High-Field-Effect Mobility of Low-Crystallinity Conjugated Polymers with Localized Aggregates.

Charge carriers typically move faster in crystalline regions than in amorphous regions in conjugated polymers because polymer chains adopt a regular arrangement resulting in a high degree of π-π stacking in crystalline regions. In contrast, the random polymer chain orientation in amorphous regions hinders connectivity between conjugated backbones; thus, it hinders charge carrier delocalization. Various studies have attempted to enhance charge carrier transport by increasing crystallinity. However, these approaches are inevitably limited by the semicrystalline nature of conjugated polymers. Moreover, high-crystallinity conjugated polymers have proven inadequate for soft electronics applications because of their poor mechanical resilience. Increasing the polymer chain connectivity by forming localized aggregates via π-orbital overlap among several conjugated backbones in amorphous regions provides a more effective approach to efficient charge carrier transport. A simple strategy relying on the density of random copolymer alkyl side chains was developed to generate these localized aggregates. In this strategy, steric hindrance caused by these side chains was modulated to change their density. Interestingly, a random polymer exhibiting low alkyl side chain density and crystallinity displayed greatly enhanced field-effect mobility (1.37 cm(2)/(V·s)) compared with highly crystalline poly(3-hexylthiophene).

Synthesis of ultrathin polymer insulating layers by initiated chemical vapour deposition for low-power soft electronics.

Insulating layers based on oxides and nitrides provide high capacitance, low leakage, high breakdown field and resistance to electrical stresses when used in electronic devices based on rigid substrates. However, their typically high process temperatures and brittleness make it difficult to achieve similar performance in flexible or organic electronics. Here, we show that poly(1,3,5-trimethyl-1,3,5-trivinyl cyclotrisiloxane) (pV3D3) prepared via a one-step, solvent-free technique called initiated chemical vapour deposition (iCVD) is a versatile polymeric insulating layer that meets a wide range of requirements for next-generation electronic devices. Highly uniform and pure ultrathin films of pV3D3 with excellent insulating properties, a large energy gap (>8 eV), tunnelling-limited leakage characteristics and resistance to a tensile strain of up to 4% are demonstrated. The low process temperature, surface-growth character, and solvent-free nature of the iCVD process enable pV3D3 to be grown conformally on plastic substrates to yield flexible field-effect transistors as well as on a variety of channel layers, including organics, oxides, and graphene.

High-performance p-channel transistors with transparent Zn doped-CuI.

'Ideal' transparent p-type semiconductors are required for the integration of high-performance thin-film transistors (TFTs) and circuits. Although CuI has recently attracted attention owing to its excellent opto-electrical properties, solution processability, and low-temperature synthesis, the uncontrolled copper vacancy generation and subsequent excessive hole doping hinder its use as a semiconductor material in TFT devices. In this study, we propose a doping approach through soft chemical solution process and transparent p-type Zn-doped CuI semiconductor for high-performance TFTs and circuits. The optimised TFTs annealed at 80 °C exhibit a high hole mobility of over 5 cm2 V-1 s-1 and high on/off current ratio of ~107 with good operational stability and reproducibility. The CuI:Zn semiconductors show intrinsic advantages for next-generation TFT applications and wider applications in optoelectronics and energy conversion/storage devices. This study paves the way for the realisation of transparent, flexible, and large-area integrated circuits combined with n-type metal-oxide semiconductor.

Spontaneous Doping at the Polymer-Polymer Interface for High-Performance Organic Transistors.

Low- k amorphous fluorinated polymers such as poly(perfluoroalkenylvinyl ether) (CYTOP) have widely been used as gate dielectrics for organic field-effect transistors (OFETs) because of their strong hydrophobicity to prevent the penetration of moisture and other contaminants and their perfect solvent orthogonality with organic semiconductors. Here, we report a new functionality of the fluorinated low- k polymer dielectrics, which is spontaneous p doping at the dielectric-semiconductor interface in OFETs. This functionality makes the ambipolar charge transport a unipolar p type. In the OFETs based on indacenodithiophene- co-benzothiadiazole and diketopyrrolopyrrole-thieno[3,2- b]thiophene, the charge transport is obviously ambipolar when paired with common polymer dielectrics such as poly(methyl methacrylate); however, it is perfectly modulated to the unipolar p type by applying the fluorinated dielectrics of CYTOP and poly(tetrafluoroethylene) (Teflon). We propose that this modulation of charge transport results from the rearrangement of C-F bonds at the interface between the fluorine-containing dielectrics and the conjugated polymer semiconductors by proper thermal annealing. These well-aligned dipole moments lead to an abrupt downshift of the Fermi level of the semiconductor toward the highest occupied molecular orbitals near the dielectric-semiconductor interface, which provides a p-doping effect on the channel transport and results in unipolar p-type characteristics in the composed OFETs. This study reveals a new functionality of the fluorinated dielectrics for future organic electronics.

Control of Crystallite Orientation in Diketopyrrolopyrrole-Based Semiconducting Polymers via Tuning of Intermolecular Interactions.

Numerous previous studies have focused on the notion that semiconducting polymers with an edge-on dominant orientation are advantageous for horizontal charge transport, whereas polymers with a face-on dominant orientation are advantageous for vertical charge transport, since the crystallite orientation determines the π-π stacking direction, which in turn affects the interchain charge transport direction. Here, we report that the crystallite orientation is dependent on the intermolecular interactions in the semiconducting polymer. In this study, we control the intermolecular interactions in a donor-acceptor (D-A) semiconducting polymer via side chain engineering. To perform side chain engineering, we use two different polymers: one with side chains on only A units (PDPP-B) and the other with side chains on both D and A units (PDPP-C8). We observe that PDPP-C8 is characterized by weaker intermolecular interactions due to the additional side chains on D units. A morphological analysis reveals that PDPP-B and PDPP-C8 films have microstructures that are characterized by edge-on and face-on dominant orientations, respectively. Therefore, we demonstrate that our strategies effectively control intermolecular interactions and, consequently, the crystallite orientation. Finally, we compare the vertical and horizontal mobilities of both polymer films. These results show that the crystallite orientation has significant influence on charge transport behaviors.

Room-Temperature Solution-Synthesized p-Type Copper(I) Iodide Semiconductors for Transparent Thin-Film Transistors and Complementary Electronics.

Here, room-temperature solution-processed inorganic p-type copper iodide (CuI) thin-film transistors (TFTs) are reported for the first time. The spin-coated 5 nm thick CuI film has average hole mobility (µFE ) of 0.44 cm2 V-1 s-1 and on/off current ratio of 5 × 102 . Furthermore, µFE increases to 1.93 cm2 V-1 s-1 and operating voltage significantly reduces from 60 to 5 V by using a high permittivity ZrO2 dielectric layer replacing traditional SiO2 . Transparent complementary inverters composed of p-type CuI and n-type indium gallium zinc oxide TFTs are demonstrated with clear inverting characteristics and voltage gain over 4. These outcomes provide effective approaches for solution-processed inorganic p-type semiconductor inks and related electronics.

Thiophene-Thiazole-Based Semiconducting Copolymers for High-Performance Polymer Field-Effect Transistors.

We report a newly synthesized donor (D)-acceptor (A)type semiconducting copolymer, consisting of thiophene as an electron-donating unit and thiazole as an electron-accepting unit (PQTBTz-TT-C8) for the active layer of the organic field-effect transistors (OFETs). Specifically, this study investigates the structure and electrical property relationships of PQTBTz-TT-C8 with comprehensive analyses on the charge-transporting properties corresponding to the spin rate of the spin coater during the formation of the PQTBTz-TT-C8 film. The crystallinity of PQTBTz-TT-C8 films is examined with grazing incidence X-ray diffraction. Temperature-dependent transfer measurements of the OFETs are conducted to extract the density of states (DOS) and characterize the charge-transport properties. Comparative analyses on charge transports within the framework of the physical model, based on polaron hopping and Gaussian DOS, reveal that the prefactors of both physical charge-transport models are independent of the spin-coating condition for the films. For staggered structural transistors, however, the thickness of the PQTBTz-TT-C8 films, which strongly affect the series resistance along the charge-transfer path in a vertical direction, is changed in accordance with the spin-coating rate. In other words, the spin-coating rate of the PQTBTz-TT-C8 films influences the thickness of the polymer films, yet any significant changes in the crystallinity of the film or electronic coupling between the neighboring molecules upon the spin-coating condition were barely noticeable. Because the PQTBTz-TT-C8 backbone chains inside the thin film are stacked up with the edge-on, the series resistances are changed according to the thickness of the film and thus the performance of the device varies depending on the thickness.

Ambipolar Small-Molecule:Polymer Blend Semiconductors for Solution-Processable Organic Field-Effect Transistors.

We report on the fabrication of an organic thin-film semiconductor formed using a blend solution of soluble ambipolar small molecules and an insulating polymer binder that exhibits vertical phase separation and uniform film formation. The semiconductor thin films are produced in a single step from a mixture containing a small molecular semiconductor, namely, quinoidal biselenophene (QBS), and a binder polymer, namely, poly(2-vinylnaphthalene) (PVN). Organic field-effect transistors (OFETs) based on QBS/PVN blend semiconductor are then assembled using top-gate/bottom-contact device configuration, which achieve almost four times higher mobility than the neat QBS semiconductor. Depth profile via secondary ion mass spectrometry and atomic force microscopy images indicate that the QBS domains in the films made from the blend are evenly distributed with a smooth morphology at the bottom of the PVN layer. Bias stress test and variable-temperature measurements on QBS-based OFETs reveal that the QBS/PVN blend semiconductor remarkably reduces the number of trap sites at the gate dielectric/semiconductor interface and the activation energy in the transistor channel. This work provides a one-step solution processing technique, which makes use of soluble ambipolar small molecules to form a thin-film semiconductor for application in high-performance OFETs.

Control of Threshold Voltage for Top-Gated Ambipolar Field-Effect Transistor by Gate Buffer Layer.

The threshold voltage and onset voltage for p-channel and n-channel regimes of solution-processed ambipolar organic transistors with top-gate/bottom-contact (TG/BC) geometry were effectively tuned by gate buffer layers in between the gate electrode and the dielectric. The work function of a pristine Al gate electrode (-4.1 eV) was modified by cesium carbonate and vanadium oxide to -2.1 and -5.1 eV, respectively, which could control the flat-band voltage, leading to a remarkable shift of transfer curves in both negative and positive gate voltage directions without any side effects. One important feature is that the mobility of transistors is not very sensitive to the gate buffer layer. This method is simple but useful for electronic devices where the threshold voltage should be precisely controlled, such as ambipolar circuits, memory devices, and light-emitting device applications.

Precisely Controlled Ultrathin Conjugated Polymer Films for Large Area Transparent Transistors and Highly Sensitive Chemical Sensors.

A uniform ultrathin polymer film is deposited over a large area with molecularlevel precision by the simple wire-wound bar-coating method. The bar-coated ultrathin films not only exhibit high transparency of up to 90% in the visible wavelength range but also high charge carrier mobility with a high degree of percolation through the uniformly covered polymer nanofibrils. They are capable of realizing highly sensitive multigas sensors and represent the first successful report of ethylene detection using a sensor based on organic field-effect transistors.

Effect of Polymer Gate Dielectrics on Charge Transport in Carbon Nanotube Network Transistors: Low-k Insulator for Favorable Active Interface.

Charge transport in carbon nanotube network transistors strongly depends on the properties of the gate dielectric that is in direct contact with the semiconducting carbon nanotubes. In this work, we investigate the dielectric effects on charge transport in polymer-sorted semiconducting single-walled carbon nanotube field-effect transistors (s-SWNT-FETs) by using three different polymer insulators: A low-permittivity (εr) fluoropolymer (CYTOP, εr = 1.8), poly(methyl methacrylate) (PMMA, εr = 3.3), and a high-εr ferroelectric relaxor [P(VDF-TrFE-CTFE), εr = 14.2]. The s-SWNT-FETs with polymer dielectrics show typical ambipolar charge transport with high ON/OFF ratios (up to ∼105) and mobilities (hole mobility up to 6.77 cm2 V-1 s-1 for CYTOP). The s-SWNT-FET with the lowest-k dielectric, CYTOP, exhibits the highest mobility owing to formation of a favorable interface for charge transport, which is confirmed by the lowest activation energies, evaluated by the fluctuation-induced tunneling model (FIT) and the traditional Arrhenius model (EaFIT = 60.2 meV and EaArr = 10 meV). The operational stability of the devices showed a good agreement with the activation energies trend (drain current decay ∼14%, threshold voltage shift ∼0.26 V in p-type regime of CYTOP devices). The poor performance in high-εr devices is accounted for by a large energetic disorder caused by the randomly oriented dipoles in high-k dielectrics. In conclusion, the low-k dielectric forms a favorable interface with s-SWNTs for efficient charge transport in s-SWNT-FETs.

Universal diffusion-limited injection and the hook effect in organic thin-film transistors.

The general form of interfacial contact resistance was derived for organic thin-film transistors (OTFTs) covering various injection mechanisms. Devices with a broad range of materials for contacts, semiconductors, and dielectrics were investigated and the charge injections in staggered OTFTs was found to universally follow the proposed form in the diffusion-limited case, which is signified by the mobility-dependent injection at the metal-semiconductor interfaces. Hence, real ohmic contact can hardly ever be achieved in OTFTs with low carrier concentrations and mobility, and the injection mechanisms include thermionic emission, diffusion, and surface recombination. The non-ohmic injection in OTFTs is manifested by the generally observed hook shape of the output conductance as a function of the drain field. The combined theoretical and experimental results show that interfacial contact resistance generally decreases with carrier mobility, and the injection current is probably determined by the surface recombination rate, which can be promoted by bulk-doping, contact modifications with charge injection layers and dopant layers, and dielectric engineering with high-k dielectric materials.

Purification of PEDOT:PSS by Ultrafiltration for Highly Conductive Transparent Electrode of All-Printed Organic Devices.

A highly conductive, air stable and scalable poly(3,4-ethylenedioxythiophene) (PEDOT): poly(4-styrenesulfonate) (PEDOT:PSS) are prepared by using mass production ultrafiltration. By effectively removing excess PSS and various reaction impurities using repeated 100 nm pore membrane filtration, purified PEDOT:PSS exhibit conductivity as high as 2000 S cm-1 .

Large Enhancement of Carrier Transport in Solution-Processed Field-Effect Transistors by Fluorinated Dielectric Engineering.

The universal role of high-k fluorinated dielectrics in assisting the carrier transport in transistors for a broad range of printable semiconductors is explored. These results present general rules for how to design dielectric materials and achieve devices with a high carrier concentration, low disorder, reliable operation, and robust properties.

Large-Scale Precise Printing of Ultrathin Sol-Gel Oxide Dielectrics for Directly Patterned Solution-Processed Metal Oxide Transistor Arrays.

Ultrathin and dense metal oxide gate di-electric layers are reported by a simple printing of AlOx and HfOx sol-gel precursors. Large-area printed indium gallium zinc oxide (IGZO) thin-film transistor arrays, which exhibit mobilities >5 cm(2) V(-1) s(-1) and gate leakage current of 10(-9) A cm(-2) at a very low operation voltage of 2 V, are demonstrated by continuous simple bar-coated processes.

Synergistic High Charge-Storage Capacity for Multi-level Flexible Organic Flash Memory.

Electret and organic floating-gate memories are next-generation flash storage mediums for printed organic complementary circuits. While each flash memory can be easily fabricated using solution processes on flexible plastic substrates, promising their potential for on-chip memory organization is limited by unreliable bit operation and high write loads. We here report that new architecture could improve the overall performance of organic memory, and especially meet high storage for multi-level operation. Our concept depends on synergistic effect of electrical characterization in combination with a polymer electret (poly(2-vinyl naphthalene) (PVN)) and metal nanoparticles (Copper). It is distinguished from mostly organic nano-floating-gate memories by using the electret dielectric instead of general tunneling dielectric for additional charge storage. The uniform stacking of organic layers including various dielectrics and poly(3-hexylthiophene) (P3HT) as an organic semiconductor, followed by thin-film coating using orthogonal solvents, greatly improve device precision despite easy and fast manufacture. Poly(vinylidene fluoride-trifluoroethylene) [P(VDF-TrFE)] as high-k blocking dielectric also allows reduction of programming voltage. The reported synergistic organic memory devices represent low power consumption, high cycle endurance, high thermal stability and suitable retention time, compared to electret and organic nano-floating-gate memory devices.

A highly planar fluorinated benzothiadiazole-based conjugated polymer for high-performance organic thin-film transistors.

High-mobility and low-voltage-operated organic field-effect transistors (OFETs) are demonstrated by the design of a new fluorinated benzothiadiazole-based conjugated polymer with fluorinated high-k polymer dielectrics. A record-breaking high hole mobility of 9.0 cm(2) V(-1) s(-1) for benzothiadiazole-based semiconducting polymers is achieved by the excellent planarity of the semiconducting polymer.

Facile Routes To Improve Performance of Solution-Processed Amorphous Metal Oxide Thin Film Transistors by Water Vapor Annealing.

Here, we report on a simple and high-rate oxidization method for producing solution-based compound mixtures of indium zinc oxide (IZO) and indium gallium zinc oxide (IGZO) metal-oxide semiconductors (MOS) for thin-film transistor (TFT) applications. One of the issues for solution-based MOS fabrication is how to sufficiently oxidize the precursor in order to achieve high performance. As the oxidation rate of solution processing is lower than vacuum-based deposition such as sputtering, devices using solution-processed MOS exhibit relatively poorer performance. Therefore, we propose a method to prepare the metal-oxide precursor upon exposure to saturated water vapor in a closed volume for increasing the oxidization efficiency without requiring additional oxidizing agent. We found that the hydroxide rate of the MOS film exposed to water vapor is lower than when unexposed (≤18%). Hence, we successfully fabricated oxide TFTs with high electron mobility (27.9 cm(2)/V·s) and established a rapid process (annealing at 400 °C for 5 min) that is much shorter than the conventional as-deposited long-duration annealing (at 400 °C for 1 h) whose corresponding mobility is even lower (19.2 cm(2)/V·s).

Simultaneous Improvement of Hole and Electron Injection in Organic Field-effect Transistors by Conjugated Polymer-wrapped Carbon Nanotube Interlayers.

Efficient charge injection is critical for flexible organic electronic devices such as organic light-emitting diodes (OLEDs) and field-effect transistors (OFETs). Here, we investigated conjugated polymer-wrapped semiconducting single-walled carbon nanotubes (s-SWNTs) as solution-processable charge-injection layers in ambipolar organic field-effect transistors with poly(thienylenevinylene-co-phthalimide)s. The interlayers were prepared using poly(9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT) or poly(9,9-dioctylfluorene) (PFO) to wrap s-SWNTs. In the contact-limited ambipolar OFETs, the interlayer led to significantly lower contact resistance (Rc) and increased mobilities for both holes and electrons. The resulting PTVPhI-Eh OFETs with PFO-wrapped s-SWNT interlayers showed very well-balanced ambipolar transport properties with a hole mobility of 0.5 cm(2)V(-1)S(-1) and an electron mobility of 0.5 cm(2)V(-1)S(-1) in linear regime. In addition, the chirality of s-SWNTs and kind of wrapping of conjugated polymers are not critical to improving charge-injection properties. We found that the improvements caused by the interlayer were due to the better charge injection at the metal/organic semiconductor contact interface and the increase in the charge concentration through a detailed examination of charge transport with low-temperature measurements. Finally, we successfully demonstrated complementary ambipolar inverters incorporating the interlayers without excessive patterning.

Benzodipyrrolidone (BDP)-based polymer semiconductors containing a series of chalcogen atoms: comprehensive investigation of the effect of heteroaromatic blocks on intrinsic semiconducting properties.

In order to determine the effects of actual 'chalcogen atoms' on semiconducting properties for application in a variety of optoelectronic devices, a class of donor (D)-acceptor (A) polymer semiconductors, namely PBDP-Fu, PBDP-Th, and PBDP-Se, containing the recently formulated benzodipyrrolidone (BDP) accepting unit and furan (Fu), thiophene (Th), or selenophene (Se) as a donating unit has been synthesized, characterized, and used in an active layer of organic field-effect transistors (OFETs). With the LUMO levels being comparatively consistent for all three polymers (-3.58 to -3.60 eV) due to the dominant BDP contribution to the polymer backbone, the HOMO energies are somewhat sensitive to the structurally distinctive feature of the donor counits used. Utilizing a combination of X-ray diffraction (XRD) and atomic force microscopy (AFM), it is apparent that further crystalline domains occur with edge-on orientation for the polymers (PBDP-Th and PBDP-Se) with relatively heavier chalcogen atoms such as Th and Se, compared with PBDP-Fu which has a rather amorphous nature. Investigation of their OFET performance indicates that all the polymers show well balanced ambipolar operations. The desirable morphological structures of both the PBDP-Th and PBDP-Se result in higher mobilities in OFETs than those of PBDP-Fu. In particular, 200 °C annealed PBDP-Se OFETs results in ambipolarity being mobile for both holes of up to 1.7 × 10(-2) cm(2)/V·s and electrodes of up to 1.9 × 10(-2) cm(2)/V·s. In addition, OFETs with PBDP-Th show nearly equivalent charge carrier mobilities for both holes (µ(h) = 1.2 × 10(-2) cm(2)/V·s) and electrons (µ(e) = 1.1 × 10(-2) cm(2)/V·s). Consequently, we systematically demonstrate how the manipulation of existing heteroaromatics can modulate the electronic properties of conjugated D-A polymers, elucidating structure-property relationships that are desirable for the rational design of next generation materials.