Diketopyrrolopyrrole Copolymers for n-Type Thin-Film Transistors.

Diketopyrrolopyrrole (DPP)-based copolymers have received considerable attention as promising semiconducting materials for high-performance organic thin-film transistors (OTFTs). However, these polymers typically exhibit p-type or ambipolar charge-transporting characteristics in OTFTs due to their high-lying highest occupied molecular orbital (HOMO) energy levels. In this work, a new series of DPP-based n-type polymers have been developed by incorporating fused bithiophene imide oligomers (BTIn) into DPP polymers. The resulting copolymers BTIn-DPP show narrow band gaps as low as 1.27 eV and gradually down-shifted frontier molecular orbital energy levels upon the increment of imide group number. Benefiting from the coplanar backbone conformation, well-delocalized π-system, and favorable polymer chain packing, the optimal polymer in the series shows promising n-type charge transport with an electron mobility up to 0.48 cm2 V-1 s-1 in OTFTs, which is among the highest values for the DPP-based n-type polymers reported to date. The results demonstrate that incorporating fused bithiophene imide oligomers into polymers can serve as a promising strategy for constructing high-performance n-type polymeric semiconductors.

Regioregular-block-Regiorandom Poly(3-hexylthiophene) Copolymers for Mechanically Robust and High-Performance Thin-Film Transistors

In this work, we develop mechanically robust and high-performance organic thin-film transistors (OTFTs) based on poly(3-hexylthiophene) (P3HT) regioblock copolymers (block-P3HTs). These block-P3HTs...

Spontaneous Generation of a Molecular Thin Hydrophobic Skin Layer on a Sub-20 nm, High-k Polymer Dielectric for Extremely Stable Organic Thin-Film Transistor Operation.

Polymer dielectric materials with hydroxyl functionalities such as poly(4-vinylphenol) and poly(vinyl alcohol) have been utilized widely in organic thin-film transistors (OTFTs) because of their excellent insulating performance gained by hydroxyl-mediated cross-linking. However, the polar hydroxyl functionality also deleteriously affects the performance of OTFTs and significantly impairs the device stability. In this study, a sub-20 nm, high-k copolymer dielectric with hydroxyl functionality, poly(2-hydroxyethyl acrylate-co-di(ethylene glycol) divinyl ether), was synthesized in the vapor phase via initiated chemical vapor deposition. The inherently dry environment offered by the vapor-phase polymer synthesis prompted the snuggling of polar hydroxyl functionalities into the bulk polymer film to form a molecular thin hydrophobic skin layer at its surface, verified by near-edge X-ray absorption fine structure analysis. The chemical composition of the copolymer dielectric was optimized systematically to achieve high dielectric constant (k ≈ 6.2) as well as extremely low leakage current densities (less than 3 × 10-8 A/cm2 in the range of ±2 MV/cm) even with sub-20 nm thickness, leading to one of the highest capacitance (higher than 300 nF/cm2) achieved by a single polymer dielectric to date. Exploiting the structural advantage of the cross-linked high-k polymer dielectric, high-performance OTFTs were obtained. Notably, the spontaneously formed molecular thin, hydrophobic skin layer in the copolymer film substantially suppressed the hysteresis in the transistor operation. The trap analysis also suggested the formation of bulk trap with a high energy barrier and sufficiently low trap densities at the semiconductor/dielectric interface, owing to the surface skin layer. Furthermore, the OTFTs with the -OH-containing copolymer dielectric showed an unprecedentedly excellent operational stability. No apparent OTFT degradation was observed up to 50 000 s of high constant voltage stress (corresponding to the applied electric field of 1.4 MV/cm) because of the markedly suppressed interfacial trap density by the hydrophobic skin layer, together with the current compensation by the bulk hydroxyl functionalities. We believe that the surface modification-free, one-step polymer dielectric synthetic strategy will provide a new insight into the design of polymer dielectric materials for high-performance, low-power soft electronic devices with high operational stability.

Self-assembly crystal microribbons with nucleation additive for high-performance organic thin film transistors

We demonstrate fabrication of 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS pentacene) crystal microribbon based organic thin film transistors (OTFTs) with a solvent exchange method and the addition of a nucleation agent. TIPS pentacene crystals were formed via self-assembly as a result of solubility difference between the double solvents. At the same time, 4-hexylbenzoic acid (HBA) was added as a nucleation agent and formed an interfacial layer on the silicon dioxide gate dielectrics, which dispersed the aggregated crystals and enhanced its morphology uniformity. TIPS pentacene crystal microribbon based OTFTs with HBA nucleation additive showed a hole mobility of up to 0.36 cm2 V−1 s−1, and particularly, a 9-fold enhancement in average mobilities, as compared to pristine crystal based OTFTs. The remarkable enhancement in device performance can be attributed to the improved crystallinity, reduced defects and charge trap centers located at the grain boundaries, and controlled crystallization and dispersion effect due to the addition of the HBA nucleation agent.

Head-to-Head Linked Dialkylbifuran-Based Polymer Semiconductors for High-Performance Organic Thin-Film Transistors with Tunable Charge Carrier Polarity

A planar backbone conformation is essential for enabling polymer semiconductors with high charge carrier mobility in organic thin-film transistors. Benefiting from the smaller van der Waals radius ...

Fabrication of Two-Dimensional Crystalline Organic Films by Tilted Spin Coating for High-Performance Organic Field-Effect Transistors.

We developed a facile method for fabricating large-area, two-dimensional (2D), organic, highly crystalline films and extended it to organic thin-film transistor arrays. Tilted spinning provided oriented flow at the three-phase contact line, and a 2D crystalline film that consisted of layer-by-layer stacked 2,7-diocty[1]benzothieno[3,2- b]benzothiophene (C8-BTBT) was obtained facilely for organic thin-film transistors (OTFTs). The extracted field-effect mobility is 4.6 cm2 V-1 s-1, but with nonideal features. By applying this method to microdroplet arrays, an oriented crystal was fabricated, and the channel region for OTFTs was covered by adjusting the spinning speed. By tuning the tilt angle (θ) of the revolving substrate, we fabricated high-performance OTFT arrays with average and maximum mobilities of 7.5 and 10.1 cm2 V-1 s-1, respectively, which exhibited high reliability factors of over 90% and were close to that of ideal transistors. These results suggest that high-quality crystalline films can be obtained via a facile tilted-spinning method.

Highly conductive, transparent and metal-free electrodes with a PEDOT:PSS/SWNT bilayer for high-performance organic thin film transistors

Abstract Conductive organic materials including polymers, small molecules, and carbon nanotubes (CNTs) are a promising alternative to inorganic materials in electronic devices. Conventionally, organic electrodes employing CNTs are designed using functionalization of their surfaces or formation of nanocomposites with a conductive polymer. However, phase separation limits the concentration of CNTs in a polymer matrix, hindering the formation of highly dense CNT networks and leading to poor electrical conductivity. In this paper, we introduce bilayer electrodes comprising poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) and single-walled CNTs (SWNTs) chemically modified by HNO3 treatment. Impressive conductivities of 2432 and 2438 S cm−1 are found for the SWNT/PEDOT:PSS (S/P) and PEDOT:PSS/SWNT (P/S) electrodes, respectively. Further, an increase in the work function of the electrodes after HNO3 treatment lowers the hole injection barrier, which facilitates hole injection from pentacene. The smooth surface of PEDOT:PSS also contributes to growth of large pentacene grains; consequently, the field-effect mobility of pentacene-based thin film transistors is 1.88 cm2 V−1 s−1 when the P/S electrode is employed. The metal-free electrodes also exhibit a high optical transparency of 88.7%, which suggests that they have great potential for applications in optoelectronics.

Polyimide-based gate dielectrics for high-performance organic thin film transistors

In this work, polyimide-based novel polymer dielectric materials, containing a cross-linkable olefin group and a long alkyl chain with biphenyl, were designed and synthesized by a mild chemical synthesis method to avoid thermal imidization so that they can be widely utilized.

A facile post-peeling modification approach of elastic dielectrics for high-performance conformal organic thin-film transistors

A facile post-peeling modification approach is developed to form an ultrasmooth monolayer on elastic dielectrics for constructing high-performance conformal organic thin-film transistors.

Revealing the mechanism of contrasting charge transport properties for phenyl and thienyl substituent organic semiconductors.

The aromatic substituents such as phenyl and thienyl have a direct impact on the structure-property relationship of conjugated semiconducting molecules and thus play a significant role in determining the performance of organic thin film transistors (OTFTs). To design a molecule with good charge transport properties, it is essential to understand the charge transfer process. Herein, through the study of two groups of classical OTFT materials with different substituents, we demonstrate the fundamental reasons for the contrasting carrier mobilities between the materials in each group by means of DFT calculations. The results from our theoretical analysis on the two groups of molecules provide very good estimates of their charge transfer properties and the numerical trend from our calculation is consistent with that from the corresponding experimental results. We reveal in detail the impacts of the subtle geometric differences caused by different substituents from two aspects including (i) the significant influence of steric hindrance on reorganization energy and (ii) the overlap of the adjacent molecular orbitals (MOs) on electron coupling. Overall, our systematic investigation into the charge transfer mechanism and geometry effects allows us to employ a reliable theoretical methodology for the prediction of the material performance, which is crucial for the design of high performance OTFT materials.