Structural ordering versus energy band alignment: Effects of self-assembled monolayers on the metal/semiconductor interfaces of small molecule organic thin-film transistors

A model describing the influence of self-assembled monolayers on the contact resistance of bottom-contact organic thin-film transistors is presented. The model takes the contact geometry, the energy level alignment and the structural order of the organic films into consideration when describing the contact effects of organic transistors. The treatment of the metal source/drain electrodes of the transistors by self-assembled monolayers allows for tuning the work function of the metal contact and an improved ordering of the organic molecules on top of the source/drain contacts. The results reveal that the contact resistance is mainly determined by the molecular ordering, rather than the tuning of the work function. The model is compared to experimentally measured contact resistances for different self-assembled monolayers.     

Large enhancement of hole injection in pentacene by modification of gold with conjugated self-assembled monolayers

Planar diodes with gold electrodes and a pentacene semiconductor layer were made and electrically characterized. The gold electrodes were modified with self-assembled monolayers of biphenylthiol and biphenylthiol substituted with a terminal fluorine atom (fluorobiphenylthiol). Atomic force microscopy of the pentacene layer reveals large morphological similarities when the film is grown on gold modified with either of the two kinds of self-assembled monolayer. This is at variance with the significant increase of the current observed when the gold electrodes are treated with fluorobiphelylthiol, with a bulk mobility rising up to 1 cm²/V s, while the treatment with biphelylthiol leads to a substantial decrease of the current. These results are interpreted in terms of adjustment of the injection barrier height as a result of the interface dipole induced by the self-assembled monolayer.     

Patterning organic transistors by dry-etching: The double layer lithography

Structuring of organic layers is essential for large-scale integration and manufacturing of organic devices. A novel photo-patterning method for organic semiconductors is presented, which allows to use dry-etching to transfer resist patterns into metal layers on top of organic layers. Apart from the general advantages of dry-etching, such as reduced processing times and high pattern fidelity, it is shown that the new processing protocol leads to a high yield and reproducibility. Furthermore, in contrast to wet-chemical etching, the presented patterning method is versatile and can as well be used for materials known to be unintentionally doped by wet-chemical etching such as pentacene. Comparing pentacene transistors processed by shadow masking and lithography shows no obvious deterioration, which indicates that the protocol proposed here is compatible with a wide range of materials.     

Relation between injection barrier and contact resistance in top-contact organic thin-film transistors

We theoretically investigate the carrier injection into top-contact bottom-gate organic thin film transistors. By means of a two-dimensional drift–diffusion model, we explicitly consider thermionic and tunneling injection in combination with subsequent carrier transport into the device. Based on numerical simulations with this model, we determine the contact resistance as a function of the nominal hole injection barrier height and temperature. Depending on the barrier height or the operating temperature, we find three distinct injection regimes. Our work reveals that in all three regimes self-regulating processes exist due to which the influx of current is adjusted according to the needs of the channel at the given point of operation.     

Contactless charge carrier mobility measurement in organic field-effect transistors

With the increasing performance of organic semiconductors, contact resistances become an almost fundamental problem, obstructing the accurate measurement of charge carrier mobilities. Here, a generally applicable method is presented to determine the true charge carrier mobility in an organic field-effect transistor (OFET). The method uses two additional finger-shaped gates that capacitively generate and probe an alternating current in the OFET channel. The time lag between drive and probe can directly be related to the mobility, as is shown experimentally and numerically. As the scheme does not require the injection or uptake of charges it is fundamentally insensitive to contact resistances. Particularly for ambipolar materials the true mobilities are found to be substantially larger than determined by conventional (direct current) schemes.     

Ionic self-assembled monolayer for low contact resistance in inkjet-printed coplanar structure organic thin-film transistors

To reduce the contact resistance in inkjet-printed organic thin-film transistors (OTFTs), the use of a newly synthesized ionic self-assembled monolayer (SAM) consisting of an anchoring group, a linker group, and an ionic functional group, is investigated. According to the gated transmission line method (TLM) measurements of a series of OTFT devices, where one type has no charge injection layer, another type having a pentafluorobenzenethiol (PFBT) injection layer, and a third type containing a (6-mercaptohexyl)trimethylammonium bromide (MTAB) ionic SAM, the latter exhibits the lowest contact resistance value of ∼3.1 K Ω cm. The OTFTs without charge injection layer and with the PFBT SAM have relatively higher contact resistance values of ∼6.4 K Ω cm and ∼5.0 K Ω cm, respectively. The reduced contact resistance in the OTFTs with ionic SAMs is attributed to the large charge carrier density induced by the ionic SAM, which allows sufficient tunneling-assisted injection of the carriers from the metal electrode to the polymer semiconductor. These results suggest that the use of appropriate ionic SAM injection layer is an effective way to reduce the contact resistance, hence improving the charge transport characteristics of inkjet-printed OTFTs.     

An easily made thienoacene comprising seven fused rings for ambient-stable organic thin film transistors

A novel easily made thienoacene-based organic semiconductor, i.e., dinaphtho[3,4-d:3′,4′-d′]benzo[1,2-b:4,5-b′]dithiophene (Ph5T2), was synthesized in high yield, and its thermal stability, electrochemical properties, thin-film morphology and field-effect mobility were investigated. Ph5T2 exhibit excellent thermal stability with a decomposition temperature (T_d) of 427 °C. Thin-film X-ray diffraction (XRD) and atomic force microscopy (AFM) characterizations indicate that Ph5T2 can form highly ordered films with large domain size on the para-sexiphenyl (6P)-modified substrates. Organic thin-film transistors (OTFTs) with top-contact geometry based on Ph5T2 exhibit mobilities up to 1.2 cm² V⁻¹ s⁻¹ in ambient. The devices are highly stable and exhibit almost no performance degradation during 3 months storage under ambient conditions with relative humidity up to 80%.     

Characterization of ohmic contacts in polymer organic field-effect transistors

It is well known that contact resistance R_c limits the performance of organic field-effect transistors (OFETs) that have high field-effect mobilities (μ_FET ≳ 0.3 cm² V⁻¹ s⁻¹) and short channel lengths (L_ch ≲ 30 μm). The usual transfer-line method (TLM) to analyze R_c calls for extrapolation of total resistance to zero L_ch at constant drain and gate voltages. This requires an unrealistic assumption that R_c does not vary with source−drain current I_sd (nor with channel carrier density σ). Here we describe a self-consistent TLM analysis that instead imposes the condition of constant I_sd and σ. The results explicitly reveal the dependence of R_c on I_sd and σ. We further describe how this R_c(I_sd, σ) surface can be modelled to yield the specific contact resistivity ρ_c of the metal/organic semiconductor (OSC) interface, a key parameter that has so far been neglected in OFETs. We illustrate the application of these analyses to high-performance staggered top-gate bottom-contact poly(2,5-bis(alkyl)-1,4-dioxopyrrolo [3,4-c]pyrrole-3,6-diyl-terthiophene-2,5″-diyl) (DPPT2-T) OFETs fabricated on bottom Au source–drain electrode arrays, with high contact-corrected μ_FET of 0.5 cm² V⁻¹ s⁻¹. We show that when these electrodes are modified to impose weak, and then strong hole-doping of the DPPT2-T interface, R_c diminishes and its dispersion, i.e. dependence on I_sd and σ, weakens. The ultimate ρ_c attained for the strongly hole-doped contact is ca. 1 Ω cm², broadly independent of I_sd and σ, which we propose is a hallmark of a true metal/OSC ohmic contact. For comparison, the bare Au/DPPT2-T contact gives ρ_c of the order of 10 Ω cm² with a marked σ dependence. The lowest ρ_c reached here shortens the current transfer length down to ca. 5 μm, enabling short electrode lengths to be advantageously employed in technology.     

Charge transport and recombination in heterostructure organic light emitting transistors

Light-emitting field effect transistors (LEFETs) are a class of organic optoelectronic device capable of simultaneously delivering the electrical switching characteristics of a transistor and the light emission of a diode. We report on the temperature dependence of the charge transport and emissive properties in a model organic heterostructure LEFET system from 300 K to 135 K. We study parameters such as carrier mobility, brightness, and external quantum efficiency (EQE), and observe clear thermally activated behaviour for transport and injection. Overall, the EQE increases with decreasing temperature and conversely the brightness decreases. These contrary effects can be explained by a higher recombination efficiency occurring at lower temperatures, and this insight delivers new knowledge concerning the optimisation of both the transport and emissive properties in LEFETs.     

Dialkylated dibenzotetrathienoacene derivative as semiconductor for organic field effect transistors

A novel semiconductor material based on dialkylated thienoacene is designed and synthesized. The dihexyl-substituted dibenzotetrathienoacene derivative C6-DBTTA exhibits high stability which is evidenced by thermogravimetric analysis (TGA), UV–vis spectroscopy and electrochemistry. X-ray diffraction measurements of the vacuum-evaporated thin films show strong diffraction and indicate that the molecules are stacked nearly perpendicular to the substrate. AFM images reveal that the morphology of thin films depended on the deposition temperature. Thin film FETs devices based on C6-DBTTA were constructed and showed high mobility up to 0.48 cm² V⁻¹ s⁻¹ and an on/off ratio over 10⁷. These results suggest that this new dihexylated thienoacene is an important organic semiconductor for field effect transistors.     

Below-one-volt organic thin-film transistors with large on/off current ratios

In many of the applications envisioned for organic thin-film transistors (TFTs), the electrical power will be supplied by small batteries or energy harvesters, which implies that it will be beneficial if the TFTs can be operated with voltages of 1 V or even below 1 V. At the same time, the TFTs should have large on/off current ratios, especially for applications in digital circuits and active matrices. Here we demonstrate p-channel and n-channel organic TFTs fabricated on a flexible plastic substrate that have a turn-on voltage of exactly 0 V, a subthreshold slope of 100 mV/decade, and an on/off current ratio of 2 × 10⁵ when operated with gate-source voltages between 0 and 0.7 V. Complementary inverters fabricated using these TFTs have a small-signal gain of 90 and a minimum noise margin of 79% at a supply voltage of 0.7 V. Complementary ring oscillators can be operated with supply voltages as small as 0.4 V.     

Megahertz operation of flexible low-voltage organic thin-film transistors

Bottom-gate, top-contact (inverted staggered) organic thin-film transistors with a channel length of 1 μm have been fabricated on flexible plastic substrates using the vacuum-deposited small-molecule semiconductor 2,9-didecyl-dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (C₁₀-DNTT). The transistors have an effective field-effect mobility of 1.2 cm²/V s, an on/off ratio of 10⁷, a width-normalized transconductance of 1.2 S/m (with a standard deviation of 6%), and a signal propagation delay (measured in 11-stage ring oscillators) of 420 ns per stage at a supply voltage of 3 V. To our knowledge, this is the first time that megahertz operation has been achieved in flexible organic transistors at supply voltages of less than 10 V.     

Characterisation of charge carrier transport in thin organic semiconductor layers by time-of-flight photocurrent measurements

The paper reviews recent advances in characterisation of charge carrier transport in organic semiconductor layers by time-of-flight photocurrent measurements, with the emphasis on the measurements of the samples with co-planar electrodes. These samples comprised an organic semiconductor layer whose thickness is on the order of a μm or less, and thus mimic the structures of organic thin film transistors. In the review we emphasise the importance of considering spatial variation of electric field in these, essentially two-dimensional structures, in interpretation of photocurrent transients. We review the experimental details of this type of measurements and give examples that demonstrate exceptional sensitivity of the method to minute concentration of electrically active defects in the organic semiconductors as well as the capability of probing charge transport along the channels of different mobility that reside in the same sample.     

Low-voltage organic transistors with steep subthreshold slope fabricated on commercially available paper

Organic thin-film transistors were fabricated directly on the surface of commercially available cleanroom paper using the vacuum-deposited small-molecule semiconductor dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (DNTT). A thin, high-capacitance gate dielectric that allows the TFTs to be operated with low voltages of 2 V was employed. The TFTs have a charge-carrier mobility of 1.6 cm²/Vs, an on/off current ratio of 10⁶, and a subthreshold slope of 90 mV/decade. In addition, the TFTs also display a very large differential output resistance, which is an important requirement for applications in analog circuits and active-matrix displays.     

Mapping charge carrier density in organic thin-film transistors by time-resolved photoluminescence lifetime studies

The device performance of organic transistors is strongly influenced by the charge carrier distribution. A range of factors effect this distribution, including injection barriers at the metal-semiconductor interface, the morphology of the organic film, and charge traps at the dielectric/organic interface or at grain boundaries. In our comprehensive experimental and analytical work we demonstrate a method to characterize the charge carrier density in organic thin-film transistors using time-resolved photoluminescence spectroscopy. We developed a numerical model that describes the electrical and optical responses consistently. We determined the densities of free and trapped holes at the interface between the organic layer and the SiO₂ gate dielectric by comparison to electrical measurements. Furthermore by applying fluorescence lifetime imaging microscopy we determine the local charge carrier distribution between source and drain electrodes of the transistor for different biasing conditions. We observe the expected hole density gradient from source to drain electrode.     

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.     

Physical model of Seebeck coefficient under surface dipole effect in organic thin-film transistors

The surface dipole effect can play an important role in the performance of charge carrier transport in organic thin-film transistors (OTFTs). In this work, we propose a physical model of Seebeck coefficient based on variable-range hopping theory in OTFTs to characterize carrier thermoelectric transport. The model effectively explains the influence of a dipole on the carrier density, energetic disorder and temperature dependence of the Seebeck effect. The gate-voltage and temperature dependence of the Seebeck effect are remarkably enhanced by a dipole, while the energetic disorder exhibits a weak dependent nature. The Seebeck coefficients calculated in this study and those obtained experimentally in a previous study were found to be in good agreement.     

Inserting a Mn-doped TiO2 layer for improving performance of pentacene organic thin-film transistors

Device performance of pentacene organic thin-film transistors (OTFTs) was significantly improved via inserting a Mn-doped TiO₂ layer between pentacene semiconductor and the source–drain electrodes. In comparison with the OTFTs with only-Au electrodes, the introduction of a thin Mn-doped TiO₂ layer leads to saturation current increasing from 31.9 μA to 0.22 mA, effective field-effect mobility improving from 0.24 to 1.13 cm²/V s, and threshold voltage downshifting from −11 to −2 V. These performance enhancements are ascribed to the significant reduction of contact resistance and smoothed surface of pentacene layer. This work may provide an effective approach to improve the performance of the pentacene based OTFTs by inserting a Mn-doped TiO₂ layer.     

High-mobility organic thin-film transistors based on a small-molecule semiconductor deposited in vacuum and by solution shearing

The small-molecule organic semiconductor 2,9-di-decyl-dinaphtho-[2,3-b:2′,3′-f]-thieno-[3,2-b]-thiophene (C₁₀-DNTT) was used to fabricate bottom-gate, top-contact thin-film transistors (TFTs) in which the semiconductor layer was prepared either by vacuum deposition or by solution shearing. The maximum effective charge-carrier mobility of TFTs with vacuum-deposited C₁₀-DNTT is 8.5 cm²/V s for a nominal semiconductor thickness of 10 nm and a substrate temperature during the semiconductor deposition of 80 °C. Scanning electron microscopy analysis reveals the growth of small, isolated islands that begin to coalesce into a flat conducting layer when the nominal thickness exceeds 4 nm. The morphology of the vacuum-deposited semiconductor layers is dominated by tall lamellae that are formed during the deposition, except at very high substrate temperatures. Atomic force microscopy and X-ray diffraction measurements indicate that the C₁₀-DNTT molecules stand approximately upright with respect to the substrate surface, both in the flat conducting layer near the surface and within the lamellae. Using the transmission line method on TFTs with channel lengths ranging from 10 to 100 μm, a relatively small contact resistance of 0.33 kΩ cm was determined. TFTs with the C₁₀-DNTT layer prepared by solution shearing exhibit a pronounced anisotropy of the electrical performance: TFTs with the channel oriented parallel to the shearing direction have an average carrier mobility of (2.8 ± 0.3) cm²/V s, while TFTs with the channel oriented perpendicular to the shearing direction have a somewhat smaller average mobility of (1.3 ± 0.1) cm²/V s.     

The role of local potential minima on charge transport in thin organic semiconductor layers

We have performed a systematic study of dependence of time-resolved photocurrent on the point of charge excitation within the organic semiconductor channel formed by two coplanar metal electrodes. The results confirm that spatial variation of electric field between the electrodes crucially determines transport of photogenerated charge carriers through the organic layer. Time-of-flight measurements of photocurrent demonstrate that the transit time of photogenerated charge carrier packets drifting between the two electrodes decreases with increasing travelling distance. Such counterintuitive result cannot be reconciled with the spatial distribution of electric field between coplanar electrodes, alone. It is also in contrast to expected role of space-charge screening of external electric field. Supported by Monte Carlo simulations of hopping transport in disordered organic semiconductor layer, we submit that the space-charge screens the external electric field and captures slower charge carriers from the photogenerated charge carrier packet. The remaining faster carriers, exhibit velocity distribution with significantly higher mean value and shorter transit time.