Charge Injection Engineering of Ambipolar Field-Effect Transistors for High-Performance Organic Complementary Circuits

An ultra-thin natural-source-based cellulose derivate is used in a bilayer gate dielectric for organic complementary inverters. Extraordinarily high small-signal gains up to 1600, a very sharp transition region (as low as 40 mV), a full rail-to-rail swing, a balanced noise margin of 92.5%, and “long-time” stability are shown, revealing that these inverters are highly suitable for complex circuit designs. For more than a decade now the research in organic electronics was driven by unique consumer markets demanding for electronic circuits on flexible substrates over large areas and ideally at low cost. Meanwhile, versatile macroelectronic applications with attractive form factors such as flexible displays,1-4 large-area sensor arrays,5-11 e-paper,12, 13 low-cost radio-frequency identification tags,14-18 and bendable microprocessors19 have been realized using organic thin-film transistors (OTFTs) as the essential element. In the majority of these applications OTFTs are integrated either in the form of arrays or as digital logic. The fundamental building block of digital logic is the inverter, a circuit that inverts an input signal. Much work has been devoted in the last five years to design unipolar inverters using p-type-only OTFTs.18-23 Unfortunately, unipolar logic based on single gate OTFTs always suffers from high power consumption and low noise margin coupled with high noise margin variability and therefore impedes the fabrication of complex circuits having hundreds or more logic gates.19, 22, 23 In this context, it stands beyond doubt that the integration of both n-type and p-type transistors in complementary organic-based circuits12 is very advantageous due to a lower power dissipation, higher noise margin, better operational stability, and easier design of the circuit.24-27 To date, several major obstacles complicated the development of organic complementary circuits, which are as follows: i) the lack of n-channel OTFTs with a performance comparable to the p-channel OTFTs, ii) the challenge of device stability (difficulty in fabricating OTFTs with hysteresis-free characteristics), and iii) the difficulty in fabricating sufficiently thin gate dielectrics allowing for low supply voltages. Although many recently reported complementary organic inverters are impressive with respect to their low operation voltages (≤5 V),27-36 high static gains (>100 V/V),25, 28, 30, 32 and large noise margins (>80%),25, 35, 37, 38 only few of those can combine low-voltage operation with high gain and sufficient immunity against electrical noise.39 Moreover, there have been few investigations of the influence of hysteresis and threshold voltage shifts on the inverter characteristics, which typically gives rise to electrical instabilities and performance limitations of those devices.32, 39 The inverter's noise margin is the most critical parameter, since it directly determines the maximum complexity of circuits.22 Particularly, interesting applications of organic electronic circuits are found in analog electronics that allow for the read-out and processing of signals from printed large-area sensors and form an interface to silicon electronics. Examples are analog-to-digital (A/D) converters, operational amplifiers, and comparators, all including several tens of transistors, thus requiring both high gain and a large noise margin to be functional as well as sufficient processability. It is interesting to note that the majority of organic complementary inverters already mentioned24-34, 36-40 relied on pentacene as the p-type semiconductor (14 incidences), fluorinated copper phthalocyanine (6 incidences), or N,N′-ditridecylperylene-3,4,9,10-tetracarboxylic diimide (5 incidences) as the n-type material. On the contrary, the variation in gate dielectric materials that are used is much higher with an emphasis on hybrid dielectric systems. Hybrid systems allow accounting for both a high dielectric breakdown voltage and an engineered interface to the semiconductor. Moreover, the implementation of biodegradable and biocompatible materials represents a new niche in the organic electronics research, aimed to address the issues of cost and toxicity to humans and environment posed by nowadays electronics, a topic that was recently reviewed elsewhere.41-43 Accordingly, we have demonstrated the usage of a novel hybrid and biodegradable high-k gate dielectric material system based on a cellulose derivative for low-voltage complementary organic circuits with exceptional high noise margins.35 Previous work done in our laboratories demonstrated the fabrication feasibility of complex circuits, where the electrode patterning was performed by a self-aligned photolithography technique.44, 45 This process can easily be transferred to an anodized aluminum (Al2O3) + trimethylsilyl cellulose (TMSC) based bilayer system; the respective results will be published soon. To follow on this preliminary work we have developed an extraordinarily well-performing complementary inverter technology based on a hybrid dielectric composed of a bilayer of alumina (Al2O3) and trimethylsilyl cellulose (TMSC) and pentacene or C60 for the p-channel and the n-channel organic semiconductor, respectively. It outperforms any inverter reported so far with respect to the combination of excellent key parameters, such as record DC gain of above 500 V/V, low operation voltage of only 4 V, and large noise margin up to 92.5%. In order to clarify the origin for this high performance, special attention is given to the investigation of the semiconductor–dielectric interface, the semiconductor morphology, the nature of traps, the influence of mobility levels on the inverter performance and its long-term stability. This article is not meant to report new materials and systems, but rather find explanations and present a thorough analysis of the extraordinary performance of the cellulose derivative (TMSC) dielectric and the TMSC to semiconductor interface in organic field-effect transistors and simple inverter circuits. All OTFTs presented in this work have a bottom gate, top contact device architecture, as illustrated in Figure 1a. The transistor fabrication process is described in detail in the Experimental Section. The semiconducting layer is pentacene for p-type and C60 (fullerene) for n-type conduction. For the gate dielectric, an inorganic (Al2O3)–organic (TMSC) bilayer is chosen with 28 and 30 nm layer thickness, respectively. The dielectric properties of both single-layer TMSC films and bilayer Al2O3 + TMSC films, were investigated by current–voltage (I(V)), capacitance–frequency (C(f)), and capacitance–voltage (C(V)) measurements in appropriate capacitor structures with 72 nm insulator layer thickness of pure TMSC and 28 + 30 nm of bilayer film of Al2O3 + TMSC, respectively. In Figure 1b, the I(V) curves of a representative capacitor formed by a single layer cellulose dielectric is shown, whereas in Figure S1a (in the Supporting Information) the curve with bilayer dielectric is displayed. A comparison of I(V) curves of a single layer and bilayer dielectric is displayed in Figure 1c. At an electric field of 3.0 MV cm−1 (equivalent to ≈22 V) a current density on the order of 10−6 A cm−2 is observed for the single-layer TMSC. A breakdown field of 4.5 ± 0.3 MV cm−1 is extracted from eight appropriate capacitor structures. One representative C(V) measurement is displayed in Figure 1d. Its capacitance of about 29 nF cm−2 corresponds to a dielectric constant of εR = 2.4 ± 0.2 at 1 kHz with an excellent stability at frequencies down to 0.5 mHz (virtually flat dielectric constant and low dielectric losses which are indicative of a high purity and negligible amount of mobile ionic species) as illustrated in Figure 1e.46 In comparison, capacitors based on the bilayer dielectric have three orders of magnitude lower leakage currents (≈10−9 A cm−2) at an electric field of 3.0 MV cm−1 corresponding to ≈17.5 V and an effective capacitance of 53 nF cm−2 at 1 kHz (see Figure S1a,b, Supporting Information). As can be derived from Figure S1c (in the Supporting Information) the permittivity of the bilayer dielectric also shows excellent stability over the tested frequency range (1 mHz to 10 kHz). The measured capacitance value of the dielectric is in good agreement with calculations by assuming a permittivity of 9 and a thickness of 28 nm for the Al2O3 layer as well as a measured permittivity of 2.4 ± 0.2 (Figure 1e) and 30 nm thickness for the TMSC layer (see the Experimental Section). In any OTFT with bottom gate architecture the surface properties of the gate dielectric (surface energy, surface roughness) decisively affect the arrangement and growth of small molecule semiconductors. The surface energy of spin-coated TMSC thin films was determined by contact angle measurements. With a water contact angle of 98.5°, TMSC can be regarded as a hydrophobic, low energy surface material with a total surface energy of γ = 24.2 ± 0.6 mN m−1, separable in a small polar component γP = 1.8 ± 0.5 mN m−1 and a dispersive component γD = 22.4 ± 0.1 mN m−1. The average surface roughness, indicated by the root mean square (rms)–roughness values, was found to be only 0.77 ± 0.1 nm by atomic force microscopy (AFM) measurements. On this smooth and low energy TMSC surface, a small-grain growth mode with average grain sizes between 150 and 300 nm for pentacene (shown in Figure 1a) and 50 nm for C60 was observed by AFM measurements. In Figure 2, typical electrical characteristics of OTFTs with either C60 or pentacene as the semiconducting layer are plotted. Both p- and n-type transistors are based on the inorganic–organic bilayer gate dielectric composed of Al2O3 and TMSC. The output characteristics ID(VDS) are displayed in Figure 2a,b, whereas the transfer characteristics ID(VGS) are shown in Figure 2c,d. Both transistor types display very small hysteresis between forward and reverse voltage sweeps. The output characteristics show clear saturation, but for the pentacene-based OTFT a non-linear behavior of the drain current at very low drain voltages is observable (Figure 2b). Such an S-shape of the output curve has been already observed and reported for many different device configurations and has sometimes been attributed to a lateral field dependent contact resistance.47-55 In Table 1, the critical device parameters Von (onset voltage), Vthr (threshold voltage), S (subthreshold swing), μlin (charge carrier mobility in the linear regime), and μsat (charge carrier mobility in the saturation regime) are compiled and averaged over eight devices for each transistor type. On average, C60-based OTFTs show a charge carrier mobility of 0.7 cm2 V−1 s−1 in the saturation regime, a threshold voltage of 1.3 V, and a small subthreshold swing of 305 mV dec−1. Pentacene-based OTFTs have on average a mean threshold voltage of −4.7 V, a very small subthreshold swing of 225 mV dec−1, and a field-effect mobility of 0.22 cm2 V−1 s−1 in the saturation regime. The gate leakage currents are very low and in the range of 10−10 A. The balanced performance of our p- and n-type OTFTs, as well as the fact that both transistor types strictly behave as normally off transistors at zero applied gate voltage is a good base for integrating them in complementary organic inverters. A schematic image of such a complementary inverter circuit is displayed in Figure 3a together with the voltage transfer characteristics (VTCs) of a typical device and the static gain measured for operation voltages of VDD = 4, 5, 6, and 7 V. The inverter exhibits extraordinarily high small-signal gains; for all operation voltages, gains above 500 V/V are measured with a maximum value of about 1000 V/V for VDD = 7 V. The best performing device even has a maximum gain value of 1600 V/V. Moreover, a very sharp transition regime (ΔVin ≤ 40 mV) and a full rail-to-rail swing are observed. The extracted inverter parameters are compiled in Table 2. The switching threshold voltages VM are found to be very close to the ideal value of VDD/2 at all operation voltages with a nearly perfect fit (e.g., VM = 2.04 V at VDD = 4 V). In Figure 3b, the mismatches of the threshold voltages to the ideal values (ΔVM) are plotted as a function of VDD revealing a linear increase of ΔVM with the supply voltage. This means that the asymmetry of the VTCs increase with increasing the operation voltages. Additionally, the noise margins (NM) are plotted in Figure 3b as a function of VDD, illustrating the linear decrease of the NM with increasing operation voltage. Such a behavior reveals the direct correlation between ΔVM and NM and is an indication of the deviation of the VTCs from perfect symmetry. The noise margin is an important figure of merit of an inverter stage and measures the immunity against inevitable transistor parameter variations and electrical noise.56 There are several ways to determine the noise margin of an inverter. One convenient way is called the “maximum equal criterion” (MEC), where the NM is found by the maximum square that fits between inverter transition curve and the mirrored inverter curve as shown in Figure 3c.22, 35 The NM values for all the supplied voltages are listed in Table 2. The noise margin is mainly limited by the steepness of the transition ΔVin and the position of the switching threshold voltage VM (VM = Vin = Vout) as shown in Figure 3c. High and balanced noise margins are found when the ideal condition VM = VDD/2 is met, thus when VM = Vin =VDD/2 = Vout. The inverter in Figure 3c has a NM of 1.79, which is 90% of the maximum theoretical value for a supply voltage of 4 V, determined by the “maximum equal criterion.” Additionally, the “negative slope criteria” reveals a balanced NM of 1.85 V (92.5%) for a supply voltage of 4 V. The OTFTs with pentacene and C60 semiconductor layers (as used in the complementary inverters) were also analyzed with regard to their long-term stability. The dependence of their onset voltage and charge carrier mobility on the time period after preparation is plotted in Figure 4 based on measurements of at least five devices for each transistor type. The error bars display the standard deviations. p- and n-type devices exhibit an onset voltage shift of +1.3 and +0.95 V, respectively, over a period of 45 days. The main part of the shift occurred either after the first or after the second measurement and then the onset voltage shift tended to saturate. It seems that both pentacene- and fullerene-based devices stabilized their electrical properties after few days. Between day 8 and day 45 no significant change in the transfer characteristics was observed. Concerning the subthreshold swing, no significant change was observed over 45 days (S = 215 mV dec−1 (0 days), 210 mV dec−1 (8 days), and 225 mV dec−1 (45 days)) in the pentacene OTFTs, indicating that the interface trap density is stable. On the contrary, after 8 days an increase of the swing was observed for the C60 devices from 305 mV dec−1 (0 days), to 410 mV dec−1 (8 days), to 430 mV dec−1 (45 days). The mean value of the charge carrier mobility of the pentacene OTFTs showed no significant variation over 45 days: 0.22 cm2 V−1 s−1(fresh sample), 0.19 cm2 V−1 s−1 (after 8 days), 0.21 cm2 V−1 s−1 (after 45 days). In contrast, a strong reduction of about one order of magnitude (from 0.7 to 0.06 cm2 V−1 s−1 within the first 8 days and to 0.05 cm2 V−1 s−1 after 45 days) was observed for the fullerene transistors. In order to test the reliability of our OTFT devices we have also performed negative and positive bias stress tests. The bias stress was done 1 day after fabrication, on devices which had been previously measured only once. A reversible negative onset voltage shift of about 400 mV was observed under negative bias of −7.5 V over 21 hours stress (see Figure 5a,b) The main part of the negative voltage shift occurred during the first 2 hours (300 mV) whereas shift saturation was reached after 6 hours. The positive bias stress resulted in a significantly smaller positive onset voltage shift (ca. +100 mV over 4 hours stressing the device). Devices that were stored for seven months in the glovebox showed no bias stress effect at all (i.e., shift of the onset voltage) when their transistor characteristics were measured at regular intervals during the storage period. In order to investigate the “long-time” behavior of complementary inverters, electrical measurements were done after 1, 4, 8, and 45 days of the respective device preparation. Inverters were measured 1 day after device stabilization (see Figure 4a,b). The “long-time” behavior of complementary inverters is shown in Figure 4c,d where the VTC and gain curves are plotted as a function of time. For the lowest VDD of only 4 V, a small shift of the switching threshold voltage was measured: starting from 2.04 V after 1 day to an identical value of 2.17 V after 8 and 45 days, respectively, with a related exceptional high noise margin of 1.79 V (90% of the theoretical maximum) after 1 day and 1.74 V (87%) after 8 and 45 days. It is interesting to note that, after 8 days of storage time, the hysteresis in inverter characteristics was virtually negligible (<100 mV, see Figure 4d) and moreover, repeated measurements did not change the inverter transition, although the gain was somewhat reduced (from 503 (0 days) to 320 (8 days) and 195 (45 days)). The operational stability of the VTC was shown over a period of at least 45 days (Figure 4c for VDD = 4 V). Furthermore, the remarkable long-term stability of these TMSC-based complementary inverters was demonstrated by 16 consecutively recorded inverter curves that are virtually superimposed over one another (Figure 5c). The current–voltage characteristics show that the Al2O3 + TMSC bilayer capacitors have substantially lower leakage currents than the single TMSC layer devices. Due to the roughness of the aluminum bottom electrode with spikes up to 10 nm, the anodization process is a convenient method to reduce the leakage currents for at least three orders of magnitude at an electric field of 3 MV cm−1 as displayed in Figure 1d and make the dielectric layer more robust.57 Another advantage of the anodization step is the substitution of the hydroxide of the native oxide layer. Finally, the subsequent short oxygen plasma treatment (see the Experimental Section) is sufficiently removing all residuals left after the anodization process. This procedure allows for the generation of a pure and trap-reduced dielectric interface to the organic semiconductors, by measurements at low revealing a virtually flat permittivity in the mHz to kHz frequency range and low dielectric losses which both are indicative of a high purity and negligible amount of mobile ionic The generation of this excellent interface is in virtually hysteresis-free characteristics of all the One important that the performance of OTFTs, and in the charge carrier is the of the As shown by several the of the surface energy of the to that of the is one important the growth For a low surface energy material with a smooth surface TMSC, a growth mode is and with a rather high density and small grain sizes are formed (see Figure The high density of grain a significant decrease of the charge carrier since grain as charge On the a better between pentacene on low surface energy materials TMSC with and better reduce the of trap thus the mobility of charge in the In there is an between grain related and interface with regard to their influence on charge carrier The low subthreshold swing observed in all our pentacene-based OTFTs is indicative of a low interface trap density which the influence of the large grain trap density on the charge carrier Accordingly, a mobility 0.2 cm2 V−1 s−1 is observed in the p-type devices. In C60 films, the influence of on the charge carrier mobility is by far not as significant as in pentacene films, which is attributed to the of the fullerene In the pentacene OTFTs (see Figure a non-linear current increase in the linear regime of the ID(VDS) output characteristics is at higher gate have been in to such a which can be observed in bottom gate The explanations i) the of the charge carrier mobility for semiconductor ii) currents that the of the mobile by an effective under the drain and iii) large at the electrode from an energy between the work of contact material and semiconductor films, a gate or large contact are found in our of these it has been shown that a mobility in combination with a small contact in a non-linear drain voltage dependence of the current due to The from a of from trap and a dependence of on the drain A respective of the pentacene output curve in Figure the dependence in the regime 2 V, thus indicating that a mobility has to be The of any hysteresis in the I(V) curves and the low and value of the subthreshold swing a low density of interface in the pentacene are not for the observed and the of the as by the of the pentacene layer gives rise to which to a field dependence of the charge carrier This is all the more given that the pentacene grain sizes are 300 nm at a large density of grain As by Figure 4 the characteristics of both pentacene- and C60-based OTFTs show a positive onset voltage shifts storage which after a of measurements. The virtually subthreshold swing in pentacene as well as the negligible hysteresis as the origin of the On the contrary, it seems that trap are for the positive onset voltage shift in are either over time or during the first measurements by the applied positive gate be easily by the gate bias and therefore are not to the swing, but the small onset voltage in pentacene-based It has been reported by many that the of the of trap in pentacene trap also be due to such as at the a at the or a at the fabrication and transfer from the to the measurement stage the semiconductor layer and rise to such For oxygen can even the devices are to but transferred directly and measured in a glovebox with reduced oxygen and water have also observed that the of oxygen with pentacene is in the that these are under device operation with the of oxygen in the grain observed that the storage of devices in and their subsequent measurement in did not a change in their I(V) also observed that the storage time to the first measurement has influence on the device (i.e., on the onset voltage in this of and the first measurement the of to the of oxygen or with the which in a second are by Moreover, also are are not as in the as the (see and This an for the positive shift of the onset voltage between first and second measurement (Figure and also for the saturation of the onset voltage shift in In order to clarify which of are present in our we performed measurements on pentacene films (in and after storage in for (see Figure Supporting Information). storage under a small increase of the at energy is observed that can be attributed to the to and The analysis reveals an increase of the from 0.2 to At the position no change is that trap in our devices for bias stress and the positive onset voltage can mainly be attributed to It be that the of any mobility in pentacene OTFTs against an of pentacene both are to oxygen For the C60 transistors, one a strong decrease of the charge carrier mobility during 8 days of storage which is by all over the device grain This is a effect of The decrease in charge carrier mobility and the at the interface that the subthreshold swing is in a positive onset voltage shift of the C60 transistors. With respect to the complementary inverters, noise margin values beyond from the maximum theoretical value for all supply voltages are and the high operational of the OTFT devices. At a very low supply voltage of 4 V, our bilayer organic complementary inverters have a static gain of more than 500 V/V with a noise margin of 92.5%, which is already reported devices with architecture (see the of inverter performance given in 38 and also gain values above 1000 V/V values up to 1600 were measured for our devices. This is all the most as the charge carrier mobility values of the transistors are not thus the that the of the mobility values between p- and n-channel with the virtually hysteresis are the factors for high gain and high noise margin Accordingly, a mobility 1 be the the is not high ≤ it can be by and p-channel transistors with different In our the mobility is The static of a complementary inverter is determined by technology parameters, the parameters of p- and n-type transistors. A good of these parameters a good saturation of both output can to a significant increase of the gain A is shown in the Supporting Furthermore, high gain values are also determined by the interface An insulator with an low trap density (as this is the for is in having I(V) curves with virtually zero Accordingly, it is to measurements with a very high voltage small voltage thus one to the high gain value of the complementary inverter it by hysteresis The noise margin with increasing VDD due to their strong this is also for the of the VTCs by see Figure A for this behavior can be found in the bias stress that was observed for both types of transistors. The negative shift of Von under negative gate and the positive

Modeling of bias-induced changes of organic field-effect transistor characteristics

We report ambipolar organic field effect transistors (OFETs) and complementary inverters based on polyazine containing diketopyrrolopyrrole (PBTDAZ). PDBTAZ OFETs showed well-balanced electron and hole mobilities of 0.13 and 0.12 cm2/(V·s) at a low annealing temperature of 100oC using bottom-contact, top-gate geometry with a CYTOPTM gate dielectric layer. The mobilities were improved to 0.56 cm2/(V·s) by thermal annealing (150°C). The ambipolar complementary-inverter-based PDBTAZ OFETs showed ideal Vinv near half of VDD with a high gain of 15∼20 due the well-balanced electron and hole mobilities.

Fabrication of ambipolar organic field-effect transistors (OFETs) is essential for the achievement of an organic complementary logic circuit. Ambipolar transports in OFETs with heterojunction structures are realized. We select pentacene as a P-type material and N,N′-bis(4-trifluoromethylben-zyl)perylene-3,4,9,10-tetracarboxylic diimide (PTCDI-TFB) as a n-type material in the active layer of the OFETs. The field-effect transistor shows highly air-stable ambipolar characteristics with a field-effect hole mobility of 0.18 cm2/(V.s) and field-effect electron mobility of 0.031 cm2/(V.s). Furthermore the mobility only slightly decreases after being exposed to air and remains stable even for exposure to air for more than 60 days. The high electron affinity of PTCDI-TFB and the octadecyltrichlorosilane (OTS) self-assembly monolayer between the SiO2 gate dielectric and the organic active layer result in the observed air-stable characteristics of OFETs with high mobility. The results demonstrate that using the OTS as a modified gate insulator layer and using high electron affinity semiconductor materials are two effective methods to fabricate OFETs with air-stable characteristics and high mobility.

Organic semiconductors have unique properties compared to traditional inorganic materials such as amorphous or crystalline silicon. Some important advantages include their adaptability to low-temperature processing on flexible substrates, low cost, amenability to high-speed fabrication, and tunable electronic properties. These features are essential for a variety of next-generation electronic products, including low-power flexible displays, inexpensive radio frequency identification (RFID) tags, and printable sensors, among many other applications. Accordingly, the preparation of new materials based on π-conjugated organic molecules or polymers has been a central scientific and technological research focus over the past decade. Currently, p-channel (hole-transporting) materials are the leading class of organic semiconductors. In contrast, high-performance n-channel (electron-transporting) semiconductors are relatively rare, but they are of great significance for the development of plastic electronic devices such as organic field-effect transistors (OFETs). In this Account, we highlight the advances our team has made toward realizing moderately and highly electron-deficient n-channel oligomers and polymers based on oligothiophene, arylenediimide, and (bis)indenofluorene skeletons. We have synthesized and characterized a "library" of structurally related semiconductors, and we have investigated detailed structure-property relationships through optical, electrochemical, thermal, microstructural (both single-crystal and thin-film), and electrical measurements. Our results reveal highly informative correlations between structural parameters at various length scales and charge transport properties. We first discuss oligothiophenes functionalized with perfluoroalkyl and perfluoroarene substituents, which represent the initial examples of high-performance n-channel semiconductors developed in this project. The OFET characteristics of these compounds are presented with an emphasis on structure-property relationships. We then examine the synthesis and properties of carbonyl-functionalized oligomers, which constitute second-generation n-channel oligothiophenes, in both vacuum- and solution-processed FETs. These materials have high carrier mobilities and good air stability. In parallel, exceptionally electron-deficient cyano-functionalized arylenediimide derivatives are discussed as early examples of thermodynamically air-stable, high-performance n-channel semiconductors; they exhibit record electron mobilities of up to 0.64 cm(2)/V·s. Furthermore, we provide an overview of highly soluble ladder-type macromolecular semiconductors as OFET components, which combine ambient stability with solution processibility. A high electron mobility of 0.16 cm(2)/V·s is obtained under ambient conditions for solution-processed films. Finally, examples of polymeric n-channel semiconductors with electron mobilities as high as 0.85 cm(2)/V·s are discussed; these constitute an important advance toward fully printed polymeric electronic circuitry. Density functional theory (DFT) computations reveal important trends in molecular physicochemical and semiconducting properties, which, when combined with experimental data, shed new light on molecular charge transport characteristics. Our data provide the basis for a fundamental understanding of charge transport in high-performance n-channel organic semiconductors. Moreover, our results provide a road map for developing functional, complementary organic circuitry, which requires combining p- and n-channel transistors.

This thesis describes the study of the development and device physics of organic field-effect transistors and organic light-emitting field-effect transistors. Using chemical and physical properties of organic semiconductors such as light emission, multi-functional devices, or “Active Channel Field-Effect Transistors” can be created. This thesis first describes the creation of basic ambipolar FETs before building on this knowledge to develop ambipolar as well as hole-dominated light emitting field-effect transistors. Ambipolar FETs using a diketopyrrolopyrrole-based copolymer were first investigated in this thesis. When gold electrodes were used, the devices could transport only holes. The charge injection was altered by changing the contacts to aluminium. The devices then were able to conduct both electrons and holes with maximum electron and hole mobilities of order 10−4 cm2 V−1 s−1 and 10−3 cm2 V−1 s−1 respectively. Light-emitting field-effect transistors were first studied using the model emissive polymer Super Yellow. Charge injection was studied by altering the electron-injecting contact. Materials used included the low work function metals Ca, Ba and Sm, the inorganic salt Cs2CO3 and the organic material TPBi. Ambipolar devices were created using a neat Super Yellow layer. Electron and hole mobilities in these devices were both of the order of 10−4 cm2 V−1 s−1. The maximum external quantum efficiency was 1.2 ± 0.2 % with a Sm electron-injecting contact, however this occurred at a brightness of less than 1 cd m−2. A maximum brightness of 43 ± 9 cd m−2 was obtained using a Cs2CO3-Ag electron-injecting contact in electron accumulation mode. At this brightness, the external quantum efficiency was 0.19 ± 0.04 %. Unipolar devices were also fabricated by adding high mobility charge transport layer of PBTTT underneath the Super Yellow. Since PBTTT had a hole mobility that was orders of magnitude greater than the charge carrier mobilities of Super Yellow, charges were transported in the PBTTT, and recombined within the Super Yellow layer. Super Yellow acted as an emissive layer only. Using this bilayer device architecture, a maximum brightness of 100 ± 4 cd m−2 was obtained with a Ca electron-injecting contact. An external quantum efficiency of 0.04 ± 0.01 % was achieved at the maximum brightness. In order to improve the external quantum efficiency of LEFETs, phosphorescent materials were chosen for use as the emissive layer. A co-evaporated layer of the iridium complex Ir(ppy)3 in a host of CBP was initially used in the devices. Charge injection was studied by using either a Ba or a TPBi/Ba electron-injecting contact. Devices were first fabricated using PBTTT as a hole-dominated charge transport layer. Using a TPBi/Ba electron-injecting contact, the maximum brightness achieved was 200 ± 40 cd m−2 with an external quantum efficiency of 0.18 ± 0.01 % at the maximum brightness. Devices were then fabricated using a charge transport layer of DPP-DTT to create ambipolar devices. Electron and hole mobilities in these devices were both of order 10−2 cm2 V−1 s−1. The maximum external quantum efficiency was 0.4 ± 0.2 % at the maximum brightness of 500 ± 200 cd m−2 in hole accumulation mode using an electron-injecting contact of TPBi/Ba. In order to avoid using a co-deposited emissive layer, a solution-processed iridium-cored dendrimer layer that could be deposited without a host material was used. Like in the previous work, a charge transport layer of PBTTT was deposited underneath the emissive layer. Charge injection in the devices was altered using a change in the device geometry. Non-planar source and drain contacts were used, where one contact was deposited directly on top of the charge transport layer and the other contact on top of the emissive layer. Planar contacts were also used as control devices. There was clear evidence for transport of both holes and electrons when planar contacts were used, with light emission occurring at both contacts. The maximum mobility, brightness and external quantum efficiency was achieved using the non-planar contact geometry. Holes could be directly injected into the charge transport layer, rather than via the emissive layer. The hole mobility in these devices was 3.5 × 10−3 ± 6 × 10−4 cm2 V−1 s−1. The maximum brightness was 140 ± 50 cd m−2 with an external quantum efficiency of 0.11 ± 0.02 % at the maximum brightness. This thesis describes work on the study of charge injection into organic field-effect transistors by changing either the material used for the electron-injecting contact, or by changing the device geometry. This was achieved in devices that were either dominated by holes, or showed evidence of both electron and hole transport within the device. By changing the charge injection into the device, it was possible to improve the charge carrier mobilities, the brightness or the external quantum efficiency. Improving one or more of these things brings light emitting transistors towards becoming a viable technology.

The properties of solution-processed top-gate-type n-channel organic field-effect transistors (OFETs) utilizing perylene dimide derivative films with silver (Ag) source/drain (S/D) electrodes are investigated. With an increase in the annealing temperature, the electron transport characteristics are improved. The increase in grain size leads to an increase in electron field-effect mobility. An OFET with Ag-nanowire (AgNW) S/D electrode fabricated on a polymer substrate exhibits n-channel characteristics with electron field-effect mobility of 0.04 cm 2 V -1 s -1 in air. We demonstrate the possibility of producing flexible and air-stable n-channel OFETs using AgNW electrodes.

Organic Field Effect Transistors (OFET) possess wide applications in large area electronics owing to their attractive features like easy fabrication process, light weight, flexibility, cost effectiveness etc. But instability, high operational voltages and low carrier mobility act as inhibitors to commercialization of OFETs and various approaches were tried on a regular basis so as to make it viable. In this work, Poly 3-hexylthiophene-2,5diyl (P3HT) based OFETs with bottom-contact top-gate configuration using Poly vinyl alcohol (PVA) and Poly (methyl methacrylate) (PMMA) as gate dielectrics, aluminium and copper as source-drain electrodes are investigated. An effort is made to compare the effect of these dielectric materials and electrodes on the performance of OFET. Also, an attempt has been made to optimize the channel width of the device. These devices are characterised with mobility (μ), threshold voltage (VT), on-off ratio (Ion/Ioff) and their comparative analysis is reported.

The charge carrier transport in organic field effect transistors (OFETs) is determined by the transport properties of the insulator / organic semiconductor interface. We demonstrate that an adequate treatment of this interface results in a polarity change of the OFET charge carrier transport properties, without further altering the device structure. Illuminating the utilized PMMA polymer dielectric, by using UV radiation, leads to the introduction of mainly electron traps at the dielectric interface. This results in the suppression of the electron transport for an otherwise n-type pentacene OFET. However, as a consequence of trapped electrons in the near surface layer of the PMMA dielectric, the hole transport of the device is enabled though a hole blocking source/drain metallization. This effect, as well as the impact of the UV irradiation on the PMMA dielectric will be discussed in detail. The UV treatment yields a PMMA interface rich on polar groups. The influence of these groups on the OFET characteristics is investigated by studying several polymer dielectrics with varying content of the emerging groups.

We have investigated the scaling of top-gate (TG)/bottom-contact (BC) pentacene-based organic field-effect transistor (OFET) with amorphous rubrene (α-rubrene) gate insulator utilizing lift-off processes for source/drain (S/D) and gate patterning. The TG/BC OFETs with the channel length below 10 μm were successfully fabricated. The fabrication yield of 100% was achieved for the OFET with minimum channel length of 2.3 μm by using the Au-7.4%Ge S/D electrodes. The mobility of 5.1 × 10–3 cm2 V−1 s−1 was obtained for the TG/BC OFET with channel length of 2.3 μm. However, it was found that the device characteristics markedly degraded below the channel length of 6.5 μm. This was probably due to the defective region in the pentacene channel formed at the S/D regions with approximately 3 μm width from both sides of the S/D interface. The back-gate OFET with the channel length of 2.4 μm did not show the remarkable degradation. Therefore, the worse interface properties at α-rubrene gate insulator and defective region caused the degradation of scaled pentacene-based TG/BC OFET characteristics.

We fabricate N, N'-ditridecylperylene-3,4,9,10-tetracarboxylic diimide and pentacene heterostructure organic field effect transistors with a MoO3 ultrathin layer between Al source-drain electrode and active layer. By inserting the MoO3 layer, the injection barrier of hole carriers is lowered and the contact resistance is reduced. Thus, the performance of the device is improved. The device shows typical ambipolar transport characteristics with effective hole mobility of 4.838 × 10−3 cm2/V·s and effective electron mobility of 1.909 × 10−3 cm2/V·s, respectively. This result indicates that using a MoO3 ultrathin layer is an effective way to improve the performance of ambipolar organic field effect transistors.

Bimolecular recombination in ambipolar organic field effect transistors

The electrical characteristics of bottom-contact organic field-effect transistors fabricated with the air-stable n-type semiconductor N,N′-bis(n-octyl)-dicyanoperylene-3,4:9,10-bis(dicarboximide) (PDI-8CN2) are described. The mobility, threshold voltage, subthreshold swing, and Ion∕Ioff ratio(VDS=40V, VG=0∼40V) are 0.14cm2∕Vs, 1.6V, 2.0V/decade, and 1.2×103, respectively. The effect of electrode/dielectric surface treatment on these devices is also examined, with a combination of 1-octadecanethiol and hexamethyldisilazane. Organic complementary five-stage ring oscillators were fabricated using pentacene and PDI-8CN2, and operated at an oscillation frequency of 34kHz and a propagation delay per stage of 3μs.

We report the nonvolatile memory characteristics of pentacene-based organic field-effect transistors (OFET) using polystyrenepara-substituted with π-conjugated oligofluorenes (P(St-Fl)n (n = 1–3)) as chargeable polymer electrets. Effects of fluorene conjugated length on the surface structure and memory characteristics of pentacene OFET were investigated. Among these polymer electrets, the device with the P(St-Fl) exhibited the highest field-effect mobility of 0.47 cm2 V−1 s−1 due to the largest grain size of pentacene growth. The device with P(St-Fl)3 revealed the largest hysteresis window of 76 V due to it having the longest fluorene conjugation length among the studied electrets. The smallest difference of the HOMO energy level between pentacene and P(St-Fl)3 facilitated the charge transfer from pentacene to the polymer electret. The shifts on the transfer curves in both positive and negative directions could be reversibly controlled when applied an external gate bias of ±100 V for a short time (1 μs), indicating the fast trapping-detrapping ability of the polymer electrets. The devices showed excellent nonvolatile behaviors for bistable switching. The ON and OFF states were maintained over 104 s with the Ion/Ioff current ratio of 105–106. The write-read-erase-read (WRER) cycles could be operated over 100 cycles. This study suggested that surface characteristics, charge transport, and memory characteristics of pentacene-based OFET can be manipulated by polymer electrets with different pendent conjugation length.

Thioxanthene has been converted into 9-(1,3-dithiol-2-ylidene)thioxanthene derivatives which are new two-electron π-donors; an ambipolar OFET has been fabricated from the covalent 9-(1,3-dithiol-2-ylidene)thioxanthene–C60 diad system 6.