Solution‐Processed Small‐Molecule Bulk Heterojunction Ambipolar Transistors

Solution‐processed small‐molecule bulk heterojunction (BHJ) ambipolar organic thin‐film transistors are fabricated based on a combination of [2‐phenylbenzo[d,d']thieno[3,2‐b;4,5‐b']dithiophene (P‐BTDT) : 2‐(4‐n‐octylphenyl)benzo[d,d ']thieno[3,2‐b;4,5‐b']dithiophene (OP‐BTDT)] and C₆₀. Treating high electrical performance vacuum‐deposited P‐BTDT organic semiconductors with a newly developed solution‐processed organic semiconductor material, OP‐BTDT, in an optimized ratio yields a solution‐processed p‐channel organic semiconductor blend with carrier mobility as high as 0.65 cm² V^?1 s^?1. An optimized blending of P‐BTDT:OP‐BTDT with the n‐channel semiconductor, C₆₀, results in a BHJ ambipolar transistor with balanced carrier mobilities for holes and electrons of 0.03 and 0.02 cm² V^?1 s^?1, respectively. Furthermore, a complementary‐like inverter composed of two ambipolar thin‐film transistors is demonstrated, which achieves a gain of 115.     

A Review of Low‐Temperature Solution‐Processed Metal Oxide Thin‐Film Transistors for Flexible Electronics

Solution processing, including printing technology, is a promising technique for oxide thin‐film transistor (TFTs) fabrication because it tends to be a cost‐effective process with high composition controllability and high throughput. However, solution‐processed oxide TFTs are limited by low‐performance and stability issues, which require high‐temperature annealing. This high thermal budget in the fabrication process inhibits oxide TFTs from being applied to flexible electronics. There have been numerous attempts to promote the desired electrical characteristics of solution‐processed oxide TFTs at lower fabrication temperatures. Recent techniques for achieving low‐temperature (<350 °C) solution‐processed and printed oxide TFTs, in terms of the materials, processes, and structural engineering methods currently in use are reviewed. Moreover, the core techniques for both n‐type and p‐type oxide‐based channel layers, gate dielectric layers, and electrode layers in oxide TFTs are addressed. Finally, various multifunctional and emerging applications based on low‐temperature solution‐processed oxide TFTs are introduced and future outlooks for this highly promising research are suggested.     

Controllable Molecular Doping and Charge Transport in Solution‐Processed Polymer Semiconducting Layers

Here, controlled p‐type doping of poly(2‐methoxy‐5‐(2′‐ethylhexyloxy)‐p‐phenylene vinylene) (MEH‐PPV) deposited from solution using tetrafluoro‐tetracyanoquinodimethane (F4‐TCNQ) as a dopant is presented. By using a co‐solvent, aggregation in solution can be prevented and doped films can be deposited. Upon doping the current–voltage characteristics of MEH‐PPV‐based hole‐only devices are increased by several orders of magnitude and a clear Ohmic behavior is observed at low bias. Taking the density dependence of the hole mobility into account the free hole concentration due to doping can be derived. It is found that a molar doping ratio of 1 F4‐TCNQ dopant per 600 repeat units of MEH‐PPV leads to a free carrier density of 4 × 10²² m^?3. Neglecting the density‐dependent mobility would lead to an overestimation of the free hole density by an order of magnitude. The free hole densities are further confirmed by impedance measurements on Schottky diodes based on F4‐TCNQ doped MEH‐PPV and a silver electrode.     

Gate Capacitance‐Dependent Field‐Effect Mobility in Solution‐Processed Oxide Semiconductor Thin‐Film Transistors

Solution‐processed oxide semiconductors (OSs) used as channel layer have been presented as a solution to the demand for flexible, cheap, and transparent thin‐film transistors (TFTs). In order to produce high‐performance and long‐sustainable portable devices with the solution‐processed OS TFTs, the low‐operational voltage driving current is a key issue. Experimentally, increasing the gate‐insulator capacitances by high‐k dielectrics in the OS TFTs has significantly improved the field‐effect mobility of the OS TFTs. But, methodical examinations of how the field‐effect mobility depends on gate capacitance have not been presented yet. Here, a systematic analysis of the field‐effect mobility on the gate capacitances in the solution‐processed OS TFTs is presented, where the multiple‐trapping‐and‐release and hopping percolation mechanism are used to describe the electrical conductivity of the nanocrystalline and amorphous OSs, respectively. An intuitive single‐piece expression showing how the field‐effect mobility depends on gate capacitance is developed based on the aforementioned mechanisms. The field‐effect mobility, depending on the gate capacitances, of the fabricated ZnO and ZnSnO TFTs clearly follows the theoretical prediction. In addition, the way in which the gate insulator properties (e.g., gate capacitance or dielectric constant) affect the field‐effect mobility maximum in the nanocrystalline ZnO and amorphous ZnSnO TFTs are investigated.     

Metal Oxide Transistors via Polyethylenimine Doping of the Channel Layer: Interplay of Doping,Microstructure, and Charge Transport

Polymer doping of solution‐processed In₂O₃ with small amounts of the electron‐rich polymer, polyethylenimine (PEI), affords superior transistor performance, including higher electron mobility than that of the pristine In₂O₃ matrix. PEI doping of In₂O₃ films not only frustrates crystallization and controls the carrier concentration but, more importantly, acts as electron dopant and/or scattering center depending on the polymer doping concentration. The electron donating capacity of PEI combined with charge trapping and variation in the matrix film microstructure yields, for optimum PEI doping concentrations of 1.0%–1.5%, electron mobilities as high as ≈9 cm² V^?1 s^?1 on a 300 nm SiO₂ gate dielectric, an excellent on/off ratio of ≈10⁷, and an application optimal V _T. Importantly, these metrics exceed those of the pure In₂O₃ matrix with a maximum mobility ≈4 cm² V^?1 s^?1. Furthermore, we show that this approach is extendible to other oxide compositions such as IZO and the technologically relevant IGZO. This work opens a new means to fabricate amorphous semiconductors via solution processing at low temperatures, while preserving or enhancing the mobility of the pristine polycrystalline semiconductor.     

Load‐Controlled Roll Transfer of Oxide Transistors for Stretchable Electronics

A stretchable and transparent In‐Ga‐Zn‐O (IGZO) thin film transistors with high electrical performance and scalability is demonstrated. A load‐controlled roll transfer method is realized for fully automated and scalable transfer of the IGZO TFTs from a rigid substrate to a nonconventional elastomeric substrate. The IGZO TFTs exhibit high electrical performance under stretching and cyclic tests, demonstrating the potentiality of the load‐controlled roll transfer in stretchable electronics. The mechanics of the load‐controlled roll transfer is investigated and simulated, and it is shown that the strain level experienced by the active layers of the device can be controlled to well below their maximum fracture level during transfer.     

Effect of Non‐Chlorinated Mixed Solvents on Charge Transport and Morphology of Solution‐Processed Polymer Field‐Effect Transistors

Using non‐chlorinated solvents for polymer device fabrication is highly desirable to avoid the negative environmental and health effects of chlorinated solvents. Here, a non‐chlorinated mixed solvent system, composed by a mixture of tetrahydronaphthalene and p­‐xylene, is described for processing a high mobility donor‐acceptor fused thiophene‐diketopyrrolopyrrole copolymer (PTDPPTFT4) in thin film transistors. The effects of the use of a mixed solvent system on the device performance, e.g., charge transport, morphology, and molecular packing, are investigated. p‐Xylene is chosen to promote polymer aggregation in solution, while a higher boiling point solvent, tetrahydronaphthalene, is used to allow a longer evaporation time and better solubility, which further facilitates morphological tuning. By optimizing the ratio of the two solvents, the charge transport characteristics of the polymer semiconductor device are observed to significantly improve for polymer devices deposited by spin coating and solution shearing. Average charge carrier mobilities of 3.13 cm² V^?1 s^?1 and a maximum value as high as 3.94 cm² V^?1 s^?1 are obtained by solution shearing. The combination of non‐chlorinated mixed solvents and the solution shearing film deposition provide a practical and environmentally‐friendly approach to achieve high performance polymer transistor devices.     

High‐Mobility Air‐Stable Solution‐Shear‐Processed n‐Channel Organic Transistors Based on Core‐Chlorinated Naphthalene Diimides

High charge carrier mobility solution‐processed n‐channel organic thin‐film transistors (OTFTs) based on core‐chlorinated naphthalene tetracarboxylic diimides (NDIs) with fluoroalkyl chains are demonstrated. These OTFTs were prepared through a solution shearing method. Core‐chlorination of NDIs not only increases the electron mobilities of OTFTs, but also enhances their air stability, since the chlorination in the NDI core lowers the lowest unoccupied molecular orbital (LUMO) levels. The air‐stability of dichlorinated NDI was better than that of the tetrachlorinated NDIs, presumably due to the fact that dichlorinated NDIs have a denser packing of the fluoroalkyl chains and less grain boundaries on the surface, reducing the invasion pathway of ambient oxygen and moisture. The devices of dichlorinated NDIs exhibit good OTFT performance, even after storage in air for one and a half months. Charge transport anisotropy is observed from the dichlorinated NDI. A dichlorinated NDI with ?CH₂C₃F₇ side chains reveals high mobilities of up to 0.22 and 0.57 cm² V^?1 s^?1 in parallel and perpendicular direction, respectively, with regard to the shearing direction. This mobility anisotropy is related to the grain morphology. In addition, we find that the solution‐shearing deposition affects the molecular orientation in the crystalline thin films and lowers the d(001)‐spacing (the out‐of‐plane interlayer spacing), compared to the vapor‐deposited thin films. Core‐chlorinated NDI derivatives are found to be highly suitable for n‐channel active materials in low‐cost solution‐processed organic electronics.     

非晶氧化物半导体薄膜晶体管沟道层的研究进展

薄膜晶体管(TFT)作为开关元件广泛应用于平板显示领域,沟道层材料的选择直接影响了TFT的性能.近年来,基于非晶氧化物半导体(AOS)沟道层材料的TFT已成为具有潜力替代传统硅材料(非晶硅或多晶硅)沟道层TFT的新一代技术,有望应用于超大屏显示、3D显示、柔性显示以及透明显示等新一代显示领域.综述了AOS TFT沟道层的研究进展,重点介绍了AOS TFT用AOS沟道层在材料体系、成膜技术、薄膜的后续处理工艺、材料体系中各元素含量以及掺杂等方面的研究成果,并分析了AOS沟道层对AOS TFT性能的影响以及存在的问题,对AOS TFT的未来发展趋势进行了预测和展望.     

Heterogeneous Nucleation Promotes Carrier Transport in Solution‐Processed Organic Field‐Effect Transistors

A new way to investigate and control the growth of solution‐cast thin films is presented. The combination of in situ quartz crystal microbalance measurements with dissipation capabilities (QCM‐D) and in situ grazing‐incidence wide‐angle X‐ray scattering (GIWAXS) in an environmental chamber provides unique quantitative insights into the time‐evolution of the concentration of the solution, the onset of nucleation, and the mode of growth of the organic semiconductor under varied drying conditions. It is demonstrated that careful control over the kinetics of solution drying enhances carrier transport significantly by promoting phase transformation predominantly via heterogeneous nucleation and sustained surface growth of a highly lamellar structure at the solid‐liquid interface at the expense of homogeneous nucleation.     

Carrier Modulation of Ambipolar Few‐Layer MoTe2 Transistors by MgO Surface Charge Transfer Doping

Semiconducting molybdenum ditelluride (2H‐MoTe₂), a fast‐emerging 2D material with an appropriate band gap and decent carrier mobility, is configured as field‐effect transistors and is the focus of substantial research interest, showing hole‐dominated ambipolar characteristics. Here, carrier modulation of ambipolar few‐layer MoTe₂ transistors is demonstrated utilizing magnesium oxide (MgO) surface charge transfer doping. By carefully adjusting the thickness of MgO film and the number of MoTe₂ layers, the carrier polarity of MoTe₂ transistors from p‐type to n‐type can be reversely controlled. The electron mobility of MoTe₂ is significantly enhanced from 0.1 to 20 cm² V^?1 s^?1 after 37 nm MgO film doping, indicating a greatly improved electron transport. The effective carrier modulation enables to achieve high‐performance complementary inverters with high DC gain of >25 and photodetectors based on few‐layer MoTe₂ flakes. The results present an important advance toward the realization of electronic and optoelectronic devices based on 2D transition‐metal dichalcogenide semiconductors.     

Beryllium‐Assisted p‐Type Doping for ZnO Homojunction Light‐Emitting Devices

A key step in realization of a ZnO homojunction light‐emitting diode is the effective p‐type doping in ZnO:N. In this article, a feasible route is demonstrated to enhance hole doping in ZnO:N films by the assistance of Beryllium. The newly synthesized p‐type ZnO is applied in light‐emitting devices. The corresponding p–i–n junction exhibits excellent diode characteristics, and strong near band edge ultraviolet emissions is also observed even at temperatures as high as 400 K under the injection of continuous current. The results represent a critical advance toward the development of high‐efficiency and stabilized p‐type ZnO, which is also a desirable key step for future ZnO‐based optoelectronic applications.     

A Facile Solution‐Doping Method to Improve a Low‐Temperature Zinc Oxide Precursor: Towards Low‐Cost Electronics on Plastic Foil

Optimization of thin‐film transistors performance is usually accompanied by an increase of the process temperature. This work presents a method to raise the field effect mobility by a factor of 3 without a change of the process parameters. The modification involves a solution doping process where an ammine zinc complex is formed in the presence of metal ions of the 13^th group, namely gallium and indium. Morphological studies, including scanning electron microscopy and atomic force microscopy, reveal the difference among the resulting films. Moreover, X‐ray diffraction results show that the doping affects the preferred orientation of the zinc oxide crystals in the resulting film. The electrical properties vary distinctly and are best for a solution doped with both gallium and indium. With a double‐layer system the performance of this new precursor exceeds field effect mobility values of 1 cm² V^?1 s^?1 after a maximum process temperature of 160 °C.     

p‐Doping of Copper(I) Thiocyanate (CuSCN) Hole‐Transport Layers for High‐Performance Transistors and Organic Solar Cells

The ability to tune the electronic properties of soluble wide bandgap semiconductors is crucial for their successful implementation as carrier‐selective interlayers in large area opto/electronics. Herein the simple, economical, and effective p‐doping of one of the most promising transparent semiconductors, copper(I) thiocyanate (CuSCN), using C₆₀F₄₈ is reported. Theoretical calculations combined with experimental measurements are used to elucidate the electronic band structure and density of states of the constituent materials and their blends. Obtained results reveal that although the bandgap (3.85 eV) and valence band maximum (?5.4 eV) of CuSCN remain unaffected, its Fermi energy shifts toward the valence band edge upon C₆₀F₄₈ addition—an observation consistent with p‐type doping. Transistor measurements confirm the p‐doping effect while revealing a tenfold increase in the channel's hole mobility (up to 0.18 cm² V^?1 s^?1), accompanied by a dramatic improvement in the transistor's bias‐stress stability. Application of CuSCN:C₆₀F₄₈ as the hole‐transport layer (HTL) in organic photovoltaics yields devices with higher power conversion efficiency, improved fill factor, higher shunt resistance, and lower series resistance and dark current, as compared to control devices based on pristine CuSCN or commercially available HTLs.     

Impact of Layer Configuration and Doping on Electron Transport and Bias Stability in Heterojunction and Superlattice Metal Oxide Transistors

The astonishing recent progress in the field of metal oxide thin‐film transistors (TFTs) and their debut in commercial displays is accomplished using vacuum‐processed multicomponent oxide semiconductors. However, emulating this success with their solution‐processable counterparts poses numerous scientific challenges. Here, the development of high mobility n‐channel TFTs based on ultrathin (<10 nm) alternating layers of In₂O₃ and ZnO that are sequentially deposited to form heterojunction and superlattice channels is reported. The resulting TFTs exhibit high electron saturation mobility (13 cm² V^?1 s^?1), excellent current on/off ratios (>10⁸) with nearly zero onset voltages and hysteresis‐free operation despite the low temperature processing (≤200 °C). The enhanced performance is attributed to the formation of a quasi‐2D electron gas‐like system at the In₂O₃/ZnO heterointerface due to the conduction band offset. It is shown that altering the oxide deposition sequence has an adverse effect on electron transport due to formation of trap states. Optimized multilayer TFTs are shown to exhibit improved bias‐stress stability compared to single‐layer TFTs. Modulating the electron concentration within the superlattice channel via selective n‐doping of the ZnO interlayers leads to almost 100% saturation mobility increase (≈25 cm² V^?1 s^?1) even when the TFTs are fabricated on flexible plastic substrates.     

Efficient Charge Carrier Injection and Balance Achieved by Low Electrochemical Doping in Solution‐Processed Polymer Light‐Emitting Diodes

Charge carrier injection and transport in polymer light‐emitting diodes (PLEDs) is strongly limited by the energy level offset at organic/(in)organic interfaces and the mismatch in electron and hole mobilities. Herein, these limitations are overcome via electrochemical doping of a light‐emitting polymer. Less than 1 wt% of doping agent is enough to effectively tune charge injection and balance and hence significantly improve PLED performance. For thick single‐layer (1.2 µm) PLEDs, dramatic reductions in current and luminance turn‐on voltages (V_J = 11.6 V from 20.0 V and V_L = 12.7 V from 19.8 V with/without doping) accompanied by reduced efficiency roll‐off are observed. For thinner (<100 nm) PLEDs, electrochemical doping removes a thickness dependence on V_J and V_L, enabling homogeneous electroluminescence emission in large‐area doped devices. Such efficient charge injection and balance properties achieved in doped PLEDs are attributed to a strong electrochemical interaction between the polymer and the doping agents, which is probed by in situ electric‐field‐dependent Raman spectroscopy combined with further electrical and energetic analysis. This approach to control charge injection and balance in solution‐processed PLEDs by low electrochemical doping provides a simple yet feasible strategy for developing high‐quality and efficient lighting applications that are fully compatible with printing technologies.     

Systematic Study of Widely Applicable N‐Doping Strategy for High‐Performance Solution‐Processed Field‐Effect Transistors

A specific design for solution‐processed doping of active semiconducting materials would be a powerful strategy in order to improve device performance in flexible and/or printed electronics. Tetrabutylammonium fluoride and tetrabutylammonium hydroxide contain Lewis base anions, F^? and OH^?, respectively, which are considered as organic dopants for efficient and cost‐effective n‐doping processes both in n‐type organic and nanocarbon‐based semiconductors, such as poly[[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)] (P(NDI2OD‐T2)) and selectively dispersed semiconducting single‐walled carbon nanotubes by π‐conjugated polymers. The dramatic enhancement of electron transport properties in field‐effect transistors is confirmed by the effective electron transfer from the dopants to the semiconductors as well as controllable onset and threshold voltages, convertible charge‐transport polarity, and simultaneously showing excellent device stabilities under ambient air and bias stress conditions. This simple solution‐processed chemical doping approach could facilitate the understanding of both intrinsic and extrinsic charge transport characteristics in organic semiconductors and nanocarbon‐based materials, and is thus widely applicable for developing high‐performance organic and printed electronics and optoelectronics devices.     

High‐Mobility ZnO Thin Film Transistors Based on Solution‐processed Hafnium Oxide Gate Dielectrics

The properties of metal oxides with high dielectric constant (k) are being extensively studied for use as gate dielectric alternatives to silicon dioxide (SiO₂). Despite their attractive properties, these high‐k dielectrics are usually manufactured using costly vacuum‐based techniques. In that respect, recent research has been focused on the development of alternative deposition methods based on solution‐processable metal oxides. Here, the application of the spray pyrolysis (SP) technique for processing high‐quality hafnium oxide (HfO₂) gate dielectrics and their implementation in thin film transistors employing spray‐coated zinc oxide (ZnO) semiconducting channels are reported. The films are studied by means of admittance spectroscopy, atomic force microscopy, X‐ray diffraction, UV–Visible absorption spectroscopy, FTIR, spectroscopic ellipsometry, and field‐effect measurements. Analyses reveal polycrystalline HfO₂ layers of monoclinic structure that exhibit wide band gap (≈5.7 eV), low roughness (≈0.8 nm), high dielectric constant (k ≈ 18.8), and high breakdown voltage (≈2.7 MV/cm). Thin film transistors based on HfO₂/ZnO stacks exhibit excellent electron transport characteristics with low operating voltages (≈6 V), high on/off current modulation ratio (～10⁷) and electron mobility in excess of 40 cm² V^?1 s^?1.