The hybridization and optimization of complementary DNA molecules on organic field-effect transistors

A DNA sensor based on pentacene thin film transistors (TFTs) is an excellent candidate for disposable sensor applications on account of their low-cost fabrication process and fast detection. We fabricated pentacene TFTs for the optimization of DNA hybridization. Different temperature and hybridization time were introduced during the DNA hybridization process in order to improve the hybridization efficiency of DNA molecules on the pentacene substrate. In this case, the optimized process conditions (45 °C and a hybridization of 30 min) for the DNA hybridization on the pentacene film were obtained, which are essential to enhance the sensitivity of OTFT-based DNA sensors.     

Disorder-mediated ordering by self-interfactant effect in organic thin film growth of pentacene on silicon

We have studied the morphology of pentacene films on different silicon surfaces with orientations between Si(1 1 1) and Si(0 0 1). Pentacene molecules are immobile on the Si surface, covering and passivating reactive defect sites. Molecules deposited on top of a closed amorphous wetting layer exhibit isotropic diffusion with diffusion lengths of several tens of micrometers. Neither steps, nor the surface structure affect the film morphology. The wetting layer thus acts as an interfactant, and isolates the molecular film from the substrate, explaining the high quality of pentacene films.     

Environmental effects on the electrical behavior of pentacene thin-film transistors with a poly(methyl methacrylate) gate insulator

The electrical properties of top-contact pentacene thin-film transistors (TFTs) with a poly(methyl methacrylate) (PMMA) gate dielectric were analyzed in air and vacuum environments. Compared to the vacuum case, the pentacene TFT in air exhibited lower drain currents and more pronounced shifts in the threshold voltage upon reversal of the gate voltage sweep direction, together with a decrease in the field-effect mobility. These characteristic variations were explained in terms of two distinctive actions of polar H₂O molecules in pentacene TFT. H₂O molecules were suggested to diffuse under the source and drain contacts and interrupt the charge injection into the pentacene film, whereas those that permeate at the pentacene/PMMA interface retard hole depletion in and around the TFT channel. The diffusion process was much slower than the permeation process. The degraded TFT characteristics in air could be recovered mostly by storing the device under vacuum, which suggests that the air instability of TFTs is due mainly to the physical adsorption of H₂O molecules within the pentacene film.     

Effect of thickness of polymer electret on charge trapping properties of pentacene-based nonvolatile field-effect transistor memory

In this report, a set of pentacene-based organic field-effect transistor (OFET) memory devices using different thicknesses (ranged from 17.8 to 100.4 nm) of Poly (N-vinylcarbazole) (PVK) as charge trapping layers were fabricated, and the dependences of thickness on charge trapping behaviors were systematically investigated. As the thickness increased, the charge trapping capacity shows a Gaussian distributed growth behavior while the surface tunneling distance demonstrates the property of exponential decrease, which is ascribed to the synergistic effects of potential redistribution of trapped charge carriers and the co-existence of direct tunneling and Fowler–Nordheim (FN) tunneling. The optimum thickness (d_ot) to possess the most efficient charge trapping properties, which means a reasonably low programming voltage and high charge trapping capacity with good bias stress stability, is approximately 40 ± 5 nm. By calculating the threshold thickness (d_th) of PVK for an ultrathin memory, we proposed a model of superficial tunneling distance to deconstruct the continuous chargeable polymer electret-based OFET memory. Our work provided a quantitative evaluation method and can improve the understanding of charge trapping process from the aspect of electret thickness.     

Interface dipole: Effects on threshold voltage and mobility for both amorphous and poly-crystalline organic field effect transistors

We report a detailed comparison on the role of a self-assembled monolayer (SAM) of dipolar molecules on the threshold voltage and charge carrier mobility of organic field-effect transistor (OFET) made of both amorphous and polycrystalline organic semiconductors. We show that the same relationship between the threshold voltage and the dipole-induced charges in the SAM holds when both types of devices are fabricated on strictly identical base substrates. Charge carrier mobilities, almost constant for amorphous OFET, are not affected by the dipole in the SAMs, while for polycrystalline OFET (pentacene) the large variation of charge carrier mobilities is related to change in the organic film structure (mostly grain size).     

Oriented growth of rubrene thin films on aligned pentacene buffer layer and its anisotropic thin-film transistor characteristics

Oriented growth of polycrystalline rubrene thin film on oriented pentacene buffer layer was investigated. The oriented pentacene buffer layer was created by thermal evaporation of pentacene on a rubbed polyvinylalcohol (PVA) surface. The pentacene layer in turn induced the oriented growth of rubrene crystals upon thermal deposition. The structures of successive layers were characterized by using grazing incidence X-ray diffraction (GIXD) and atomic force microscopy. Highly oriented rubrene crystallites with the a-axis aligning along the surface normal and the (0 0 2) plane preferentially oriented 45° away from the rubbing direction were found. In contrast, the rubrene thin film deposited on PVA or rubbed-PVA substrate without a pentacene buffer layer only gave amorphous phases. With the aligned pentacene/rubrene film as the active layer of organic field-effect transistor, anisotropic mobilities were observed. The highest field-effect mobility (0.105 cm²/V s) was observed along the direction 45° away from the rubbing direction and is ∼4 times higher than that for similar device prepared on unrubbed PVA. The direction was consistent with the GIXD observation that a large number of rubrene crystallites are having their [0 0 2] direction aligning in this direction. A favourable C–H⋯π interaction between an oriented pentacene layer and the rubrene layer on the control of molecular orientation in the conduction channel of the OFET is suggested.     

Controlled surface doping for operating stability enhancement in organic field-effect transistors

The introduction of an inorganic/organic or organic/organic heterojunction in the pentacene-based organic field-effect transistors is demonstrated to be in favor of improving their operating stability. The heterojunction-induced p-type doping of pentacene is nondestructive, and it can be controlled by varying the adlayer thickness. The bias stress effects are compared at similar surface carrier density for the doped and undoped devices, and the current flow in the pentacene bulk is found to be more stable than that in the conducting channel close to the gate dielectric. In the initial stage of the bias stress characteristics, the carrier trapping associated with the gate dielectric is mainly responsible for the current instability. On the other hand, in the prolonged stage, the carrier trapping in the active layer may become dominant.     

Organic field-effect transistors as new paradigm for large-area molecular junctions

Self-Assembly Monolayers (SAMs) are considered a promising route for solving technological hindrances (such as bias-stress, contact resistance, charge trapping) affecting the electrical performances of the Organic Field-Effect Transistors (OFETs). Here we use an OFET based on pentacene thin film to investigate the charge transport across conjugated SAMs at the Au/pentacene interface. We synthesized a homolog series of π-conjugated molecules, termed Tn-C8-SH, consisting of a n-unit oligothienyl Tn (n = 1…4) bound to an octane-1-thiol (C8-SH) chain that self-assembles on the Au electrodes. The multi-parametric response of such devices yields an exponential behavior of the field-effect mobility (μ), current density (J), and total resistivity (R), due to the SAM at the charge injection interface (i.e. Au-SAM-pentacene). The surface treatment of the OFETs induces a clear stabilization of different parameters, like sub-threshold slope and threshold voltage, thanks to standardized steps in the fabrication process.     

Electrical instability in short channel organic thin-film transistors induced by lucky-polaron mechanism

In this work we study the electrical stability under both gate bias stress and gate and drain bias stress of short channel (L = 5 μm) bottom contact/top gate OTFTs made on flexible substrate with solution-processed organic semiconductor and fluoropolymer gate dielectric. These devices show high field-effect mobility (μ_FE> 1 cm²V⁻¹s⁻¹) and excellent stability under gate bias stress (bias stress V_ds = 0V). However, after prolonged bias stress performed at high drain voltage, V_ds, the transfer characteristics show a decreased threshold voltage, degradation of the subthreshold slope and an apparent increase in the field effect mobility. Furthermore, the output characteristics show an asymmetry when measured in forward and reverse mode. These experimental results can be explained considering that the bias stress induces the damage of a small part of the device channel, localized close to the source contact. The analysis of the experimental data through 2D numerical simulations supports this explanation showing that the electrical characteristics after bias stress at high V_ds can be reproduced considering the creation of donor-like interface states and trapping of positive charge into the gate dielectric at the source end of the device channel. In order to explain this degradation mechanism, we suggest a new physical model that, assuming holes injection from the source contact into the channel in bounded polarons, envisages the defect creation at the interface near the source end of the channel induced by injection of holes that gained energy from both the high longitudinal electric fields and the polaron dissolution.     

High air stability of threshold voltage on gate bias stress in pentacene TFTs with a hydroxyl-free and amorphous fluoropolymer as gate insulators

We investigated the air stabilities of threshold voltages (V_th) on gate bias stress in pentacene thin-film transistors (TFTs) with a hydroxyl-free and amorphous fluoropolymer as gate insulators. The 40-nm-thick thin films of spin-coated fluoropolymer had excellent electrical insulating properties, and the pentacene TFTs exhibited negligible current hysteresis, low leakage current, a field-effect mobility of 0.45 cm²/Vs and an on/off current ratio of 3 × 10⁷ when it was operated at −20 V in ambient air. After a gate bias stress of 10⁴ s, a small V_th shift below 1.1 V was obtained despite non-passivation of the pentacene layer. We have discussed that the excellent air stability of V_th was attributed to the insulator surface without hydroxyl groups.     

Charge Trapping in Intergrain Regions of Pentacene Thin Film Transistors

A scanning Kelvin probe microscopy (SKPM) study of the surface potential of vacuum sublimed pentacene transistors under bias stress and its correlation with the film morphology is presented. While for thicker films there are some trapping centers inhomogeneously distributed over the film, as previously reported by other authors, by decreasing the film thickness the effect of thin intergrain regions (IGRs) becomes clear and a very good correlation between the topography and the potential data is observed. It is shown that in the thick pentacene grains the potential is homogeneous and independent of the gate bias applied with negligible charge trapping, while in the thin IGRs the potential varies with the applied gate bias, indicating that only an incomplete accumulation layer can be formed. Clear evidence for preferential charge trapping in the thin IGRs is obtained.     

Influence of Electric Field on Microstructures of Pentacene Thin‐Films in Field‐Effect Transistors

We report on electric‐field‐induced irreversible structural modifications in pentacene thin films after long‐term operation of organic field‐effect transistor (OFET) devices. Micro‐Raman spectroscopy allows for the analysis of the microstructural modifications of pentacene in the small active channel of OFET during device operation. The results suggest that the herringbone packing of pentacene molecules in a solid film is affected by an external electric field, particularly the source‐to‐drain field that parallels the a–b lattice plane. The analysis of vibrational frequency and Davydov splitting in the Raman spectra reveals a singular behavior suggesting a reduced separation distance between pentacene molecules after long‐term operations and, thus, large intermolecular interactions. These results provide evidence for improved OFET performance after long‐term operation, related to the microstructures of organic semiconductors. It is known that the application of large electric fields alters the semiconductor properties of the material owing to the generation of defects and the trapping of charges. However, we first suggest that large electric fields may alter the molecular geometry and further induce structural phase transitions in the pentacene films. These results provide a basis for understanding the improved electronic properties in test devices after long‐term operations, including enhanced field‐effect mobility, improved on/off current ratio, sharp sub‐threshold swing, and a slower decay rate in the output drain current. In addition, the effects of source‐to‐drain electric field, gate electric field, current and charge carriers, and thermal annealing on the pentacene films during OFET operations are discussed.     

Employing microspectroscopy to track charge trapping in operating pentacene OFETs

Ultrathin pentacene films resemble benchmark and model materials for organic field-effect transistors (OFETs). We employ scanning transmission X-ray microspectroscopy (STXM) and confocal Raman microspectroscopy as highly resolving probes to obtain insight into the correlation of morphology and charge transport in pentacene OFETs. By combining the operation-induced intensity increase in Raman-active bands with micromorphology, we are able to visualize charge-induced effects, in particular charge trapping in pentacene OFETs during operation. The high sensitivity and specificity of Raman microscopy allows to distinguish between orientation and charge-induced effects and thus to locate the trapped charges at grain boundaries.     

Organic small-molecule heterointerface for use in transistor-type non-volatile memory

A chargeable layer is an essential element for charge transfer and trapping in a transistor-based non-volatile memory device. Here we demonstrate that a heterointerface layer comprising of two different small molecules can show electrical memory characteristics. The organic heterointerface layer was fabricated with a pentacene and tris(8-hydroxyquinoline) aluminum (Alq3) layers by sequential vapor deposition without breaking the vacuum state. Pentacene was adopted as the active layer on the top, and Alq3 was used as the bottom layer for charge trapping. The bottom-gate top-contact transistor with an organic heterointerface layer showed distinct non-volatile memory behaviors and showed high air stability and reliability. We investigated the energy structure of the pentacene/Alq3 heterointerface layer to reveal the operation mechanism of the non-volatile memory and suggested that the writing/erasing gate bias-dependent energy barrier originating from the difference between the energy levels of the pentacene and Alq3 layers controls the charge transfer at the heterointerface layer. Our approach suggests a simple way to fabricate heterointerface layers for organic non-volatile memory applications with high air stability and reliability.     

Effect of electron-donating unit on crystallinity and charge transport in organic field-effect transistors with thienoisoindigo-based small molecules

We report the effect of an electron-donating unit on solid-state crystal orientation and charge transport in organic field-effect transistors (OFETs) with thienoisoindigo (TIIG)-based small molecules. End-capping of different electron-donor moieties [benzene (Bz), naphthalene (Np), and benzofuran (Bf)] onto TIIG (giving TIIG-Bz, TIIG-Np, and TIIG-Bf) is resulted in different electronic energy levels, solid-state morphologies and performance in OFETs. The 80 °C post-annealed TIIG-Np OFETs show the best device performance with a best hole mobility of 0.019 cm² V⁻¹ s⁻¹ and threshold voltage of −8.6 ± 0.9 V using top gate/bottom contact geometry and a CYTOP gate dielectric. We further investigated the morphological microstructure of the TIIG-based small molecules by using grazing incidence wide angle X-ray scattering, atomic force microscopy and a polarized optical microscope. The electronic transport levels of the TIIG-based small molecules in thin-film states were investigated using ultraviolet photoelectron spectroscopy to examine the charge injection properties of the gold electrode.     

Insight into the charge transport and degradation mechanisms in organic transistors operating at elevated temperatures in air

Operational stability of organic devices at above-room-temperatures in ambient environment is of imminent practical importance. In this report, we have investigated the charge transport and degradation mechanisms in pentacene based organic field effect transistors (OFETs) operating in the temperatures ranging from 25 °C to 150 °C under ambient conditions. The thin film characterizations techniques (X-ray photoelectron spectroscopy, X-ray diffraction and atomic force microscopy) were used to establish the structural and chemical stability of pentacene thin films at temperatures up to 150 °C in ambient conditions. The electrical behavior of OFETs varies differently in different temperature bracket. Mobility, at temperatures below 110 °C, is found to be thermally activated in presence of traps and temperature independent in absence of traps. At temperatures above 110 °C mobility degrades due to polymorphism in pentacene or interfacial properties. The degradation of mobility is compensated with the decrease in threshold voltage at high temperatures and OFETs are operational at temperatures as high as 190 °C. 70 °C has been identified as the optimum temperature of operation for our OFETs where both device behavior and material properties are stable enough to ensure sustainable performance.     

Phosphorus Doping Effect in a Zinc Oxide Channel Layer to Improve the Performance of Oxide Thin-Film Transistors

In this study, we fabricated phosphorus-doped zinc oxide-based thin-film transistors (TFTs) using direct current (DC) magnetron sputtering at a relatively low temperature of 100°C. To improve the TFT device performance, including field-effect mobility and bias stress stability, phosphorus dopants were employed to suppress the generation of intrinsic defects in the ZnO-based semiconductor. The positive and negative bias stress stabilities were dramatically improved by introducing the phosphorus dopants, which could prevent turn-on voltage (V _ON) shift in the TFTs caused by charge trapping within the active channel layer. The study showed that phosphorus doping in ZnO was an effective method to control the electrical properties of the active channel layers and improve the bias stress stability of oxide-based TFTs.     

Effect of molybdenum electrode annealing on the interface properties between metal and pentacene

Contact resistance between molybdenum (Mo) electrode and pentacene was studied with transmission line method (TLM). The Mo electrodes were annealed at 200 °C, 400 °C, 600 °C and 800 °C for 1 h and pentacene layer of 300 Å thickness was vacuum deposited on patterned Mo to form Mo–pentacene contact. Current–voltage measurement for Mo–pentacene contact showed linear relationship and it was confirmed that ohmic contact was formed. XRD and AFM measurements showed that Mo could be crystallized at annealing temperatures above 600 °C. 800 °C annealed Mo showed larger grains and work function was increased from 4.60 eV to 4.80 eV due to the decrease in defect density. The contact resistance was reduced down to 11.2 MΩ cm from 37.8 MΩ cm of as-deposited Mo. Also the pentacene film deposited on annealed Mo was denser with better crystallinity. Bottom contact organic field-effect transistor made with 800 °C annealed Mo showed better performance than as deposited Mo.     

Structural and Electrostatic Complexity at a Pentacene/Insulator Interface

The properties of organic‐semiconductor/insulator (O/I) interfaces are critically important to the operation of organic thin‐film transistors (OTFTs) currently being developed for printed flexible electronics. Here we report striking observations of structural defects and correlated electrostatic‐potential variations at the interface between the benchmark organic semiconductor pentacene and a common insulator, silicon dioxide. Using an unconventional mode of lateral force microscopy, we generate high‐contrast images of the grain‐boundary (GB) network in the first pentacene monolayer. Concurrent imaging by Kelvin probe force microscopy reveals localized surface‐potential wells at the GBs, indicating that GBs will serve as charge‐carrier (hole) traps. Scanning probe microscopy and chemical etching also demonstrate that slightly thicker pentacene films have domains with high line‐dislocation densities. These domains produce significant changes in surface potential across the film. The correlation of structural and electrostatic complexity at O/I interfaces has important implications for understanding electrical transport in OTFTs and for defining strategies to improve device performance.     

Electronic structure of the pentacene–gold interface: A density-functional theory study

The structural and electronic properties of a pentacene monolayer adsorbed on the Au(1 1 1) surface have been studied with a density-functional theory (DFT) approach. A thermally stable adsorption geometry of the pentacene monolayer on the gold surface is found, from which the adsorption energy per pentacene molecule can be evaluated. Our results illustrate how the electron charge distribution initially present over the clean gold surface is pushed back upon adsorption of the pentacene monolayer; this push-back (pillow effect) leads to a significant work-function decrease for the modified gold surface. The electronic couplings between the highest occupied molecular orbital of pentacene and the Au(1 1 1) surface and between adjacent pentacene molecules within the monolayer, were extracted from the calculated band structures; the pentacene–gold surface electronic coupling is found to be about five times smaller than the electronic coupling between pentacene molecules.