Very facile fabrication of aligned organic nanowires based high-performance top-gate transistors on flexible,transparent substrate

Aligned single-crystalline organic nanowires (NWs) show promising applications in flexible and stretchable electronics, while the use of pre-existing aligned techniques and well-developed photolithography techniques are impeded by the large incompatibility with organic materials and flexible substrates. In this work, aligned copper phthalocyanine (CuPc) organic NWs were grown on flexible and transparent poly(dimethylsiloxane) (PDMS) substrate via a grating-assisted growth approach. Furthermore, a simple yet efficient etching-assisted transfer printing (ETP) method was used to achieve CuPc NW array-based flexible top-gate organic field-effect transistors (OFETs) with a high mobility up to 2.0 cm² V⁻¹ s⁻¹, a small operating voltage within ±10 V, a high on/off ratio >10⁴, and excellent bend stability with bending radius down to 3 mm. It is expected that the high-performance organic NW array-based top-gate OFETs with exceeding bend stability will have important applications in future flexible electronics.     

Solution-processed small molecules based on indacenodithiophene for high performance thin-film transistors and organic solar cells

Solution-processed indacenodithiophene (IDT)-based small molecules with 1,3-indanedione (ID) as terminal acceptor units and 3,3′-hexyl-terthiophene (IDT-3Th-ID(I)) or 4,4′-hexyl-terthiophene (IDT-3Th-ID(II)) as π-bridges, have been designed and synthesized for the application in organic field-effect transistors (OFETs) and organic solar cells (OSCs). These molecules exhibited excellent solubility in common organic solvents, good film-forming ability, reasonable thermal stability, and low HOMO energy levels. For the OFETs devices, high hole motilities of 0.52 cm² V⁻¹ s⁻¹ for IDT-3Th-ID(I) and 0.61 cm² V⁻¹ s⁻¹ for IDT-3Th-ID(II) were achieved, with corresponding high I_ON/I_OFF of ca. 10⁷ and ∼10⁹ respectively. The OSCs based on IDT-3Th-ID(I)/PC₇₀BM (2:1, w/w) and IDT-3Th-ID(II)/PC₇₀BM (2:1, w/w) without using any treatment of solvent additive or thermal annealing, showed power conversion efficiencies (PCEs) of 3.07% for IDT-3Th-ID(I) and 2.83% for IDT-3Th-ID(II), under the illumination of AM 1.5G, 100 mW/cm². The results demonstrate that the small molecules constructed with the highly π-conjugated IDT as donor unit, 3Th as π-bridges and ID as acceptor units, could be promising organic semiconductors for high-performance OFETs and OSCs applications.     

Dielectric surface-polarity tuning and enhanced operation stability of solution-processed organic field-effect transistors

The electrical performance of triethylsilylethynyl anthradithiophene (TES-ADT) organic field-effect transistors (OFETs) was significantly affected by dielectric surface polarity controlled by grafting hexamethyldisilazane and dimethyl chlorosilane-terminated polystyrene (PS-Si(CH₃)₂Cl) to 300-nm-thick SiO₂ dielectrics. On the untreated and treated SiO₂ dielectrics, solvent–vapor annealed TES-ADT films contained millimeter-sized crystals with low grain boundaries (GBs). The operation and bias stability of OFETs containing similar crystalline structures of TES-ADT could be significantly increased with a decrease in dielectric surface polarity. Among dielectrics with similar capacitances (10.5–11 nF cm⁻²) and surface roughnesses (0.40–0.44 nm), the TES-ADT/PS-grafted dielectric interface contained the fewest trap sites and therefore the OFET produced using it had low-voltage operation and a charge-carrier mobility ∼1.32 cm² V⁻¹ s⁻¹, on–off current ratio >10⁶, threshold voltage ∼0 V, and long-term operation stability under negative bias stress.     

Top-gate organic field-effect transistors fabricated on paper with high operational stability

We report on top-gate organic field-effect transistors (OFETs) fabricated on specialty paper, PowerCoat™ HD 230 from Arjowiggins Creative Papers coated with a buffer layer composed of a polyvinyl alcohol (PVA) and polyvinylpyrrolidine (PVP) blend. OFETs operate at low voltages and display average carrier mobility values of 1.7 ± 1.1 × 10⁻¹ cm²/Vs, average threshold voltage values of −1.4 ± 0.2 V, and average on/off current ratio of 10⁵. OFETs also display excellent operational stability demonstrated by stable 1000 scans of the transfer characteristics and by stable on-currents displaying less than 6% change during a DC bias stress test at V_DS = V_GS = −10 V for 1 h. Furthermore, OFETs on paper display a decrease of only 7% in their on-state current during a bending test. The performance of these OFETs on paper is comparable to that displayed by top-gate OFETs with the same geometry fabricated on glass substrates.     

D–A copolymer with high ambipolar mobilities based on dithienothiophene and diketopyrrolopyrrole for polymer solar cells and organic field-effect transistors

Donor–acceptor (D–A) type conjugated polymers have been developed to absorb longer wavelength light in polymer solar cells (PSCs) and to achieve a high charge carrier mobility in organic field-effect transistors (OFETs). PDTDP, containing dithienothiophene (DTT) as the electron donor and diketopyrrolopyrrole (DPP) as the electron acceptor, was synthesized by stille polycondensation in order to achieve the advantages of D–A type conjugated polymers. The polymer showed optical band gaps of 1.44 and 1.42 eV in solution and in film, respectively, and a HOMO level of 5.09 eV. PDTDP and PC₇₁BM blends with 1,8-diiodooctane (DIO) exhibited improved performance in PSCs with a power conversion efficiency (PCE) of 4.45% under AM 1.5G irradiation. By investigating transmission electron microscopy (TEM), atomic force microscopy (AFM), and the light intensity dependence of J_SC and V_OC, we conclude that DIO acts as a processing additive that helps to form a nanoscale phase separation between donor and acceptor, resulting in an enhancement of μ_h and μ_e, which affects the J_SC, EQE, and PCE of PSCs. The charge carrier mobilities of PDTDP in OFETs were also investigated at various annealing temperatures and the polymer exhibited the highest hole and electron mobilities of 2.53 cm² V⁻¹ s⁻¹ at 250 °C and 0.36 cm² V⁻¹ s⁻¹ at 310 °C, respectively. XRD and AFM results demonstrated that the thermal annealing temperature had a critical effect on the changes in the crystallinity and morphology of the polymer. The low-voltage device was fabricated using high-k dielectric, P(VDF-TrFE) and P(VDF-TrFE-CTFE), and the carrier mobility of PDTDP was reached 0.1 cm² V⁻¹ s⁻¹ at V_d = −5 V. PDTDP complementary inverters were fabricated, and the high ambipolar characteristics of the polymer resulted in an output voltage gain of more than 25.     

The role of water in the device performance of n-type PTCDI-C8 organic field-effect transistors with solution-based gelatin dielectric

Gelatin is a natural protein, which works well as the gate dielectric for N,N-dioctyl-3,4,9,10-perylene tetracarboxylic diimide (PTCDI-C₈) organic field-effect transistors (OFETs). An aqueous solution process was applied to form the gelatin gate dielectric on poly(ethylene terephthalate) (PET) by spin-coating and subsequent casting. The field-effect mobility in the saturation regime (μ_FE,sat) and the threshold voltage (V_T) values of a typical 40 nm PTCDI-C₈ OFET are (0.22 cm² V⁻¹ s⁻¹, 55 V) in vacuum and (0.74 cm² V⁻¹ s⁻¹, 2.6 V) in air ambient. The maximum voltage shift in hysteresis is also reduced from 10 V to 2 V when the operation environment for PTCDI-C₈ OFETs is changed from vacuum to air ambient. Nevertheless, a slight reduction of electron mobility was found when the device was stressed in the air ambient. The change in the device performance has been attributed to the charged ions generation owing to water absorption in gelatin in air ambient.     

Performance enhancement in mechanically stable flexible organic-field effect transistors with TIPS-pentacene:polymer blend

Flexible organic field-effect transistors (OFETs) with TIPS-pentacene: polystyrene (PS) blend are demonstrated to exhibit enhanced mobility and significantly improved electrical stability compared to neat TIPS-pentacene on poly(4-vinylphenol) (PVP) dielectric (bi-layer OFETs), along with high mechanical stability. Due to merit of high quality dielectric-semiconductor interface, pristine TIPS-pentacene: PS blend OFETs exhibited maximum mobility of 0.93 cm² V⁻¹ s⁻¹ with average of 0.44(±0.25) cm² V⁻¹ s⁻¹ compared to 0.14(±0.10) cm² V⁻¹ s⁻¹ for bi-layer OFETs with high current on-off ratios on the order 10⁵ for both. Both types of devices exhibited high electrical stability upon bending with increasing magnitude of strain or its duration up to 5 days. However, significant differences in electrical stability of devices were observed upon applying constant bias-stress for 40 min to 1 h. Pristine blend devices exhibited outstanding electrical stability with very low drain current decay of <5% compared to ∼30% for bi-layer devices. Even upon bias-stress after 5 days of bending, the drain current decay levels were only changed to <10% and ∼50% for blend and bi-layer devices respectively.     

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.     

Improving solution-processed n-type organic field-effect transistors by transfer-printed metal/semiconductor and semiconductor/semiconductor heterojunctions

Solution-processed n-type organic field effect transistors (OFETs) are in need of proper metal contact for improving injection and mobility, as well as balanced hole mobility for building logic circuit units. We address the two distinct problems by a simple technique of transfer-printing. Transfer-printed Au contacts on a terrylene-based semiconductor (TDI) significantly reduced the inverse subthreshold slope by 5.6 V/dec and enhanced the linear mobility by over 5 times compared to evaporated Au contacts. Hence, devices with a high-work-function metal (Au) are comparable with those with low-work-function metals (Al and Ca), indicating a fundamental advantage of transfer-printed electrodes in electron injection. We also transfer-printed a poly(3-hexylthiophene) (P3HT) layer onto TDI to construct a double-channel ambipolar transistor by a solution process for the first time. The transistor exhibits balanced hole and electron mobility (3.0 × 10⁻³ and 2.8 × 10⁻³ cm² V⁻¹ s⁻¹) even in a coplanar structure with symmetric Au electrodes. The technique is especially useful for reaching intrinsic mobility of new materials, and enables significant enlargement of the material tanks for solution-processed functional heterojunction OFETs.     

Low power flexible organic thin film transistors with amorphous Ba0.7Sr0.3TiO3 gate dielectric grown by pulsed laser deposition at low temperature

We deposited amorphous Ba_0.7Sr_0.3TiO₃ (BST) on silicon and plastic substrate under 110 °C by pulsed laser deposition (PLD) and use it as the dielectric of the organic transistor. Depends on the thickness of BST layer, the highest mobility of the devices can achieve 1.24 cm² V^?1 s^?1 and 1.01 cm² V^?1 s^?1 on the silicon and polyethylene naphthalate (PEN) substrate, respectively. We also studied the upward and downward bending tests on the transistors and the dielectric thin films. We found that the BST dielectric pentacene transistor can maintain the mobility at 0.5 cm² V^?1 s^?1 or higher while the bending radius is around 3 mm in both upward and downward bending. Our finding demonstrates the potential application of PLD growth high-k dielectric in the large area organic electronics devices.     

Natural polyelectrolyte: Major ampullate spider silk for electrolyte organic field-effect transistors

The major ampullate (MA) silk collected from giant wood spiders Nephila pilipes consists of 12% glutamic acid (Glu) and 4% tyrosine (Tyr) acidic amino residues. The MA silk may act as a natural polyelectrolyte for organic field-effect transistors (OFETs). Pentacene and F₁₆CuPc OFETs were fabricated with the MA silk thin film as the gate dielectric. The MA silk thin film with surface roughness of 4 nm and surface energy of 36.1 mJ/m² was formed on glass using a hexafluoroisopropanol (HFIP) organic process. The MA silk gate dielectric in pentacene OFETs may improve the field-effect mobility (μ_FE,sat) value in the saturation regime from 0.11 in vacuum to 4.3 cm² V⁻¹ s⁻¹ in air ambient at ca. 70% RH. The corresponding threshold voltage (V_TH) value reduced from −6 V in vacuum to −0.5 V in air ambient. Similar to other polyelectrolytes, the changes of μ_FE,sat and V_TH may be explained by the generation of electric double layers (EDLs) in the MA silk thin film in air ambient due to water absorption.     

Interface states in polyfluorene-based metal–insulator–semiconductor devices

Hybrid metal–insulator–semiconductor structures based on ethyl-hexyl substituted polyfluorene (PF2/6) as the active polymer semiconductor were fabricated on a highly doped p-Si substrate with Al₂O₃ as the insulating oxide layer. We present detailed frequency-dependent capacitance–voltage (C–V) and conductance–voltage characteristics of the semiconductor/insulator interface. PF2/6 undergoes a transition to an ordered crystalline phase upon thermal cycling from its nematic-liquid crystalline phase, confirmed by our atomic force microscope images. Thermal cycling of the PF2/6 films significantly improves the quality of the (PF2/6)/Al₂O₃ interface, which is identified as a reduced hysteresis in the C–V curve and a decreased interface state density (D_it) from ∼3.9 × 10¹² eV⁻¹ cm⁻² to ∼3.3 × 10¹¹ eV⁻¹ cm⁻² at the flat-band voltage. Interface states give rise to energy levels that are confined to the polymer/insulator interface. A conductance loss peak, observed due to the capture and emission of carriers by the interface states, fits very well with a single time constant model from which the D_it values are inferred.     

Solution-processed single-crystal perylene diimide transistors with high electron mobility

We have successfully demonstrated a single-crystal field-effect transistors (FETs) based on an asymmetric perylenetetracarboxylic diimide (a-PDI) compound with polystyrene (PS)/SiO₂ bilayer as gate dielectric. The single crystals are in-situ grown on substrate from simple solution evaporation method, thus may be suitable for large area electronics applications. The PS modified gate dielectric could minimize charge trapping by the hydroxyl groups of the SiO₂ surface. The resulting solution processed single crystals transistors are characterized in ambient air, and exhibited maximum electron mobility of ca. 1.2 cm² V⁻¹ s⁻¹ and high I_on:I_off > 10⁵.     

High electron mobility triazine for lower driving voltage and higher efficiency organic light emitting devices

The triazine compound 4,4′-bis-[2-(4,6-diphenyl-1,3,5-triazinyl)]-1,1′-biphenyl (BTB) was developed for use as an electron transport material in organic light emitting devices (OLEDs). The material demonstrates an electron mobility of ∼7.2 × 10⁻⁴ cm² V⁻¹ s⁻¹ at a field of 8.00 × 10⁵ V cm⁻¹, which is 10-fold greater than that of the widely used material tris(8-hydroxyquinoline) aluminum (AlQ₃). OLEDs with a BTB electron transport layer showed a ∼1.7–2.5 V lower driving voltage and a significantly increased efficiency, compared to those with AlQ₃. These results suggest that BTB has a strong potential for use as an OLED electron transport layer material.     

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.     

Organic field-effect transistor and its photoresponse using a benzo[1,2-b:4,5-b′]difuran-based donor–acceptor conjugated polymer

Organic field-effect transistors (OFETs) were fabricated through a solution process with a donor–acceptor (D–A) conjugated polymer poly{4,8-bis(2′-ethylhexylthiophene)benzo [1,2-b;3,4-b′]difuran-alt-5,5-(4′,7′-di-2-thienyl-5′,6′-dioctyloxy-2′,1′,3′-benzothiadiazole)} (PBDFTDTBT) as the active layer, which is a highly efficient D–A conjugated polymer as a donor in polymer solar cells with a power conversion efficiency (PCE) over 6.0%. The OFET devices showed a hole mobility of 0.05 cm²/Vs and an on/off ratio of 4.6 × 10⁵. Those are one of the best performance parameters for OFETs based on D–A conjugated polymers including benzo[1,2-b:4,5-b′]dithiophene (BDT) or benzo[1,2-b:4,5-b′]difuran (BDF) unit. The photoresponse of OFETs was investigated by modulating light with various intensities. The devices produced a photosensitivity (I_light/I_dark) of 1.2 × 10⁵ and a photoresponsivity of 360 mA W⁻¹ under white light illumination. The drain current in saturation region increases gradually with increasing illumination intensity. The threshold voltage exhibited a positive shift from −15.6 V in darkness to 27.8 V under illumination, which can be attributed to the well-known photovoltaic effect resulting from the transport of photogenerated holes and trapping of photogenerated electrons near the source electrode in organic phototransistors. Meanwhile, the devices showed good stability and with no obvious degeneration for 3 months in air. The study suggests that D–A conjugated polymers including BDF unit can be potentially applied in OFETs and organic phototransistors in addition to highly efficient polymer solar cells.     

Low-voltage,high speed inkjet-printed flexible complementary polymer electronic circuits

We report the development of high-performance inkjet-printed organic field-effect transistors (OFETs) and complementary circuits using high-k polymer dielectric blends comprising poly(vinylidenefluoride-trifluoroethylene) (P(VDF-TrFE)) and poly(methyl methacrylate) (PMMA) for high-speed and low-voltage operation. Inkjet-printed p-type polymer semiconductors containing alkyl-substituted thienylenevinylene (TV) and dodecylthiophene (PC12TV12T) and n-type P(NDI2OD-T2) OFETs showed high field-effect mobilities of 0.1–0.4 cm² V^?1 s^?1 and low threshold voltages down to 5 V. These OFET properties were modified by changing the blend ratio of P(VDF-TrFE) and PMMA. The optimum blend – a 7:3 wt% mixture of P(VDF-TrFE) and PMMA – was successfully used to realize high-performance complementary inverters and ring oscillators (ROs). The complementary ROs operated at a supplied bias (V_DD) of 5 V and showed an oscillation frequency (f_osc) as high as ～80 kHz at V_DD = 30 V. Furthermore, the f_osc of the complementary ROs was significantly affected by a variety of fundamental parameters such as the electron and hole mobilities, channel width and length, capacitance of the gate dielectrics, V_DD, and the overlap capacitance in the circuit configuration.     

Effect of electron-donating unit on crystallinity and charge transport in organic field-effect transistors with thienoisoindigo-based small molecules

We report the effect of an electron-donating unit on solid-state crystal orientation and charge transport in organic field-effect transistors (OFETs) with thienoisoindigo (TIIG)-based small molecules. End-capping of different electron-donor moieties [benzene (Bz), naphthalene (Np), and benzofuran (Bf)] onto TIIG (giving TIIG-Bz, TIIG-Np, and TIIG-Bf) is resulted in different electronic energy levels, solid-state morphologies and performance in OFETs. The 80 °C post-annealed TIIG-Np OFETs show the best device performance with a best hole mobility of 0.019 cm² V⁻¹ s⁻¹ and threshold voltage of −8.6 ± 0.9 V using top gate/bottom contact geometry and a CYTOP gate dielectric. We further investigated the morphological microstructure of the TIIG-based small molecules by using grazing incidence wide angle X-ray scattering, atomic force microscopy and a polarized optical microscope. The electronic transport levels of the TIIG-based small molecules in thin-film states were investigated using ultraviolet photoelectron spectroscopy to examine the charge injection properties of the gold electrode.     

Post-annealing modification in structural properties of ZnO thin films on p-type Si substrate deposited by evaporation

Zinc oxide (ZnO) films of thickness ∼380 nm were deposited on p-type Si (1 1 1) substrate maintained at 300 °C under 3×10⁻⁶ Torr by a radio frequency (RF) heating source. Transmission Fourier transform infrared (FTIR) spectrum exhibited a clear Zn–O bond excitation frequency of ∼408 cm⁻¹. X-ray diffraction spectrum demonstrated four peaks (P₁–P₄) at 2θ (deg) ∼36±0.06, 40±0.09, 82±0.17 and 86±0.2, which originated from (1 0 0), (0 0 2), (2 0 1) and (0 0 4) hexagonal planes, respectively. P₂ being the highest intensity peak indicated that the growth of ZnO predominantly occurred along the c-axis i.e. (0 0 2) plane. Micrographs of the samples obtained from scanning electron microscopy (SEM) and atomic force microscopy (AFM) identically displayed scattered nanocrystallites, which grew bigger with the increase of sample annealing temperature (°C) in the range of 400–1000. AFM pictures, in particular, exposed the hexagonal structure of the deposited films along with voids. However, ZnO composition ∼6:1 (Zn:O) as calculated from the energy dispersive spectrum (EDS) revealed that the formation of ZnO was not stoichiometric, rather of Zincsuboxide structure ZnO_x (x<1). Arrhenius plot of the resistivity data yielded a donor level (zinc interstitial and/or Zn–on–O site) with ionization energy E_c–1.26 eV, thereby it supports our measured results, in general.     

Structural,optical and transport properties of SxZnO

In this paper, S-doped ZnO (S_xZnO) was prepared using sol-gel method at different S amounts. The structural, optical and transport properties were investigated. The introduction of S atoms into the ZnO network was found to lower the crystallization level which results in reducing the crystallite size up to x=0.3. The doping process is confirmed by the observed peak at ~610 cm⁻¹ in the ATR spectrum related to the Zn-S linking. EDX mapping shows a homogeneous distribution of S atoms on the particles surface. The best compromise between the band gap (Eg=2.96 eV), the charge carriers (N_A=2.139×10²² cm⁻³), the conductivity (σ=5.56×10⁻⁴ Ω⁻¹ m⁻¹) and the mobility (µ=16.26×10⁻¹⁴ m² V⁻¹ s⁻¹) is obtained for x=0.1. The conduction mechanism is assumed by small hopping polaron. The S-doping has impacted positively the photocatalytic activity of ZnO, with particularly high performance for S_0.2ZnO.