Air-flow navigated crystal growth for TIPS pentacene-based organic thin-film transistors

6,13-Bis(triisopropylsilylethynyl)pentacene (TIPS pentacene) is a promising active channel material of organic thin-film transistors (OTFTs) due to its solubility, stability, and high mobility. However, the growth of TIPS pentacene crystals is intrinsically anisotropic and thus leads to significant variation in the performance of OTFTs. In this paper, air flow is utilized to effectively improve the TIPS pentacene crystal orientation and enhance performance consistency in OTFTs, and the resulted films are examined with optical microscopy, X-ray diffraction, and thin-film transistor measurements. Under air-flow navigation (AFN), TIPS pentacene drop-cast from toluene solution has been observed to form thin films with improved crystal orientation and increased areal coverage on substrates, which subsequently lead to a fourfold increase of average hole mobility and one order of magnitude enhancement in performance consistency defined by the ratio of average mobility to the standard deviation of the field-effect mobilities.     

Tuning electric bistability in pentacene film-based transistor embedding aluminum nanoparticles

Hybrid films of pentacene and aluminum nanoparticles were prepared by depositing pentacene on a SiO₂ surface decorated with aluminum nanoparticles and used as the active channel materials in a thin film transistor. Surface pre-treatment of the aluminum nanoparticles with oxygen plasma and/or organophosphonic acids render the particles surface with different coatings and work functions, which affect the charge trapping/storing ability of the nanoparticles. This in turn results in an electric bistability of the pentacene film-based transistor/memory devices. Correlations of memory window, switching response, and memory retention characteristics with the aluminum nanoparticle surface treatment are provided.     

Controlled Topology of Block Copolymer Gate Insulators by Selective Etching of Cylindrical Microdomains in Pentacene Organic Thin Film Transistors

We investigate the effect of surface topology of a block copolymer/neutral surface/SiO₂ trilayered gate insulator on the properties of pentacene organic thin film transistor (OTFT) by the controlled etching of self assembled poly(styrene‐b‐methyl methacrylate) (PS‐b‐PMMA) block copolymer. The rms roughness of the uppermost block copolymer film directly in contact with pentacenes was systematically controlled from 0.27 nm to approximately 12.5 nm by the selective etching of cylindrical PMMA microdomains hexagonally packed and aligned perpendicular to SiO₂ layer with 20 and 38 nm of diameter and periodicity, respectively. Both mobility and On/Off ratio were significantly reduced by more than 3 orders of magnitudes with the film roughness in OTFTs having 60 nm thick pentacene active layer. The poor device performance observed with the etched thin film of block copolymer dielectric is attributed to a defective pentacene active layer and the mixed crystalline structure consisting of thin film and bulk phase arising from the massive nucleation of pentacene preferentially at the edge of each cylindrical etched hole.     

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.     

Thickness‐Dependent Structural Evolutions and Growth Models in Relation to Carrier Transport Properties in Polycrystalline Pentacene Thin Films

Thickness‐dependent crystal structure, surface morphology, surface energy, and molecular structure and microstructure of a series of polycrystalline pentacene films with different film thickness ranging from several monolayers to the several hundred nanometers have been investigated using X‐ray diffraction (XRD), atomic force microscopy (AFM), contact angle meter, and Raman spectroscopy. XRD studies indicate that thin film polymorphs transformation behaviours are from the orthorhombic phase to the thin‐film phase and then to the triclinic bulk phase as measured by the increased tilt angle (θ_tilt) of the pentacene molecule from the c‐axis toward the a‐axis. We propose a growth model that rationalizes the θ_tilt increased along with increasing film thickness in terms of grain size and surface energy varying with film growth using AFM combined with contact angle measurements. The vibrational characterizations of pentacene molecules in different thickness films were investigated by Raman spectroscopy compared to density functional theory calculations of an isolated molecule. In combination with XRD and AFM the method enables us to distinguish the molecular microstructures in different thin film polymorphs. We proposed a methodology to probe the microscopic parameters determining the carrier transport properties based on Davydov splitting and the characteristics of aromatic C–C stretching modes in Raman spectra. When compared to the triclinic bulk phase at a high thickness, we suggest that the first few monolayer structures located at the dielectric surface could have inferior carrier transport properties due to weak intermolecular interactions, large molecular relaxation energy, and more grain boundaries.     

Microstructure transformations induced by modified-layers on pentacene polymorphic films and their effect on performance of organic thin-film transistor

Phenyltrimethoxysilane was used to modify SiO₂ insulator and significantly enhanced the pentacene based organic thin-film transistors (OTFTs). The crystal structure, surface morphology, molecular structure and microstructure of pentacene polymorphic films with and without the modifications were investigated using X-ray diffraction (XRD), atomic force microscopy (AFM) and contact angle meter. XRD studies reveal a decreased tilt angle (θ_T) of pentacene molecules from c-axis toward a-axis, indicating that polymorphs transformation from the “triclinic bulk” phase to the “thin film” phase and orthorhombic phase occurs. AFM images show that the surface roughness of gate insulators has no influence on performance of the pentacene based OTFT. These results provide strong evidence that the performance improvement of OTFT after PhTMS modification of SiO₂ insulator surface is related to the microstructure transformation of the semiconductor. It suggests that the modified-layer may alter the molecular geometry and further induce structural phase transitions in the pentacene films for the performance improvement.     

Non‐volatile Ferroelectric Poly(vinylidene fluoride‐co‐trifluoroethylene) Memory Based on a Single‐Crystalline Tri‐isopropylsilylethynyl Pentacene Field‐Effect Transistor

A new type of nonvolatile ferroelectric poly(vinylidene fluoride‐co‐trifluoroethylene) (P(VDF‐TrFE)) memory based on an organic thin‐film transistor (OTFT) with a single crystal of tri‐isopropylsilylethynyl pentacene (TIPS‐PEN) as the active layer is developed. A bottom‐gate OTFT is fabricated with a thin P(VDF‐TrFE) film gate insulator on which a one‐dimensional ribbon‐type TIPS‐PEN single crystal, grown via a solvent‐exchange method, is positioned between the Au source and drain electrodes. Post‐thermal treatment optimizes the interface between the flat, single‐crystalline ab plane of TIPS‐PEN and the polycrystalline P(VDF‐TrFE) surface with characteristic needle‐like crystalline lamellae. As a consequence, the memory device exhibits a substantially stable source–drain current modulation with an ON/OFF ratio hysteresis greater than 10³, which is superior to a ferroelectric P(VDF‐TrFE) OTFT that has a vacuum‐evaporated pentacene layer. Data retention longer than 5 × 10⁴ s is additionally achieved in ambient conditions by incorporating an interlayer between the gate electrode and P(VDF‐TrFE) thin film. The device is environmentally stable for more than 40 days without additional passivation. The deposition of a seed solution of TIPS‐PEN on the chemically micropatterned surface allows fabrication arrays of TIPS‐PEN single crystals that can be potentially useful for integrated arrays of ferroelectric polymeric TFT memory.     

Ultrathin,Organic, Semiconductor/Polymer Blends by Scanning Corona‐Discharge Coating for High‐Performance Organic Thin‐Film Transistors

A new thin‐film coating process, scanning corona‐discharge coating (SCDC), to fabricate ultrathin tri‐isopropylsilylethynyl pentacene (TIPS‐PEN)/amorphous‐polymer blend layers suitable for high‐performance, bottom‐gate, organic thin‐film transistors (OTFTs) is described. The method is based on utilizing the electrodynamic flow of gas molecules that are corona‐discharged at a sharp metallic tip under a high voltage and subsequently directed towards a bottom electrode. With the static movement of the bottom electrode, on which a blend solution of TIPS‐PEN and an amorphous polymer is deposited, SCDC provides an efficient route to produce uniform blend films with thicknesses of less than one hundred nanometers, in which the TIPS‐PEN and the amorphous polymer are vertically phase‐separated into a bilayered structure with a single‐crystalline nature of the TIPS‐PEN. A bottom‐gate field‐effect transistor with a blend layer of TIPS‐PEN/polystyrene (PS) (90/10 wt%) operated at ambient conditions, for example, indeed exhibits a highly reliable device performance with a field‐effect mobility of approximately 0.23 cm² V^?1 s^?1: two orders of magnitude greater than that of a spin‐coated blend film. SCDC also turns out to be applicable to other amorphous polymers, such as poly(α‐methyl styrene) and poly(methyl methacrylate) and, readily combined with the conventional transfer‐printing technique, gives rise to micropatterned arrays of TIPS‐PEN/polymer films.     

Understanding Lattice Strain‐Controlled Charge Transport in Organic Semiconductors: A Computational Study

The softness and anisotropy of organic semiconductors offer unique properties. Recently, solution‐sheared thin‐films of 6,13‐bis(triisopropylsilylethynyl) pentacene (TIPS‐P) with nonequilibrium single‐crystal domains have shown much higher charge mobilities than unstrained ones (Nature 2011 , 480, 504). However, to achieve efficient and targeted modulation of charge transport in organic semiconductors, a detailed microscopic understanding of the structure–property relationship is needed. In this work, motivated by the experimental studies, the relationship between lattice strain, molecular packing, and charge carrier mobility of TIPS‐P crystals is elucidated. By employing a multiscale theoretical approach combining nonequilibrium molecular dynamics, first‐principles calculations, and kinetic Monte Carlo simulations using charge‐transfer rates based on the tunneling enabled hopping model, charge‐transport properties of TIPS‐P under various lattice strains are investigated. Shear‐strained TIPS‐P indeed exhibits one‐dimensional charge transport, which agrees with the experiments. Furthermore, either shear or tensile strain lead to mobility enhancement, but with strong charge‐transport anisotropy. In addition, a combination of shear and tensile strains could not only enhance mobility, but also decrease anisotropy. By combining the shear and tensile strains, almost isotropic charge transport could be realized in TIPS‐P crystal with the hole mobility improved by at least one order of magnitude. This approach enables a deep understanding of the effect of lattice strain on charge carrier transport properties in organic semiconductors.     

Memory effects in hybrid silicon-metallic nanoparticle-organic thin film structures

We report on the electrical behaviour of metal–insulator–semiconductor (MIS) structures fabricated on silicon substrates and using organic thin films as the dielectric layers. These insulating thin films were produced by different methods, including spin-coating (polymethylmethacrylate), thermal evaporation (pentacene) and Langmuir–Blodgett deposition (cadmium arachidate). Gold nanoparticles, deposited at room temperature by chemical self-assembly, were used as charge storage elements. In all cases, the MIS devices containing the nanoparticles exhibited hysteresis in their capacitance versus voltage characteristics, with a memory window depending on the range of the voltage sweep. This hysteresis was attributed to the charging and discharging of the nanoparticles from the gate electrode. A maximum memory window of 2.5 V was achieved by scanning the applied voltage of an Al/pentacene/Au nanoparticle/SiO₂/p-Si structure between 9 and −9 V.     

Boosting Direct X‐Ray Detection in Organic Thin Films by Small Molecules Tailoring

The attention focused on the application of organic electronics for the detection of ionizing radiation is rapidly growing among the international scientific community, due to the great potential of organic technology to enable large‐area conformable sensor panels. However, high‐energy photon absorption is challenging as organic materials are constituted of atoms with low atomic numbers. Here it is reported how, by synthesizing new solution‐processable organic molecules derived from 6,13‐bis(triisopropylsilylethynyl)pentacene (TIPS‐pentacene) and 2,8‐difluoro‐5,11‐bis(triethylsilylethynyl)anthradithiophene, with Ge‐substitution in place of the Si atoms to increase the material atomic number, it is possible to boost the X‐ray detection performance of organic thin films on flexible plastic substrates. Bis(triisopropylgermylethynyl)‐pentacene based flexible organic thin film transistors show high electrical performance with higher mobility (0.4 cm² V^?1 s^?1) and enhanced X‐ray sensitivity, up to 9.0 × 10⁵ µC Gy^?1 cm^?3, with respect to TIPS‐pentacene‐based detectors. Moreover, similar results are obtained for 5,11‐bis(triethylgermylethynyl)anthradithiophene devices, confirming that the proposed strategy, that is, increasing the atomic number of organic molecules by chemical tailoring to improve X‐ray sensitivity, can be generalized to organic thin film detectors, combining high X‐ray absorption, mechanical flexibility, and large‐area processing.     

Tunable Crystal Nanostructures of Pentacene Thin Films on Gate Dielectrics Possessing Surface‐Order Control

To enhance the electrical performance of pentacene‐based field‐effect transistors (FETs) by tuning the surface‐induced ordering of pentacene crystals, we controlled the physical interactions at the semiconductor/gate dielectric (SiO₂) interface by inserting a hydrophobic self‐assembled monolayer (SAM, CH₃‐terminal) of organoalkyl‐silanes with an alkyl chain length of C8, C12, C16, or C18, as a complementary interlayer. We found that, depending on the physical structure of the dielectric surfaces, which was found to depend on the alkyl chain length of the SAM (ordered for C18 and disordered for C8), the pentacene nano‐layers in contact with the SAM could adopt two competing crystalline phases—a “thin‐film phase” and “bulk phase” – which affected the π‐conjugated nanostructures in the ultrathin and subsequently thick films. The field‐effect mobilities of the FET devices varied by more than a factor of 3 depending on the alkyl chain length of the SAM, reaching values as high as 0.6 cm² V^?1 s^?1 for the disordered SAM‐treated SiO₂ gate‐dielectric. This remarkable change in device performance can be explained by the production of well π‐conjugated and large crystal grains in the pentacene nanolayers formed on a disordered SAM surface. The enhanced electrical properties observed for systems with disordered SAMs can be attributed to the surfaces of these SAMs having fewer nucleation sites and a higher lateral diffusion rate of the first seeding pentacene molecules on the dielectric surfaces, due to the disordered and more mobile surface state of the short alkyl SAM.     

An Orientation‐Controlled Pentacene Film Aligned by Photoaligned Polyimide for Organic Thin‐Film Transistor Applications

We have demonstrated that the photoalignment method could be used to control the structural anisotropy of pentacene films, an active semiconducting layer, in thin‐film transistors (TFTs) with conspicuously anisotropic electrical characteristics. The photoaligned pentacene films were characterized with respect to structure and morphology using X‐ray diffraction and atomic force microscopy. Compared to the pentacene films that are not controlled, a maximal 25‐times increase in field‐effect mobility (up to 0.75 cm V^–1 s^–1) has been achieved in the photoaligned pentacene‐based TFTs by aligning pentacene orientation parallel to the direction of current flow with the help of a photoaligned polyimide layer. Mobility anisotropic ratio in the range of 2.7–8.3 for the current flow parallel and perpendicular to the alignment of the photoaligned pentacene films have been observed for photoaligned pentacene‐based TFTs.     

High-mobility pentacene phototransistor with nanostructured SiO2 gate dielectric synthesized by sol-gel method

We have fabricated a pentacene based phototransistor by employing a modified nanostructured SiO₂ gate dielectric. The photosensing properties of the pentacene thin film transistor fabricated on n-Si substrate with nanostructured SiO₂ as gate dielectric have been investigated. The photocurrent of the transistor increases with an increase in illumination intensity. This suggests that the pentacene thin film transistor behaves as a phototransistor with p-channel characteristics. The photosensitivity and responsivity values of the transistor are 630.4 and 0.10 A/W, respectively at the off state under AM 1.5 light illumination. The field effect mobility of the pentacene phototransistor was also found to be 2.96 cm²/Vs. The nanostructured surface of the gate possibly is the cause of the high-mobility value of the phototransistor due to light scattering from the increased surface area.     

Mechanical Restoration of Damaged Polymer Films by “Repair‐and‐Go”

A microencapsulation and nanoparticle deposition technique, termed “repair‐and‐go,” is employed for inducing mechanical restoration of damaged polymer films. In “repair‐and‐go,” polymer‐stabilized emulsion droplets, containing surface‐functionalized SiO₂ nanoparticles, traverse a substrate and deposit their nanoparticle contents selectively into the damaged regions. Surface‐oxidized poly(dimethylsiloxane) is employed as the substrate, and dynamic mechanical analysis reveals the enhanced mechanical properties of the film following nanoparticle deposition. Healing efficiency is optimal when using thinner test substrates, repeated deposition cycles, and functional SiO₂ nanoparticles that afford access to postdeposition curing.     

CoFe2O4 and CoFe2O4‐SiO2 Nanoparticle Thin Films with Perpendicular Magnetic Anisotropy for Magnetic and Magneto‐Optical Applications

This paper presents an efficient colloidal approach to process CoFe₂O₄ and SiO₂ nanoparticles into thin films for magnetic and magneto‐optical applications. Thin films of varying CoFe₂O₄‐to‐SiO₂ ratios (from 0 to 90 wt%) are obtained by sequential spin coating‐calcination cycles from the corresponding nanoparticle dispersions. Scanning electron microscopy analysis reveals a crack free and nanoparticulate structure of the sintered films with thicknesses of 480–1200 nm. Results from the optical characterization indicate a direct band gap ranging from 2.6 to 3.9 eV depending on the SiO₂ content. Similarly, the refractive indices and absorption coefficients are tunable upon SiO₂ incorporation. In‐plane measurements of the magnetic properties of the CoFe₂O₄ films reveal a superparamagnetic behavior with both Co²⁺ and Fe³⁺ contributing to the magnetism. Polar Kerr measurements show the presence of a spontaneous magnetization in the CoFe₂O₄ and CoFe₂O₄‐SiO₂ (with SiO₂ < 50 wt%) films, pointing to magnetic anisotropy perpendicular to the substrate. The origin of this effect is attributed to the constrained sintering conditions of the nano­particulate film and the negative magnetostriction of CoFe₂O₄.     

Printable Ferroelectric PVDF/PMMA Blend Films with Ultralow Roughness for Low Voltage Non‐Volatile Polymer Memory

Here, a facile route to fabricate thin ferroelectric poly(vinylidene fluoride) (PVDF)/poly(methylmethacrylate) (PMMA) blend films with very low surface roughness based on spin‐coating and subsequent melt‐quenching is described. Amorphous PMMA in a blend film effectively retards the rapid crystallization of PVDF upon quenching, giving rise to a thin and flat ferroelectric film with nanometer scale β‐type PVDF crystals. The still, flat interfaces of the blend film with metal electrode and/or an organic semi‐conducting channel layer enable fabrication of a highly reliable ferroelectric capacitor and transistor memory unit operating at voltages as low as 15 V. For instance, with a TIPS‐pentacene single crystal as an active semi‐conducting layer, a flexible ferroelectric field effect transistor shows a clockwise I–V hysteresis with a drain current bistability of 10³ and data retention time of more than 15 h at ±15 V gate voltage. Furthermore, the robust interfacial homogeneity of the ferroelectric film is highly beneficial for transfer printing in which arrays of metal/ferroelectric/metal micro‐capacitors are developed over a large area with well defined edge sharpness.     

On the Relation between Morphology and FET Mobility of Poly(3‐alkylthiophene)s at the Polymer/SiO2 and Polymer/Air Interface

The influence of the interface of the dielectric SiO₂ on the performance of bottom‐contact, bottom‐gate poly(3‐alkylthiophene) (P3AT) field‐effect transistors (FETs) is investigated. In particular, the operation of transistors where the active polythiophene layer is directly spin‐coated from chlorobenzene (CB) onto the bare SiO₂ dielectric is compared to those where the active layer is first spin‐coated then laminated via a wet transfer process such that the film/air interface of this film contacts the SiO₂ surface. While an apparent alkyl side‐chain length dependent mobility is observed for films directly spin‐coated onto the SiO₂ dielectric (with mobilities of ≈10^?3 cm² V^?1 s^?1 or less) for laminated films mobilities of 0.14 ± 0.03 cm² V^?1 s^?1 independent of alkyl chain length are recorded. Surface‐sensitive near edge X‐ray absorption fine structure (NEXAFS) spectroscopy measurements indicate a strong out‐of‐plane orientation of the polymer backbone at the original air/film interface while much lower average tilt angles of the polymer backbone are observed at the SiO₂/film interface. A comparison with NEXAFS on crystalline P3AT nanofibers, as well as molecular mechanics and electronic structure calculations on ideal P3AT crystals suggest a close to crystalline polymer organization at the P3AT/air interface of films from CB. These results emphasize the negative influence of wrongly oriented polymer on charge carrier mobility and highlight the potential of the polymer/air interface in achieving excellent “out‐of‐plane” orientation and high FET mobilities.     

Temperature gradient controlled crystal growth from TIPS pentacene-poly(α-methyl styrene) blends for improving performance of organic thin film transistors

6,13-bis(triisopropylsilylethynyl) pentacene (TIPS pentacene) from simple drop casting typically forms crystals with random orientation and poor areal coverage, which leads to device-to-device performance variation of organic thin film transistors (OTFTs). Previously, a temperature gradient technique was developed to address these problems. However, this approach simultaneously introduced thermal cracks due to the thermally induced stress during crystallization. These thermal cracks accounted for a reduction of charge transport, thereby impacting the device performance of TIPS pentacene based OTFTs. In this work, an insulating polymer, poly(α-methyl styrene) (PαMS) was blended with TIPS pentacene to relieve the thermal stress and effectively prevent the generation of thermal cracks. The results demonstrate that the incorporation of PαMS polymer combined with the temperature gradient technique improves both the hole mobility and performance consistency of TIPS pentacene based OTFTs.     

1D versus 2D Growth of Soluble Acene Crystals from Soluble Acene/Polymer Blends Governed by a Residual Solvent Reservoir in a Phase‐Separated Polymer Matrix

The growth mechanism of soluble acene is highly dependent on the remaining residual solvent following solution processing. The relationship between the amount of residual solvent and the growth modes of a prototypical soluble acene, 6,13‐bis(triisopropylsilylethynyl)pentacene (TIPS‐pentacene) are examined under spin casting TIPS‐pentacene/insulating polymer blends. Changing spin time of the blend solution allows to control the amount of residual solvent, which significantly determines the growth modes of TIPS‐pentacene vertically segregated onto the insulating polymer. In situ observation of crystal growth reveals that excess residual solvent in short spin time induces a convective flow in a drying droplet, thereby resulting in 1D growth of TIPS‐pentacene crystals. On the other hand, optimal amount of residual solvent in a moderate spin time results in 2D growth of TIPS‐pentacene crystals. The well‐developed 2D spherulites allow for higher field‐effect mobility than that of the 1D crystals because of the higher perfectness and coverage of TIPS‐pentacene crystals. The use of other types of soluble acene and insulating polymer only changes the kinetics of crystallization, while the transition of growth mode from 1D to 2D is still observed. This general growth mechanism facilitates the understanding of crystallization behavior of soluble acene for the development of high‐performance organic transistors.