We studied the influence of oxygen on the electronic trap states in a pentacene thin film. This was done by carrying out gated four-terminal measurements on thin-film transistors as a function of temperature and without ever exposing the samples to ambient air. Photooxidation of pentacene is shown to lead to a peak of trap states centered at 0.28 eV from the mobility edge, with trap densities of the order of 10(18) cm(-3). These trap states need to be occupied at first and cause a reduction in the number of free carriers, i.e. a consistent shift of the density of free holes as a function of gate voltage. Moreover, the exposure to oxygen reduces the mobility of the charge carriers above the mobility edge. We correlate the change of these transport parameters with the change of the essential device parameters, i.e. subthreshold performance and effective field-effect mobility. This study supports the assumption of a mobility edge for charge transport, and contributes to a detailed understanding of an important degradation mechanism of organic field-effect transistors. Deep traps in an organic field-effect transistor reduce the effective field-effect mobility by reducing the number of free carriers and their mobility above the mobility edge.
We demonstrate an organic memory-transistor device based on a pentacene-gold nanoparticles active layer. Gold (Au) nanoparticles are immobilized on the gate dielectric (silicon dioxide) of a pentacene transistor by an amino-terminated self-assembled monolayer. Under the application of writing and erasing pulses on the gate, large threshold voltage shift (22 V) and on/off drain current ratio of ~3E4 are obtained. The hole field-effect mobility of the transistor is similar in the on and off states (less than a factor 2). Charge retention times up to 4500 s are observed. The memory effect is main…
Gate bias stress instability in organic field-effect transistors (OFETs) is a major conceptual and device issue. This effect manifests itself by an undesirable shift of the transfer characteristics and is associated with long term charge trapping. We study the role of the dielectric and the semiconductor separately by producing OFETs with the same semiconductor (pentacene) combined with different dielectrics (SiO$_2$ and Cytop). We show, it is possible to fabricate devices which are immune to gate bias stress. For other material combinations, charge trapping occurs in the semiconductor alone, …
Pentacenequinone (PnQ) impurities have been introduced into a pentacene source material at number densities from 0.001 to 0.474 to quantify the relative effects of impurity content and grain boundary structure on transport in pentacene thin-film transistors. Atomic force microscopy (AFM) and electrical measurements of top-contact pentacene thin-film transistors have been employed to directly correlate initial structure and final film structures, with the device mobility as a function of added impurity content. The results reveal a factor four decrease in mobility without significant changes in…
We present the first thermoelectric measurements on pentacene field effect transistors. We report high values of the Seebeck coefficient at room temperature between 240 and 500 micro V/K depending on the dielectric surface treatment. These values are independent of the thickness of the channel and of the applied gate voltage. Two contributions to the Seebeck coefficient are clearly identified: the expected contribution that is dependent on the position of the transport level and reflects the activated character of carrier generation, and an unexpected intrinsic contribution of 265 plus minus 4…
Funtionalized pentacene, 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene), field-effect transistors(FET's) were made by thermal evaporation or solution deposition method and the mobility was measured as a function of temperature and light power. The field-effect mobility ($μ$$_{\rm FET}$) has a gate-voltage dependent activation energy. A non-monotonic temperature dependence was observed at high gate voltage (V$_G$ $<$ -30 V) with activation energy E$_a$ $\sim$ 60 - 170 meV,depending on the fabrication procedure. The gate-voltage dependent mobility and non-monotonic temperature depe…
We report on a healing of defects at room temperature in the organic semiconductor pentacene. This peculiar effect is a direct consequence of the weak intermolecular interaction which is characteristic of organic semiconductors. Pentacene thin-film transistors were fabricated and characterized by in situ gated four-terminal measurements. Under high vacuum conditions (base pressure of order 10E-8 mbar), the device performance is found to improve with time. The effective field-effect mobility increases by as much as a factor of two and mobilities up to 0.45 cm2/Vs were achieved. In addition, the…
In recent years, thin-film organic field-effect transistors (OFETs) have begun to be considered as a possible alternative to the hydrogenated amorphous silicon thin-film transistors (a-Si:H TFT's) used in active matrix flat panel displays and other large-area electronics applications. Low-temperature processability, low-cost fabrication and compatibility with arbitrary substrates are some of the promising advantages of OFETs, among others. Of the many organic materials available, pentacene, in particular, is one of the leading candidates for use in current thin-film OFET architectures - this b…
We report on the generation of a discrete trap state during negative gate bias stress in pentacene single crystal "flip-crystal" field-effect transistors with a SiO2 gate dielectric. Trap densities of up to 2*10^12 cm^-2 were created in the experiments. Trap formation and trap relaxation are distinctly different above and below ~280 K. In devices in which a self-assembled monolayer on top of the SiO2 provides a hydrophobic insulator surface we do not observe trap formation. These results indicate the microscopic cause of the trap state to be water adsorbed on the SiO2 surface.
The 1/f noise in pentacene thin film transistors has been measured as a function of device thickness from well above the effective conduction channel thickness to only two conducting layers. Over the entire thickness range, the spectral noise form is 1/f, and the noise parameter varies as (gate voltage)-1, confirming that the noise is due to mobility fluctuations, even in the thinnest films. Hooge's parameter varies as an inverse power-law with conductivity for all film thicknesses. The magnitude and transport characteristics of the spectral noise are well explained in terms of percolative eff…
We measure the complex impedance between source/drain electrodes and the gate electrode of a pentacene thin-film transistor (TFT) at frequencies 50 Hz < omega/2pi < 20 kHz. Modeling the TFT as a distributed RC network (RC transmission line), we find that the data cannot be explained by a model including only a real, frequency-independent sheet conductivity. Instead, we use the RC transmission line model to extract the frequency-dependent complex sheet conductivity sigma(omega) = sigma'(omega) + jsigma"(omega) of the pentacene film. At high frequencies, sigma(omega) increases with frequency, si…
Electrons and holes are locally injected in a single pentacene monolayer island. The two-dimensional distribution and concentration of the injected carriers are measured by electrical force microscopy. In crystalline monolayer islands, both carriers are delocalized over the whole island. On disordered monolayer, carriers stay localized at their injection point. These results provide insight into the electronic properties, at the nanometer scale, of organic monolayers governing performances of organic transistors and molecular devices.
We show that the performance of pentacene transistors can be significantly improved by maximizing the interfacial area at single walled carbon nanotube (SWCNT)/pentacene. The interfacial areas are varied by anchoring short SWCNTs of different densities (0-30/μm) to the Pd electrodes. The average mobility is increased three, six and nine times for low, medium and high SWCNT densities, respectively, compared to the devices with zero SWCNT. The current on-off ratio and on-current are increased up to 40 times and 20 times with increasing the SWCNT density. We explain the improved device performanc…
The thermal deposition and transfer Printing method had been used to produce pentacene thin-films on SiO2/Si and plastic substrates (PMMA and PVP), respectively. X-ray diffraction patterns of pentacene thin films showed reflections associated with highly ordered polycrystalline films and a coexistence of two polymorph phases classified by their d-spacing, d(001): 14.4 and 15.4 A.The dependence of the c-axis correlation length and the phase fraction on the film thickness and printing temperature were measured. A transition from the 15.4 A phase towards 14.4 A phase was also observed with increa…
We present a simple but powerful method to determine the thicknesses of the accumulation and depletion layers and the distribution curve of injected carriers in organic field effect transistors. The conductivity of organic semiconductors in thin film transistors was measured in-situ and continuously with a bottom contact configuration, as a function of film thickness at various gate voltages. Using this method, the thicknesses of the accumulation and depletion layers of pentacene were determined to be 0.9 nm (VG=-15 V) and 5 nm (VG=15 V).
The spectral density of localized states in the band gap of pentacene (trap DOS) was determined with a pentacene-based thin-film transistor from measurements of the temperature dependence and gate-voltage dependence of the contact-corrected field-effect conductivity. Several analytical methods to calculate the trap DOS from the measured data were used to clarify, if the different methods lead to comparable results. We also used computer simulations to further test the results from the analytical methods. Most methods predict a trap DOS close to the valence band edge that can be very well appro…
We developed a novel method for obtaining the distribution of trapped carriers over their degree of localization in organic transistors, based on the fine analysis of electron spin resonance spectra at low enough temperatures where all carriers are localized. To apply the method to pentacene thin-film transistors, we proved through continuous wave saturation experiments that all carriers are localized at below 50 K. We analyzed the spectra at 20 K and found that the major groups of traps comprise localized states having wave functions spanning around 1.5 and 5 molecules and a continuous distri…
We discuss the environmental instability of amorphous indium oxide (InOx)-based thin-film transistors (TFTs) in terms of the excess oxygen in the semiconductor films. A comparison between amorphous InOx doped with low and high concentrations of oxygen binder (SiO2) showed that out-diffusion of oxygen molecules causes drastic changes in the film conductivity and TFT turn-on voltages. Incorporation of sufficient SiO2 could suppress fluctuations in excess oxygen because of the high oxygen bond-dissociation energy and low Gibbs free energy. Consequently, the TFT operation became rather stable. The…
The surface conductivity is measured by a four-probe technique for pentacene and rubrene single-crystals laminated on polarized and nearly unpolarized molecular monolayers with application of perpendicular electric fields. The polarization of the self-assembled monolayers (SAMs) shifts the threshold gate voltage, while maintaining a very low subthreshold swing of the single-crystal devices (0.11 V/decade). The results, excluding influences of parasitic contacts and grain boundaries, demonstrate SAM-induced nanoscale charge injection up to ~10^12 cm^-2 at the surface of the organic single cryst…
A printing process for high-resolution transfer of all components for organic electronic devices on plastic substrates has been developed and demonstrated for pentacene (Pn), poly (3-hexylthiophene) and carbon nanotube (CNT) thin-film transistors (TFTs). The nanotransfer printing process allows fabrication of an entire device without exposing any component to incompatible processes and with reduced need for special chemical preparation of transfer or device substrates. Devices on plastic substrates include a Pn TFT with a saturation, field-effect mobility of 0.09 cm^2 (Vs)^-1 and on/off ratio …
We report the effect of air exposure on the electronic properties of pentacene single crystals. Air can diffuse reversibly in and out of the crystals and controls the physical properties. We discern two competing mechanisms that modulate the electronic transport. The presence of oxygen increases the hole conduction, as in dark four O2 molecules introduce one charge carrier. This effect is enhanced by the presence of visible light. Contrarily, water, present in ambient air, is incorporated in the crystal lattice and forms trapping sites for injected charges.
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 (pent…
We have used an electro-optic technique to measure the position-dependent infrared absorption of holes injected into a thin crystal of the organic semiconductor, 6,13-bis(triisopropylsilylethynyl)-pentacene incorporated in a field-effect transistor. By applying square-wave voltages of variable frequency to the gate or drain, one can measure the time it takes for charges to accumulate on the surface, and therefore determine their mobility.
The attachment of semiconducting nanoparticles to carbon nanotubes is one of the most challenging subjects in nanotechnology. Successful high coverage attachment and control over the charge transfer mechanism and photo-current generation opens a wide field of new applications such as highly effective solar cells and fibre-enhanced polymers. In this work we study the charge transfer in individual double-wall carbon nanotubes highly covered with uniform ZnO nanoparticles. The synthetic colloidal procedure was chosen to avoid long-chained ligands at the nanoparticle-nanotube interface. The result…
We demonstrate an approach to improve poly-3-hexylthiophene field effect transistors by modifying the gold contacts with monolayer thick pentacenequinone (PQ) or naphthalene (NL). The effective contact resistance is reduced by a factor of two and sixteen for interlayers of PQ and NL, respectively. The observation is attributed to different injection barriers at the metal-organic interface caused by the functionalization and to an additional tunneling barrier enhancing the on/off ratios. This barrier yields to activation energies of 37meV (NL) and 104meV (PQ) below 190K, which are smaller than …
We show that it is possible to reach one of the ultimate goals of organic electronics: producing organic field-effect transistors with trap densities as low as in the bulk of single crystals. We studied the spectral density of localized states in the band gap (trap DOS) of small molecule organic semiconductors as derived from electrical characteristics of organic field-effect transistors or from space-charge-limited-current measurements. This was done by comparing data from a large number of samples including thin-film transistors (TFT's), single crystal field-effect transistors (SC-FET's) and…
We demonstrate the field-effect transistor (FET) operation of molecularly-thin anatase phase produced through solid state transformation from Ti0.87O2 nanosheets. Monolayer Ti0.87O2 nanosheet with a thickness of 0.7 nm is two-dimensional oxide insulators in which Ti vacancies are incorporated, rather than oxygen vacancies. Since the fabrication method, in general, largely affects the film quality, the anatase films derived from Ti0.87O2 nanosheet show interesting characteristics, such as no photocurrent peak at ~2 eV, which is related to oxygen vacancies, and a larger band gap of 3.8 eV. The 1…
Demonstrate of High-Performance Top-Gate ALD Crystalline In2O3 Transistor Enabled by Lattice-Matched HfO2 and In2O3 Heterostructure
National Key Laboratory of Advanced Micro and Nano Manufacture Technology and School of Information Science and Electronic Engineering, Shanghai Jiao Tong University（上海交通大学信息科学与工程学院及先进微纳制造技术国家重点实验室）
Understanding charge transport in organic semiconductors in large electric fields is relevant to many applications. We present transport measurements in organic field-effect transistors based on poly(3-hexylthiophene) and 6,13-bis(triisopropyl-silylethynyl) pentacene with short channels, from room temperature down to 4.2 K. Near 300 K transport in both systems is well described by thermally assisted hopping with Poole-Frenkel-like enhancement of the mobility. At low temperatures and large gate voltages, transport in both materials becomes nearly temperature independent, crossing over into fiel…
We use a frequency-dependent electro-optic technique to measure the hole mobility in small molecule organic semiconductors, such as 6,13 bis(triisopropylsilylethynyl)-pentacene. Measurements are made on semiconductor films in bottom gate, bottom contact field-effect transistors (FETs.) Because of the buried metal layer effect the maximum response, due to absorption in the charge layer, will be for a dielectric film ~ 1/4 of a wavelength (in the dielectric) (e.g. ~ 1 micron thick in the infrared.) Results are presented for FETs prepared with both spin-cast polymer and alumina dielectrics prepar…
We demonstrate controllable shift of the threshold voltage and the turn-on voltage in pentacene thin film transistors and rubrene single crystal field effect transistors (FET) by the use of nine organosilanes with different functional groups. Prior to depositing the organic semiconductors, the organosilanes were applied to the SiO2 gate insulator from solution and form a self assembled monolayer (SAM). The observed shift of the transfer characteristics range from -2 to 50 V and can be related to the surface potential of the layer next to the transistor channel. Concomitantly the mobile charge …
Amorphous metal oxide thin-film transistors (TFT) are fabricated using InOx-based semiconductors doped with TiO2, WO3 or SiO2. Although density of dopant is low in the film, change in the electrical properties showed strong dependence on the dopant species. We found that the dependence could be reasonably explained by the bond-dissociation energy. By incorporating the dopant with higher bond-dissociation energy, the film becomes less sensitive to oxygen partial pressure used during sputtering deposition and remains electrically stable to thermal annealing treatment. The concept of bond-dissoci…
Amorphous oxide semiconductors, especially indium oxide-based (InOx) thin-films, have been major candidates for high mobility with easy-to-use device processability. As one of the dopants in InOx semiconductors, we proposed Si to design a thin-film transistor (TFT) channel. Because the suppression of unstable oxygen vacancies in InOx is crucial to maintaining the semiconducting behavior, Si was selected as a strong oxygen binder that is reasonably available for large production. In this review, we focus on the overall properties observed in Si-incorporated amorphous InOx TFTs in terms of bond-…
Platinum diselenide (PtSe_2) field-effect transistors with ultrathin channel regions exhibit p-type electrical conductivity that is sensitive to temperature and environmental pressure. Exposure to a supercontinuum white light source reveals that positive and negative photoconductivity coexists in the same device. The dominance of one type of photoconductivity over the other is controlled by environmental pressure. Indeed, positive photoconductivity observed in high vacuum converts to negative photoconductivity when the pressure is rised. Density functional theory calculations confirm that phys…
Fabrication of graphene field effect transistor is described which uses an intrinsic graphene on the surface of as deposited hydrogenated amorphous carbon films. Ambipolar characteristic has been demonstrated typical for graphene devices, which changes to unipolar characteristic if the surface graphene was etched in oxygen plasma. Because amorphous carbon films can be growth easily, with unlimited dimensions and no transfer of graphene is necessary, this can open new perspective for graphene electronics.
Colloidally synthesized nanomaterials are among the promising candidates for future electronic devices due to their simplicity and the inexpensiveness of their production. Specifically, colloidal nanosheets are of great interest since they are conveniently producible through the colloidal approach while having the advantages of two-dimensionality. In order to employ these materials, according transistor behavior should be adjustable and of high performance. We show that the transistor performance of colloidal lead sulfide nanosheets is tunable by altering the surface passivation, the contact m…
We report herein fabrication and characterization of a thin-film transistor (TFT) using single-crystalline, epitaxial SrTiO3 film, which was grown by a pulsed laser deposition technique followed by the thermal annealing treatment in an oxygen atmosphere. Although TFTs on the polycrystalline epitaxial SrTiO3 films (as-deposited) exhibited poor transistor characteristics, the annealed single-crystalline SrTiO3 TFT exhibits transistor characteristics comparable with those of bulk single-crystal SrTiO3 FET: an on/off current ratio >10^5, sub-threshold swing ~2.1 V/decade, and field-effect mobility…
Electrolyte-based transistors utilizing ionic liquids/gels have been highly successful in the study of charge-density-controlled phenomena, particularly in oxides. Experimental probes beyond transport have played a significant role, despite challenges to their application in electric double-layer transistors. Here, we demonstrate application of synchrotron soft X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) as operando probes of the charge state and magnetism in ion-gel-gated ferromagnetic perovskite films. Electrochemical response via oxygen vacancies at posi…
Graphene field-effect transistors with source/drain contacts made of metals that can be easily oxidized such as ferromagnetic metals often display a double dip structure in the transfer characteristics because of charge density depinning at the contacts. Generally, transfer characteristics of field-effect transistors show no dependence on the length of the source/drain contacts because charge carrier injection occurs mainly at the edges of the contact. However, the shape of the transfer characteristics of devices fabricated using Ni contacts is found to be dependent on the length of the contac…
Using ab initio density functional total energy and molecular dynamics simulations, we study the effects of various forms of nitrogen post deposition anneal (PDA) on the electric properties of hafnia in the context of its application as a gate dielectric in field effect transistors (FET). We consider the atomic structure and energetics of nitrogen containing defects which can be formed during the PDA in various N-based ambients: N2, N+2, N, NH3, NO, N2O. We analyse the role of such defects in fixed charge accumulation, electron trapping and in the growth of the interface SiOx layer. We find th…
Within the subgap of amorphous oxide semiconductors like amorphous indium gallium zinc oxide (a-IGZO) are donor-like and acceptor-like states that control the operational physics of optically transparent thin-film transistors (TFTs). Hydrogen incorporation into the channel layer of a top-gate a-IGZO TFT exists as an electron donor that causes an observed negative shift in the drain current-gate voltage ($\mathrm{I_{D} - V_{G}}$) transfer curve turn-on voltage. Normally, hydrogen is thought to create shallow electronic states just below the conduction band mobility edge, with the donor ionizati…
We have produced solution-processed thin films of 6,13-bis(triisopropyl-silylethynyl) pentacene with grain sizes from a few micrometers up to millimeter scale by lateral crystallization from a rectangular stylus. Grains are oriented along the crystallization direction, and the grain size transverse to the crystallization direction depends inversely on the writing speed, hence forming a regular array of oriented grain boundaries with controllable spacing. We utilize these controllable arrays to systematically study the role of large-angle grain boundaries in carrier transport and charge trappin…
Metal oxide thin-film transistors are fast becoming a ubiquitous technology for application in driving backplanes of organic light-emitting diode displays. Currently all commercial products rely on metal oxides processed via physical vapor deposition methods. Transition to simpler, higher throughput manufacturing methods such as solution-based processes, are currently been explored as cost-effective alternatives. However, developing printable oxide transistors with high carrier mobility and bias-stable operation has proved challenging. Here we show that hybrid multilayer channels composed of a…
High throughput experimental methods are known to accelerate the rate of research, development, and deployment of electronic materials. For example, thin films with lateral gradients in composition, thickness, or other parameters have been used alongside spatially-resolved characterization to assess how various physical factors affect material properties under varying measurement conditions. Similarly, multi-layer electronic devices that contain such graded thin films as one or more of their layers can also be characterized spatially in order to optimize the performance. In this work, we apply…
A transition in source-drain current vs back gate voltage ID - VBG characteristics from extrinsic polar molecule dominant hysteresis to anti-hysteresis induced by an oxygen deficient surface layer that is intrinsic to the ferroelectric thin films has been observed on graphene field-effect transistors on Pb0.92La0.08Zr0.52Ti0.48O3 gates GFET/PLZT-Gate during a vacuum annealing process developed to systematically remove the polar molecules adsorbed on the GFET channel surface. This allows detangle of the extrinsic and intrinsic hysteresis on GFET/PLZT-gate devices and detection of the dynamic sw…
Achieving good quality Ohmic contacts to van der Waals materials is a challenge, since at the interface between metal and van der Waals material, different conditions can occur, ranging from the presence of a large energy barrier between the two materials to the metallization of the layered material below the contacts. In black phosphorus (bP), a further challenge is its high reactivity to oxygen and moisture, since the presence of uncontrolled oxidation can substantially change the behavior of the contacts. In this study, we investigate the influence of the metal used for the contacts to bP a…
Alloying of In/Zn oxides with various X atoms stabilizes the IXZO structures but generates electron traps in the compounds, degrading the electron mobility. To assess whether the latter is linked to the oxygen affinity or the ionic radius, of the X element, several IXZO samples are synthesized by the sol-gel process, with a large number (14) of X elements. The IXZOs are characterized by XPS, SIMS, DRX, and UV-spectroscopy and used for fabricating thin film transistors. Channel mobility and the interface defect density NST, extracted from the TFT electrical characteristics and low frequency noi…
Graphene is an ultrathin material, which allows us to control surface phenomena by means of field-effect gating. Among various surface phenomena, photo-oxidation is known to be a facile method to largely control the electronic structure of graphene. In this study, gate controllability of photo-oxidation of graphene is thoroughly examined using a field-effect-transistor configuration. The presence of water molecules enhances gate controllability, which can be explained using water-oxygen co-adsorption picture. In addition, the photo-oxidation reaction evolves from the edge and proceeds towards …
