Stable organic thin-film transistors using full solution-processing and low-temperature sintering silver nanoparticle inks

We have fabricated electronically stable organic thin-film transistor (TFT) devices that are fully solution-processed and adopt printed electrodes using silver nanoparticles dispersed in organic solvents, whose sintering temperatures are 100 °C or less. The bottom-contact organic TFT devices showed good electrical characteristics, and exhibited threshold voltage shifts less than 2.0 V after applying a DC bias voltage stress for 10⁴ s, which is attributed to relatively low contact resistance. These results demonstrate the feasibility of producing stable organic TFTs that are fully solution-processed at relatively low temperatures, for use in large-area flexible electronics applications.     

High-performance n-channel thin-film transistors with acene-based semiconductors

Two acene-based semiconductors were investigated with respect to their performance as n-type materials in organic field-effect transistors. The partially fluorinated ditetracenes (Ditetracen is protected by copywrite through the Patent WO/2007/000268. The patent is property of the Dritte Patentportfolio Beteiligungsgesellschaft mbH & Co. KG.) (DT) were synthesized in a high yield with different degrees of fluorination, one with four and another with two fluorine substituents (named as DT-4F and DT-2F, respectively). Both materials exhibit high thermal stability, with decomposition temperatures above 500 °C. Since both materials are supposed to have a lowered LUMO level compared to the non-fluorinated parent DT, n-type operation in thin-film transistors (TFTs) with gold source and drain contacts was expected. TFTs based on DT-2F, however, showed weak ambipolar transport only, which demonstrates insufficient fluorination to switch from hole-dominated to electron-dominated transport. On the other hand, high performance n-type TFTs have been achieved from DT-4F, with electron mobilities up to 1.0 cm²/V s. This result indicates that fluorinated DT material can act as excellent n-type semiconductor for applications in complementary circuits. This is demonstrated in a complementary inverter stage using DT-4F-based TFTs as n-type transistor and a non-fluorinated DT derivative-based TFT as p-type transistor.     

Solution-processable and thermal-stable triphenylamine-based dendrimers with truxene cores as hole-transporting materials for organic light-emitting devices

Two solution processable π-conjugated triphenylamine-based dendrimers, Tr-TPA3 and Tr-TPA9 were served as hole-transporting materials (HTMs) for organic light-emitting devices (OLEDs). The two dendrimers exhibit similar absorption and emission behaviors in solutions and thin films, which demonstrate that these dendrimers can form amorphous states in their films. The dendrimers showed excellent solubility, which are soluble in common organic solvents such as chloroform, tetrahydrofuran, and 1,1,2,2-tetrachloroethane, high thermal stability with high glass-transition temperature (T_g) of 115 °C for Tr-TPA3 and 140 °C for Tr-TPA9, high the highest unoccupied molecular orbital (HOMO) energy level (?5.12 eV for Tr-TPA3 and ?4.95 eV for Tr-TPA9, respectively) and good film forming property. When we employed these dendrimers as hole transport layer (HTL) in tris-(8-hydroxyquinoline) aluminum (Alq₃)-emitting electroluminescence (EL) devices, the Tr-TPA9-based double-layer device exhibited the turn-on voltage of 2.5 V, the maximum luminance of about 11,058 cd m^?2 and the maximum current efficiency of 4.01 cd A^?1. The comparison of the properties between the EL devices with dendrimers as HTL and the EL device with 1,4-bis(1-naphthylphenylamino)biphenyl (NPB) as HTL indicated that this series of dendrimers can be good candidates for HTM in OLEDs.     

Complementary integrated circuits on plastic foil using inkjet printed n- and p-type organic semiconductors: Fabrication,characterization, and circuit analysis

Complementary thin-film transistor circuits composed of 6,13-bis(triisopropyl-silylethynyl) pentacene (TIPS–PEN) and a rylene carboxylic diimide derivative for p- and n-channel thin-film transistors (TFTs) were fabricated on flexible foils. The so-called staggered TFT configuration is used, meaning that the semiconductors layers are deposited last. The work-function of the injecting gold electrodes were modified using several self-assembled monolayers (SAMs). For optimized contacts the mobility of the n- and p-channel TFTs was 0.5 cm²/Vs and 0.2 cm²/Vs, respectively. Strongly degraded performance is obtained when the n-channel material was printed on contacts optimized for the p-channel TFT, and vice versa. This illustrates that for CMOS circuits we need careful work-function engineering to allow proper injection for both electrons and holes. We show for the first time that by using a bimolecular mixture for the SAM we can systematically vary the work function, and demonstrate how this affects the performance of discrete n-type and p-type transistors, as well as CMOS inverters and ring oscillators. Under optimal processing conditions we realized complementary 19-stage ring oscillators with 10 μs stage delay operating at 20 V.     

Scaling down of organic complementary logic gates for compact logic on foil

In this work, we realize complementary circuits with organic p-type and n-type transistor integrated on polyethylene naphthalate (PEN) foil. We employ evaporated p-type and n-type organic semiconductors spaced side by side in bottom-contact bottom-gate coplanar structures with channel lengths of 5 μm. The area density is 0.08 mm² per complementary logic gate. Both p-type and n-type transistors show mobilities >0.1 cm²/V s with V_on close to zero volt. Small circuits like inverters and 19-stage ring oscillators (RO) are fabricated to study the static and the dynamic performance of the logic inverter gate. The circuits operate at V_dd as low as 2.5 V and the inverter stage delay at V_dd = 10 V is as low as 2 μs. Finally, an 8 bit organic complementary transponder chip with data rate up to 2.7 k bits/s is fabricated on foil by successfully integrating 358 transistors.     

Reduced contact resistance and highly stable operation in polymer thin-film transistor with aqueous MoOx solution contact treatment

We report on a newly developed solution process using MoO₃ for reducing source and drain (S/D) electrodes in organic thin-film transistor (TFT). By taking advantage of the difference in surface wettability between the gate dielectric layer and the S/D electrodes, the electrode treatment using the MoO_x solution was applied to polymer TFT with short channel lengths less than 10 μm. The contact resistance was noticeably reduced at the interface of the S/D electrodes in a polymer TFT using a pBTTT-C16. Furthermore, the field effect mobility for this TFT was enhanced from 0.03 to 0.1 cm²/V s. Most notably, the threshold voltage (V_th) shift under gated bias stress was less than 0.2 V after 10⁵ s, which is comparable to that of conventional poly crystalline Si TFT.     

Ambipolar transport in transparent and flexible all-organic heterojunction field effect transistors at ambient conditions

We report on the realization of fully flexible and transparent n-type and ambipolar all-organic OFETs. A double layer, pentacene-C60 heterojunction, was used as the semiconductor layer. The contacts were made with poly(ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS) and patterned by means of Soft Lithography MicroContact Printing (μCP). Interestingly, as demonstrated by atomic force microscopy and X-ray diffraction investigations, growing C60 on a pre-deposited pentacene buffer layer leads to a clear improvement in the morphology and crystallinity of the deposited film allowing to obtain n-type conduction despite the very high electron injection barrier at the interface between PEDOT:PSS and C60. As a result, it was possible to realize n-type and ambipolar all-organic OFETs by optimizing the thicknesses of the pentacene buffer layer. All devices, measured in air, worked in accumulation mode with mobilities up to 1 × 10⁻² cm²/V s and 3.5 × 10⁻⁴ cm²/V s for p-type and n-type regimes, respectively. This is particularly interesting because it demonstrates, also for n-type and ambipolar transistors, the possibility of avoiding problems normally associated to metal contacts: the lack of mechanical robustness, flexibility, and the unfeasibility of realizing contacts with low cost techniques like printing or soft lithography. These results confirm the importance of the substrate properties for the ordered growth of organic semiconductors, which determines the transport properties of organic materials.     

Synergistic effect of polymer and oligomer blends for solution-processable organic thin-film transistors

The thin-film morphologies and thin-film transistor (TFT) characteristics of a series of binary blends of poly(9,9′-dioctylfluorene-alt-bithiophene) (F8T2) and α,ω-dihexylquarterthiophene (DH4T) are reported. The blends of F8T2 and DH4T exhibit good solubility and produce TFT devices with better performances than F8T2 and DH4T devices. The 50% DH4T blend device was found to have a hole mobility of 0.011 cm ² V⁻¹ s⁻¹, which is four times higher than the mobility of the F8T2 device, with a high-on/off ratio of about 10⁵ and a low-off current of 17 pA. The polymer and oligomer domains are phase-separated with large domain size and arranged in characteristic molecular alignments. It was found that carrier transport in the blend systems is mainly controlled by the polymer component, and that the nature of the blended oligomer affects the OTFT performance of the blends.     

Hybrid dual gate ferroelectric memory for multilevel information storage

Here, we report hybrid organic/inorganic ferroelectric memory with multilevel information storage using transparent p-type SnO semiconductor and ferroelectric P(VDF-TrFE) polymer. The dual gate devices include a top ferroelectric field-effect transistor (FeFET) and a bottom thin-film transistor (TFT). The devices are all fabricated at low temperatures (∼200 °C), and demonstrate excellent performance with high hole mobility of 2.7 cm² V⁻¹ s⁻¹, large memory window of ∼18 V, and a low sub-threshold swing ∼−4 V dec⁻¹. The channel conductance of the bottom-TFT and the top-FeFET can be controlled independently by the bottom and top gates, respectively. The results demonstrate multilevel nonvolatile information storage using ferroelectric memory devices with good retention characteristics.     

Fabrication of the flexible pentacene thin-film transistors on 304 and 430 stainless steel (SS) substrate

Flexible organic thin-film transistors (OTFT) were fabricated on 304 and 430 stainless steel (SS) substrate with aluminum oxide as a gate insulator and pentacene as an organic semiconductor. Chemical mechanical polishing (CMP) process was used to study the effect of the SS roughens on the dielectric properties of the gate insulator and OTFT characteristics. The surface roughness was decreased from 33.8 nm for 304 SS and 19.5 nm for 430 SS down to ～2.5 nm. The leakage current of the metal–insulator–metal (MIM) structure (Au/Al₂O₃/SS) was reduced with polishing. Mobility and on/off ratio of pentacene TFT with bare SS showed a wide range of values between 0.005 and 0.36 cm²/Vs and between 10³ and 10⁵ depending on the location in the substrate. Pentacene TFTs on polished SS showed an improved performance with a mobility of 0.24–0.42 cm²/Vs regardless of the location in the substrate and on/off ratio of ～10⁵. With self assembled monolayer formation of octadecyltrichlorosilane (OTS) on insulator surface, mobility and on/off ratio of pentacene TFT on polished SS was improved up to 0.85cm²/Vs and ～10⁶. I–V characteristics of pentacene TFT with OTS treated Al₂O₃/304 SS was also obtained in the bent state with a bending diameter (D) of 24, 45 or 70 mm and it was confirmed that the device performed well both in the linear regime and the saturation regime.     

Amorphous SiC as a structural layer in microbridge-based RF MEMS switches for use in software-defined radio

This paper reports an effort to develop amorphous silicon carbide (a-SiC) films for use in shunt capacitor RF MEMS microbridge-based switches. The films were deposited using methane and silane as the precursor gases. Switches were fabricated using 500 nm and 300 nm-thick a-SiC films to form the microbridges. Switches made from metallized 500 nm-thick SiC films exhibited favorable mechanical performance but poor RF performance. In contrast, switches made from metallized 300 nm-thick SiC films exhibited excellent RF performance but poor mechanical performance. Load-deflection testing of unmetallized and metallized bulk micromachined SiC membranes indicates that the metal layers have a small effect on the Young’s modulus of the 500 nm and 300 nm-thick SiC MEMS. As for residual stress, the metal layers have a modest effect on the 500 nm-thick structures, but a significant affect on the residual stress in the 300 nm-thick structures.     

Ferroelectric random access memory based on one-transistor–one-capacitor structure for flexible electronics

We have demonstrated a low temperature process for a ferroelectric non-volatile random access memory cell based on a one-transistor–one-capacitor (1T1C) structure for application in flexible electronics. The n-channel thin film transistors (TFTs) and ferroelectric capacitors (FeCaps) are fabricated using cadmium sulfide (CdS) as the semiconductor and poly(vinylidene fluoride-trifluoroethylene) [P(VDF-TrFE)] copolymer as the ferroelectric material, respectively. The maximum processing temperature for the TFTs is 100 °C and 120 °C for the FeCaps. The TFT shows excellent access control of the FeCap in the 1T1C memory cell, and the stored polarization signals are undisturbed when the TFT is off. The fabricated 1T1C memory cell was also evaluated in a FRAM circuit. The memory window on the bit line was demonstrated as 2.3 V, based on the 1T1C memory cell with a TFT having dimensions of 80 μm/5 μm (W/L) and a FeCap with an area of 0.2 × 10^?3 cm² using a bit line capacitor of 1 nF pre-charged at 17.2 V. The 1T1C memory cell is fabricated using photolithographic processes, allowing the integration with other circuit components for flexible electronics systems.     

AC characterization of organic thin-film transistors with asymmetric gate-to-source and gate-to-drain overlaps

This paper presents S-parameter characterization and a corresponding physics-based small-signal equivalent circuit for organic thin-film transistors (OTFTs). Furthermore, the impact of misalignment between the source/drain contacts and the patterned gate on the dynamic TFT performance is explored and a simple method to estimate the misalignment from the measured S-parameters is proposed. An excellent fit between theoretical and experimental S-parameters is demonstrated. For this study, OTFTs based on the air-stable organic semiconductor dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (DNTT) having a channel length of 1 μm and a gate-to-contact overlap of 5 or 20 μm and being operated at a supply voltage of 3 V are utilized. The intentional asymmetry between gate-to-source and gate-to-drain overlaps is precisely controlled by the use of high-resolution silicon stencil masks.     

High performance near infrared photosensitive organic field-effect transistors realized by an organic hybrid planar-bulk heterojunction

Compared with organic photodiodes, photoresponsive organic field-effect transistors (photOFETs) exhibit higher sensitivity and lower noise. The performance of photOFETs based on conventional single layer structure operating in the near infrared (NIR) is generally poor due to the low carrier mobility of the active channel materials. We demonstrate a high performance photOFETs operating in NIR region with a structure of hybrid planar-bulk heterojunction (HPBHJ). PhotOFETs with the structures of single layer [lead phthalocyanine (PbPc) or copper phthalocyanine (CuPc)], single planar heterojunction (PHJ) of CuPc/PbPc, double PHJ of CuPc/PbPc/3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) and HPBHJ of CuPc/PbPc:PTCDA were fabricated and characterized. It is concluded that the photOFET with HPBHJ structure showed superior performance compared to that with other structures, and for NIR light of wavelength 808 nm, the photOFET with HPBHJ structure exhibited a large photoresponsivity of 322 mA/W, a high external quantum efficiency of around 50%, and a maximal photosensitivity of 9.4 × 10². The high performance of HPBHJ photOFET is attributed to its high exciton dissociation efficiency and excellent hole transport ability. For 50-nm thick CuPc layer, the optimal thickness of the PbPc:PTCDA layer is found to be around 30 nm.     

Inkjet-printed copper electrodes using photonic sintering and their application to organic thin-film transistors

We report on copper (Cu) electrodes fabricated with inkjet-printed nanoparticle inks that are photonic sintered on a polymer dielectric layer and their application to source and drain electrodes in organic thin-film transistor (TFT). By using photonic sintering with a radiant energy density of 9 J/cm², printed Cu nanoparticle layers on a glass substrate showed very low electrical resistivity levels of 7 μΩ cm. By optimizing the sintering conditions on polymer dielectric, the pentacene-based TFT using these printed Cu electrodes showed good mobility levels of 0.13 cm²/Vs and high on/off current ratios of about 10⁶. In addition, we revealed that the crystal grain growth of pentacene near the printed Cu electrodes was inhibited by the thermal damage of polymer underlayer due to the high radiant energy density of the intense light.     

High-performance n-type organic field-effect transistors fabricated by ink-jet printing using a C60 derivative

We report on the performance of ink-jet-printed n-type organic thin-film transistors (OTFTs) based on a C₆₀ derivative, namely, C₆₀-fused N-methyl-2-(3-hexylthiophen-2-yl)pyrrolidine (C₆₀TH-Hx). The new devices exhibit excellent n-channel performance, with a highest mobility of 2.8 × 10^?2 cm² V^?1 s^?1, an I_On/I_Off ratio of about 1 × 10⁶, and a threshold voltage of 7 V. The C₆₀TH-Hx films show large crystalline domains that result from the influence of an evaporation-induced flow, thus leading to high electron mobility in the ink-jet-printed devices.     

Stably anodic green electrochromic aromatic poly(amine–amide–imide)s: Synthesis and electrochromic properties

A series of new poly(amine–amide–imide)s with pendent 4-methoxy-substituted triphenylamine (TPA) units having inherent viscosities of 0.35–0.45 dL/g were prepared from various aromatic bis(trimellitimide)s and the 4-methoxy-substituted triphenylamine-based aromatic diamine, 4,4′-diamino-4″-methoxytriphenylamine (I), by direct polycondensation. All the polymers are readily soluble in polar organic solvents. Flexible and amorphous films of these poly(amine–amide–imide)s could be obtained by solution-casting, and showed excellent thermal stability, 10% weight-loss temperatures in excess of 515 °C, and char yields at 800 °C in nitrogen higher than 58% associated with high glass-transition temperatures (297–305 °C). These polymers exhibited a maximum UV–vis absorption at 302–304 nm with fluorescence emission maxima around 360–376 nm in N-methyl-2-pyrrolidinone (NMP) solution. The hole-transporting and electrochromic properties were examined by electrochemical and spectroelectrochemical methods. Cyclic voltammograms of the poly(amine–amide–imide) films cast onto an indium–tin oxide (ITO)-coated glass substrate exhibit a reversible oxidation at 0.79–0.80 V vs. Ag/AgCl in acetonitrile solution, and reveal good stability of electrochromic characteristics with a color change from yellow to green at applied potentials ranging from 0.00 to 0.95 V. These anodically polymeric electrochromic materials not only showed excellent reversible electrochromic stability with good green coloration efficiency (CE = 395 cm²/C) but also exhibited high contrast of optical transmittance change (ΔT%) up to 78% in 768 nm. After over 100 cyclic switches, the polymer films still exhibited stable electrochromic characteristics.     

Role of Schottky barrier height at source/drain contact for electrical improvement in high carrier concentration amorphous InGaZnO thin film transistors

We report the fabrication of bottom-gate thin film transistors (TFTs) at various carrier concentrations of an amorphous InGaZnO (a-IGZO) active layer from ~10¹⁶ to ~10¹⁹ cm⁻³, which exceeds the limit of the concentration range for a conventional active layer in a TFT. Using the Schottky TFTs configuration yielded high TFT performance with saturation mobility (μ_sat), threshold voltage (V_TH), and on off current ratio (I_ON/I_OFF) of 16.1 cm²/V s, −1.22 V, and 1.3×10⁸, respectively, at the highest carrier concentration active layer of 10¹⁹ cm⁻³. Other carrier concentrations (<10¹⁹ cm⁻³) of IGZO resulted in a decrease of its work function and increase in activation energy, which changes the source/drain (S/D) contact with the active layer behavior from Schottky to quasi Ohmic, resulting in achieving conventional TFT. Hence, we successfully manipulate the barrier height between the active layer and the S/D contact by changing the carrier concentration of the active layer. Since the performance of this Schottky type TFT yielded favorable results, it is feasible to explore other high carrier concentration ternary and quaternary materials as active layers.     

High-resolution spatial control of the threshold voltage of organic transistors by microcontact printing of alkyl and fluoroalkylphosphonic acid self-assembled monolayers

A dense array of 500 organic TFTs with two different threshold voltages arranged in a checkerboard pattern has been fabricated. The threshold voltages were defined by preparing self-assembled monolayers (SAMs) of either an alkyl or a fluoroalkylphosphonic acid on the gate-oxide surface of each TFT, using a combination of microcontact printing from an elastomeric stamp and dipping into a solution. The threshold voltages are −1.01 ± 0.15 V for the TFTs with the fluoroalkyl SAM and −1.28 ± 0.23 V for the TFTs with the alkyl SAM. ToF-SIMS analysis shows that the two SAMs can be patterned with a pitch of 10 μm and without significant cross-contamination. Cross-sectional TEM and NEXAFS characterization of the SAMs indicate that the properties of the SAMs prepared by microcontact printing and dipping are essentially identical.     

High-current stressing of organic light-emitting diodes with different electron-transport materials

We conducted accelerated reliability tests of electron-only devices (EODs) and organic light-emitting diodes (OLEDs) differing only in their electron-transport material (ETM). High current stressing of EODs at 50 mA/cm² showed that Bphen ~ Alq₃ > TPBi > TAZ in terms of intrinsic material stability. In addition, the lowest unoccupied molecular orbital (LUMO) level and electron mobility have been identified as two other key material factors affecting the degradation rate of OLEDs. TAZ has a low electron mobility, a LUMO level misaligned with the Fermi level of the cathode, and poor material stability, leading to extremely poor reliability of devices with a TAZ electron-transport layer (ETL). In contrast, the OLED with a Bphen ETL exhibited more stable operation and a 76 × longer luminance lifetime. Due to its relatively high electron mobility and good stability as well as perfect energy level alignment with the cathode, Bphen has proven to be the most desirable ETM from the standpoint of OLED reliability.