Tuning Contact Resistance in Top‐Contact p‐Type and n‐Type Organic Field Effect Transistors by Self‐Generated Interlayers

Contact resistance significantly limits the performance of organic field‐effect transistors (OFETs). Positioning interlayers at the metal/organic interface can tune the effective work‐function and reduce contact resistance. Myriad techniques offer interlayer processing onto the metal pads in bottom‐contact OFETs. However, most methods are not suitable for deposition on organic films and incompatible with top‐contact OFET architectures. Here, a simple and versatile methodology is demonstrated for interlayer processing in both p‐ and n‐type devices that is also suitable for top‐contact OFETs. In this approach, judiciously selected interlayer molecules are co‐deposited as additives in the semiconducting polymer active layer. During top contact deposition, the additive molecules migrate from within the bulk film to the organic/metal interface due to additive‐metal interactions. Migration continues until a thin continuous interlayer is completed. Formation of the interlayer is confirmed by X‐ray photoelectron spectroscopy (XPS) and cross‐section scanning transmission electron microscopy (STEM), and its effect on contact resistance by device measurements and transfer line method (TLM) analysis. It is shown that self‐generated interlayers that reduce contact resistance in p‐type devices, increase that of n‐type devices, and vice versa, confirming the role of additives as interlayer materials that modulate the effective work‐function of the organic/metal interface.     

Improvement of the contact resistance between ITO and pentacene using various metal-oxide interlayers

Ultra-thin Al₂O₃, Ta₂O₅, and TiO₂ films were deposited on the indium tin oxide (ITO) surfaces in organic thin film transistors using the atomic layer deposition (ALD) process at room temperature, and the contact resistance was significantly improved with the increase of the dielectric constant of the interlayer. The electronic band diagrams of the pentacene/ITO structures after ALD treatment on ITO surface with various metal-oxides were measured using in situ ultra-violet photoelectron spectroscopy during the step-by-step deposition of pentacene, and these results explained the decrease of the hole injection barriers and the resulting improvement of the contact resistance between pentacene/ITO interface.     

Orders‐of‐Magnitude Reduction of the Contact Resistance in Short‐Channel Hot Embossed Organic Thin Film Transistors by Oxidative Treatment of Au‐Electrodes

In this study we report on the optimization of the contact resistance by surface treatment in short‐channel bottom‐contact OTFTs based on pentacene as semiconductor and SiO₂ as gate dielectric. The devices have been fabricated by means of nanoimprint lithography with channel lengths in the range of 0.3 μm < L < 3.0 μm. In order to reduce the contact resistance the Au source‐ and drain‐contacts were subjected to a special UV/ozone treatment, which induced the formation of a thin AuO_x layer. It turned out, that the treatment is very effective (i) in decreasing the hole‐injection barrier between Au and pentacene and (ii) in improving the morphology of pentacene on top of the Au contacts and thus reducing the access resistance of carriers to the channel. Contact resistance values as low as 80 Ω cm were achieved for gate voltages well above the threshold. In devices with untreated contacts, the charge carrier mobility shows a power‐law dependence on the channel length, which is closely related to the contact resistance and to the grain‐size of the pentacene crystallites. Devices with UV/ozone treated contacts of very low resistance, however, exhibit a charge carrier mobility in the range of 0.3 cm² V^–1 s^–1 < μ < 0.4 cm² V^–1 s^–1 independent of the channel length.     

Enhanced Performance of Fullerene n‐Channel Field‐Effect Transistors with Titanium Sub‐Oxide Injection Layer

Enhanced performance of n‐channel organic field‐effect transistors (OFETs) is demonstrated by introducing a titanium sub‐oxide (TiO_x) injection layer. The n‐channel OFETs utilize [6,6]‐phenyl‐C₆₁ butyric acid methyl ester (PC₆₁BM) or [6,6]‐phenyl‐C₇₁ butyric acid methyl ester (PC₇₁BM) as the semiconductor in the channel. With the TiO_x injection layer, the electron mobilities of PC₆₁BM and PC₇₁BM FET using Al as source/drain electrodes are comparable to those obtained from OFETs using Ca as the source/drain electrodes. Direct measurement of contact resistance (R_c) shows significantly decreased R_c values for FETs with the TiO_x layer. Ultraviolet photoelectron spectroscopy (UPS) studies demonstrate that the TiO_x layer reduces the electron injection barrier because of the relatively strong interfacial dipole of TiO_x. In addition to functioning as an electron injection layer that eliminates the contact resistance, the TiO_x layer acts as a passivation layer that prevents penetration of O₂ and H₂O; devices with the TiO_x injection layer exhibit a significant improvement in lifetime when exposed to air.     

Enhanced Charge Injection Through Nanostructured Electrodes for Organic Field Effect Transistors

Nanosphere lithography is used to process nanopore‐structured electrodes, which are applied into the fabrication of bottom‐gate, bottom‐contact configuration organic field effect transistors (OFETs) to serve as source/drain elecrodes. The introduction of this nanopore‐structure electrode facilitates the forming of nanopore‐structure pentacene layers with small grain boundaries at the electrode interface, and then reduces the contact resistance, contact‐induces the growth of pentacene and accordingly improves the mobility of charge carriers in the OFETs about 20 times as compared with results in literature through enhancing the charge carrier injection. It is believed that this structure of electrode is a valuable approach for improving organic filed effect transistors.     

Inkjet‐Printed Organic Electrodes for Bottom‐Contact Organic Field‐Effect Transistors

A graphite thin film was investigated as the drain and source electrodes for bottom‐contact organic field‐effect transistors (BC OFETs). Highly conducting electrodes (10² S cm^?1) at room temperature were obtained from pyrolyzed poly(l,3,4‐oxadiazole) (PPOD) thin films that were prepatterned with a low‐cost inkjet printing method. Compared to the devices with traditional Au electrodes, the BC OFETs showed rather high performances when using these source/drain electrodes without any further modification. Being based on a graphite‐like material these electrodes possess excellent compatibility and proper energy matching with both p‐ and n‐type organic semiconductors, which results in an improved electrode/organic‐layer contact and homogeneous morphology of the organic semiconductors in the conducting channel, and finally a significant reduction of the contact resistance and enhancement of the charge‐carrier mobility of the devices is displayed. This work demonstrates that with the advantages of low‐cost, high‐performance, and printability, PPOD could serve as an excellent electrode material for BC OFETs.     

Tuning Interfacial Properties by Spontaneously Generated Organic Interlayers in Top‐Contact‐Structured Organic Transistors

Controlling the interfacial properties between the electrode and active layer in organic field‐effect transistors (OFETs) can significantly affect their contact properties, resulting in improvements in device performance. However, it is difficult to apply to top‐contact‐structured OFETs (one of the most useful device structures) because of serious damage to the organic active layer by exposing solvent. Here, a spontaneously controlled approach is explored for optimizing the interface between the top‐contacted source/drain electrode and the polymer active layer to improve the contact resistance (R_C). To achieve this goal, a small amount of interface‐functionalizing species is blended with the p‐type polymer semiconductor and functionalized at the interface region at once through a thermal process. The R_C values dramatically decrease after introduction of the interfacial functionalization to 15.9 kΩ cm, compared to the 113.4 kΩ cm for the pristine case. In addition, the average field‐effect mobilities of the OFET devices increase more than three times, to a maximum value of 0.25 cm² V^?1 s^?1 compared to the pristine case (0.041 cm² V^?1 s^?1), and the threshold voltages also converge to zero. This study overcomes all the shortcomings observed in the existing results related to controlling the interface of top‐contact OFETs by solving the discomfort of the interface optimization process.     

Improved ambipolar charge injection in organic field-effect transistors with low cost metal electrode using polymer sorted semiconducting carbon nanotubes

Solution-processed thin film transistors can be implemented using simple and low cost fabrication, and are the best candidates for commercialization due to their application to a range of wearable electronics. We report an ambipolar charge injection interlayer that can improve both hole and electron injection in organic field-effect transistors (OFETs) with inexpensive source-drain electrodes. The solution processed ambipolar injection layer is fabricated by selective dispersion of semiconducting single walled carbon nanotubes using poly(9,9-dioctylfluorene). OFETs with molybdenum (Mo) contacts and interlayer (Mo/interlayer OFETs) exhibit superior performance, including higher hole and electron mobilities, device yield, lower threshold voltages, and lower trap densities than those of bare transistors. While OFETs with Mo contacts show unipolar p-type behaviour, Mo/interlayer OFETs display ambipolar transport due to significant enhancement of electron injection. In the p-type region, transistor performance is comparable to devices with gold (Au). Hole mobility is increased approximately ten-fold over devices with only Mo contacts. The electron mobility of Mo/interlayer OFETs is 0.05 cm²V⁻¹s⁻¹, which is higher than devices with Au electrodes. The p-type contact resistances of Mo/interlayer OFETs are half those of OFETs with Mo contacts. Trap density in Mo/interlayer OFETs is one order magnitude lower than that of pristine devices. We also demonstrate that this approach is extendible to other metals (nickel) and n-type semiconductors with different energy levels. Injection by tunnelling is suggested as the mechanism of ambipolar injection.     

Manipulating the Hysteresis in Poly(vinyl alcohol)‐Dielectric Organic Field‐Effect Transistors Toward Memory Elements

The origins of hysteresis in organic field‐effect transistors (OFETs) and its applications in organic memory devices is investigated. It is found that the orientations of the hydroxyl groups in poly(vinyl alcohol) (PVA) gate dielectrics are correlated with the hysteresis of transfer characteristics in pentacene‐based OFETs under the forward and backward scan. The applied gate bias partially aligns the orientations of the hydroxyl groups perpendicular to the substrate as characterized by reflective absorption Fourier transform infrared spectroscopy (RA‐FTIR), in which the field‐induced surface dipoles at the pentacene/PVA interface trap charges and cause the hysteresis. Treating PVA with an anhydrous solvent eliminates the residual moisture in the dielectrics layer, allowing for more effective control of the induced dipoles by the applied gate bias. OFETs of dehydrated‐PVA dielectrics present a pronounced shift of the threshold voltage (ΔV_Th) of 35.7 V in transfer characteristics, higher than that of 18.5 V for untreated devices and results in sufficient dynamic response for applications in memory elements. This work highlights the usage of non‐ferroelectric gate dielectrics to fabricate OFET memory elements by manipulating the molecular orientations in the dielectrics layer.     

Controlling Electron and Hole Charge Injection in Ambipolar Organic Field‐Effect Transistors by Self‐Assembled Monolayers

Controlling contact resistance in organic field‐effect transistors (OFETs) is one of the major hurdles to achieve transistor scaling and dimensional reduction. In particular in the context of ambipolar and/or light‐emitting OFETs it is a difficult challenge to obtain efficient injection of both electrons and holes from one injecting electrode such as gold since organic semiconductors have intrinsically large band gaps resulting in significant injection barrier heights for at least one type of carrier. Here, systematic control of electron and hole contact resistance in poly(9,9‐di‐n‐octylfluorene‐alt‐benzothiadiazole) ambipolar OFETs using thiol‐based self‐assembled monolayers (SAMs) is demonstrated. In contrast to common believe, it is found that for a certain SAM the injection of both electrons and holes can be improved. This simultaneous enhancement of electron and hole injection cannot be explained by SAM‐induced work‐function modifications because the surface dipole induced by the SAM on the metal surface lowers the injection barrier only for one type of carrier, but increases it for the other. These investigations reveal that other key factors also affect contact resistance, including i) interfacial tunneling through the SAM, ii) SAM‐induced modifications of interface morphology, and iii) the interface electronic structure. Of particular importance for top‐gate OFET geometry is iv) the active polymer layer thickness that dominates the electrode/polymer contact resistance. Therefore, a consistent explanation of how SAM electrode modification is able to improve both electron and hole injection in ambipolar OFETs requires considering all mentioned factors.     

High‐Resolution Characterization of Pentacene/Polyaniline Interfaces in Thin‐Film Transistors

We present the first detailed report that directly correlates the reduced contact resistance in organic thin‐film transistors (TFTs) with fundamental structural and morphological characterization at the organic semiconductor/conducting polymer interface. Specifically, the pentacene grains are similar in size and continuous across the channel/electrode interface in bottom‐contact TFTs with polyaniline (PANI) electrodes. On a molecular level, the fused rings of pentacene are oriented perpendicular to the surface both in the channel and on PANI. Accordingly, the contact resistance is small in such devices. In TFTs with gold electrodes, however, the pentacene grains are different in size and are discontinuous across the channel/electrode interface. Further, the fused rings of pentacene are oriented perpendicular to the channel surface and parallel to the gold surface. Such differences across the channel/electrode interface lead to structural and electronic disorder, which manifests itself as a significantly larger contact resistance in devices with gold electrodes.     

The origins in the transformation of ambipolar to n-type pentacene-based organic field-effect transistors

With aluminum (Al) source–drain electrodes, the transfer characteristics of pentacene-based organic field-effect transistors (OFETs) change from ambipolar to n-type after 24 h of storage in a nitrogen-filled glove box Chang et al. (2011) [16]. The time-dependent decrease of hole current is associated with the interfacial reaction at the Al source–drain electrodes and pentacene, which was studied by in-situ ultraviolet photoemission spectroscopy and X-ray photoelectron spectroscopy in this work. Experimental results indicate that the interface of the Al and pentacene is partially oxidized, but the similar oxidation was not observed at the interface of the pentacene and silver. The time-dependent oxidization of Al and pentacene creates an interfacial barrier to suppress the hole injection from Al electrodes (extraction of electrons from pentacene). However, it shows minor effect in the injection of electrons from Al electrode. Since the rate of oxidation is related to the contact area of the pentacene and Al, co-evaporating a thin Al:pentacene interlayer between the pentacene and Al electrodes expands the contact surface and accelerates the reaction, which is suitable for the fabrication of n-type only pentacene-based OFETs. This study highlights the impact of the interfacial reaction in Al/pentacene interface for the transformation of ambipolar to n-type OFETs.     

Contact Doping for Vertical Organic Field‐Effect Transistors

Doping is a powerful tool to overcome contact limitations in short‐channel organic field‐effect transistors (OFETs) and has been successfully used in the past to improve the charge carrier injection in OFETs. The present study applies this familiar concept to the architecture of vertical organic field‐effect transistors (VOFETs), which are often severely limited by injection due to their very short channel lengths. The present study shows that the performance of p‐type VOFETs with pentacene as an active material can be significantly enhanced by the addition of the common p‐dopant C₆₀F₃₆ as a thin injection layer underneath the VOFET source electrode, resulting in an increase of On‐state current and On/Off ratio by one order of magnitude. The present study further investigates mixed injection layers of pentacene and the p‐dopant and finds that the improvement is less pronounced than for the pure dopant layers and depends on the concentration of dopant molecules in the injection layer. Through application of the transfer length method to equivalent OFET geometries, the present study is finally able to link the observed improvement to a decrease in transfer length and can thus conclude that this length is a crucial parameter onto which further improvement efforts have to be concentrated to realize true short‐channel VOFETs.     

Metal evaporation dependent charge injection in organic transistors

To illuminate a long-term remaining issue on how contact metallization (metal and speed) affects charge injection, we investigated top-contact pentacene transistors using two categories of metals deposited at various rates. Differing from previous studies such as those devoted to morphological influences by microscopy, in this work we concentrated on their electrical characteristics in particular combining the low-frequency noise which provided a direct quantity of trap density and its evolution with respect to contact metal and deposition rate. It turns out that the transistors with noble metal (Au) suffer from metal-diffusion related charge trapping in the pentacene bulk close to the Au/pentacene interface, and this diffusion-limited injection is greatly tuned from bulk to interface by speeding Au deposition which leads to a Schottky-like injection due to the severe thermal damage to the upper pentacene layer. Applying a conventional contacting metal (Cu), however, Ohmic contacts with much fewer traps are always observed regardless of metallization speed. This is attributed to an ultra-thin interlayer of Cu_xO that guarantees stable Ohmic injection by introducing gap states and protecting the pentacene film so that those transistors appear to be free from Cu metallization. Our results quantitatively show the limiting factors of charge injection for different metals and at various evaporation rates.     

High‐Speed Organic Single‐Crystal Transistor Responding to Very High Frequency Band

Although high carrier mobility organic field‐effect transistors (OFETs) are required for high‐speed device applications, improving the carrier mobility alone does not lead to high‐speed operation. Because the cut‐off frequency is determined predominantly by the total resistance and parasitic capacitance of a transistor, it is necessary to miniaturize OFETs while reducing these factors. Depositing a dopant layer only at the metal/semiconductor interface is an effective technique to reduce the contact resistance. However, fine‐patterning techniques for a dopant layer are still challenging especially for a top‐contact solution‐processed OFET geometry because organic semiconductors are vulnerable to chemical damage by solvents. In this work, high‐resolution, damage‐free patterning of a dopant layer is developed to fabricate short‐channel OFETs with a dopant interlayer inserted at the contacts. The fabricated OFETs exhibit high mobility exceeding 10 cm² V^?1 s^?1 together with a reasonably low contact resistance, allowing for high frequency operation at 38 MHz. In addition, a diode‐connected OFET shows a rectifying capability of up to 78 MHz at an applied voltage of 5 V. This shows that an OFET can respond to the very high frequency band, which is beneficial for long‐distance wireless communication.     

Effect of Gate Electrode Work‐Function on Source Charge Injection in Electrolyte‐Gated Organic Field‐Effect Transistors

Systematic investigation of the contact resistance in electrolyte‐gated organic field‐effect transistors (OFETs) demonstrates a dependence of source charge injection versus gate electrode work function. This analysis reveals contact‐limitations at the source metal‐semiconductor interface and shows that the contact resistance increases as low work function metals are used as the gate electrode. These findings are attributed to the establishment of a built‐in potential that is high enough to prevent the Fermi‐level pinning at the metal‐organic interface. This results in an unfavorable energetic alignment of the source electrode with the valence band of the organic semiconductor. Since the operating voltage in the electrolyte‐gated devices is on the same order as the variation of the work functions, it is possible to tune the contact resistance over more than one order of magnitude by varying the gate metal.     

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.     

Low‐Voltage,High‐Performance Organic Field‐Effect Transistors with an Ultra‐Thin TiO2 Layer as Gate Insulator

We report on our latest improvements in organic field‐effect transistors (OFETs) using ultra‐thin anodized gate insulators. Anodization of titanium (Ti) is an extremely cheap and simple technique to obtain high‐quality, very thin (～ 7.5 nm), pinhole‐free, and robust gate insulators for OFETs. The anodized insulators have been tested in transistors using pentacene and poly(triarylamine) (PTAA) as active layers. The fabricated devices display low‐threshold, normally “off” OFETs with negligible hysteresis, good carrier mobility, high gate capacitance, and exceptionally low inverse subthreshold slope. Device performance is improved via chemical modification of TiO₂ with an octadecyltrichlorosilane (OTS) self‐assembled monolayer (SAM). As the result of this combination of favorable properties, we have demonstrated OFETs that can be operated with voltages well below 1 V.     

Gradual Controlling the Work Function of Metal Electrodes by Solution‐Processed Mixed Interlayers for Ambipolar Polymer Field‐Effect Transistors and Circuits

In this paper, a technique using mixed transition‐metal oxides as contact interlayers to modulate both the electron‐ and hole‐injections in ambipolar organic field‐effect transistors (OFETs) is presented. The cesium carbonate (Cs₂CO₃) and vanadium pentoixide (V₂O₅) are found to greatly and independently improve the charge injection properties for electrons and holes in the ambipolar OFETs using organic semiconductor of diketopyrrolopyrrolethieno[3,2‐b]thiophene copolymer (DPPT‐TT) and contact electrodes of molybdenum (Mo). When Cs₂CO₃ and V₂O₅ are blended at various mixing ratios, they are observed to very finely and constantly regulate the Mo's work function from ?4.2 eV to ?4.8 eV, leading to high electron‐ and hole‐mobilities as high as 2.6 and 2.98 cm² V^?1 s^?1, respectively. The most remarkable finding is that the device characteristics and device performance can be gradually controlled by adjusting the composition of mixed‐oxide interlayers, which is highly desired for such applications as complementary circuitry that requires well matched n‐channel and p‐channel device operations. Therefore, such simple interface engineering in conjunction with utilization of ambipolar semiconductors can truly enable the promising low‐cost and soft organic electronics for extensive applications.