Reconfigurable Electronic Physically Unclonable Functions Based on Organic Thin-Film Transistors with Multiscale Polycrystalline Entropy for Highly Secure Cryptography Primitives

In this study, organic thin-film transistors (OTFTs) are investigated as a promising platform for cost-effective, reconfigurable, and strong electronic physically unclonable functions (PUFs) for highly secure cryptography primitives. Simple spin-casting of solution-processable small-molecule organic semiconductors forms unique and unclonable fingerprint thin films with randomly distributed polycrystalline structures ranging from nanoscale molecular orientations to microcrystalline orientations, which provides a stochastic entropy source of device-to-device variations for OTFT arrays. Blending organic semiconductors with polymer materials is a promising strategy to improve the reliability of OTFT-based PUFs. Studies on the relationship between the phase-separated polycrystalline microstructure of organic semiconductor/polymer blend films and PUF characteristics reveal that the 2D mosaic microcrystalline structure of organic semiconductors in the vertically phase-separated trilayered structure enables the implementation of OTFT-based PUFs that simultaneously satisfy the requirements of being unclonable and unpredictable, with reliable cryptographic properties. The inherent multiscale randomness of the crystalline structure allows random distribution in OTFT-based PUFs even with various channel dimensions. The secret bit stream generated from the OTFT-based PUF developed in this study is reconfigurable by simply changing the gate bias, demonstrating the potential to counter evolving security attack threats.     

High Frequency Solution-Processed Organic Field-Effect Transistors with High-Resolution Printed Short Channels

Organic electronics is an emerging technology that enables the fabrication of devices with low-cost and simple solution-based processes at room temperature. In particular, it is an ideal candidate for the Internet of Things since devices can be easily integrated in everyday objects, potentially creating a distributed network of wireless communicating electronics. Recent efforts allowed to boost operational frequency of organic field-effect transistors (OFETs), required to achieve efficient wireless communication. However, in the majority of cases, in order to increase the dynamic performances of OFETs, masks based lithographic techniques are used to reduce device critical dimensions, such as channel and overlap lengths. This study reports the successful integration of direct written metal contacts defining a 1.4 µm short channel, printed with ultra-precise deposition technique (UPD), in fully solution fabricated n-type OFETs. An average transition frequency as high as 25.5 MHz is achieved at 25 V. This result demonstrates the potential of additive, high-resolution direct-writing techniques for the fabrication of organic electronics operating in the high-frequency regime.     

Printed Sub‐2 V Gel‐Electrolyte‐Gated Polymer Transistors and Circuits

The fabrication and characterization of printed ion‐gel‐gated poly(3‐hexylthiophene) (P3HT) transistors and integrated circuits is reported, with emphasis on demonstrating both function and performance at supply voltages below 2 V. The key to achieving fast sub‐2 V operation is an unusual gel electrolyte based on an ionic liquid and a gelating block copolymer. This gel electrolyte serves as the gate dielectric and has both a short polarization response time (<1 ms) and a large specific capacitance (>10 µF cm^?2), which leads simultaneously to high output conductance (>2 mS mm^?1), low threshold voltage (<1 V) and high inverter switching frequencies (1–10 kHz). Aerosol‐jet‐printed inverters, ring oscillators, NAND gates, and flip‐flop circuits are demonstrated. The five‐stage ring oscillator operates at frequencies up to 150 Hz, corresponding to a propagation delay of 0.7 ms per stage. These printed gel electrolyte gated circuits compare favorably with other reported printed circuits that often require much larger operating voltages. Materials factors influencing the performance of the devices are discussed.     

Tailoring Morphology and Structure of Inkjet‐Printed Liquid‐Crystalline Semiconductor/Insulating Polymer Blends for High‐Stability Organic Transistors

Inkjet printing of semiconducting polymers is desirable for realizing low‐cost, large‐area printed electronics. However, sequential inkjet printing methods often suffer from nozzle clogging because the solubility of semiconducting polymers in organic solvents is limited. Here, it is demonstrated that the addition of an insulating polymer to a semiconducting polymer ink greatly enhances the solubility and stability of the ink, leading to the stable ejection of ink droplets. This bicomponent blend comprising a liquid‐crystalline semiconducting copolymer, poly(didodecylquaterthiophene‐alt‐didodecylbithiazole) (PQTBTz‐C12), and an insulating commodity polymer, polystyrene, is extremely useful as a semiconducting layer in organic field‐effect transistors (OFETs), providing fine control over the phase‐separated morphology and structure of the inkjet‐printed film. Tailoring the solubility‐induced phase separation of the two components leads to a bilayer structure consisting of a polystyrene layer on the top and a highly crystalline PQTBTz‐C12 layer on the bottom. The blend film is used as the semiconducting layer in OFETs, reducing the semiconductor content to several tens of pictograms in a single device without degrading the device performance. Furthermore, OFETs based on the PQTBTz‐C12/polystyrene film exhibit much greater environmental and electrical stabilities compared to the films prepared from homo PQTBTz‐C12, mainly due to the self‐encapsulated structure of the blend film.     

Strategies for Fast‐Switching in All‐Polymer Field Effect Transistors

Low‐cost printable field effect transistors (FETs) are typically associated with slow switching characteristics. Dynamic response of polymer field effect transistors (PFETs) is a manifestation of time scales involved in processes such as dielectric polarization, structural relaxation, and transport via disordered‐interfacial states. A range of dielectrics and semiconductors are studied to arrive at a parameter which serves as a figure of merit and quantifies the different processes contributing to the switching response. A cross‐over from transport limiting factors to dielectric limiting factors in the dynamics of PFETs is observed. The dielectric limited regime in the PFET dynamics is tapped in to explore high speed processes, and an enhancement of switching speed by three orders of magnitude (from 300 μs to 400 ns) is observed at channel lengths which can be accessed by low cost printing methods. The device structure utilizes polymer‐ferroelectrics (FE) as the dielectric layer and involves a fabrication‐procedure which assists in circumventing the slow dynamics within the bulk of FE. This method of enhancing the dynamic response of PFETs is universally applicable to all classes of disordered‐FE.     

Artificial Synapse Based on Oxygen Vacancy Migration in Ferroelectric-Like C-Axis-Aligned Crystalline InGaSnO Semiconductor Thin-Film Transistors for Highly Integrated Neuromorphic Electronics

Artificial synapses are a key component of neuromorphic computing systems. To achieve high-performance neuromorphic computing ability, a huge number of artificial synapses should be integrated because the human brain has a huge number of synapses (≈10¹⁵). In this study, a coplanar synaptic, thin-film transistor (TFT) made of c-axis-aligned crystalline indium gallium tin oxide (CAAC–IGTO) is developed. The electrical characteristics of the biological synapses such as inhibitory postsynaptic current (IPSC), paired-pulse depression (PPD), short-term plasticity (STP), and long-term plasticity at V_DS = 0.1 V, are demonstrated. The measured synaptic behavior can be explained by the migration of positively charged oxygen vacancies (V_o⁺/V_o⁺⁺) in the CAAC–IGTO layer. The mechanism of implementing synaptic behavior is completely new, compared to previous reports using electrolytes or ferroelectric gate insulators. The advantage of this device is to use conventional gate insulators such as SiO₂ for synaptic behavior. Previous studies use chitosan, Ta₂O₃, SiO₂ nanoparticles , Gd₂O₃, and HfZrO_x for gate insulators, which cannot be used for high integration of synaptic devices. The metal–oxide TFTs, widely used in the display industry, can be applied to the synaptic transistors. Therefore, CAAC–IGTO synaptic TFT can be a good candidate for application as an artificial synapse for highly integrated neuromorphic chips.     

基于物理并适用于电路仿真的多晶硅薄膜晶体管薄层电荷模型

本文利用薄层电荷理论,建立了一个基于表面势的、物理的多晶硅薄膜晶体管(Polysilicon Thin-Film Transistors,poly-Si TFTs)的电流模型,且该模型适用于电路仿真.推导了 poly-Si TFTs 表面势的近似解法,该求解法非迭代的计算大大地提高了计算效率,且精确度高并得到实验验证.基于物理的迁移率方程考虑了晶界势垒高度,和由于声子散射与表面粗糙散射引起的迁移率退化.基于 Brews 的薄层电荷模型和上述非迭代计算表面势,本电流模型同时考虑了漏致势垒降低(DIBL)效应、kink 效应和沟道长度调制效应.对不同沟长的器件实验数据比较发现,提出的模型在很广的工作电压内与实验数据符合得非常好.同时本模型的所有方程都具有解析形式,电流方程光滑连续,适用于电路仿真器如 SPICE.     

绝缘层/有源层界面修饰及对有机薄膜晶体管性能的影响

制备了具有修饰层的有机薄膜场效应晶体管,采用高掺杂Si作为栅极,传统的无机绝缘材料SiO2作为栅绝缘层,有机绝缘材料PMMA或OTS作为修饰层,CuPc作为有源层,Au作为源、漏极.测试结果表明,采用经过修饰的栅绝缘层SiO2/OTS和SiO2/PMMA的两种器件的开关电流比最高可达8×104,迁移率最高为1.22×10-3cm2/(V·s),而漏电流仅为10-10A,总体性能优于单层SiO2器件.     

绝缘层/有源层界面修饰及对有机薄膜晶体管性能的影响

制备了具有修饰层的有机薄膜场效应晶体管,采用高掺杂Si作为栅极,传统的无机绝缘材料SiO2作为栅绝缘层,有机绝缘材料PMMA或OTS作为修饰层,CuPc作为有源层,Au作为源、漏极.测试结果表明,采用经过修饰的栅绝缘层SiO2/OTS和SiO2/PMMA的两种器件的开关电流比最高可达8×104,迁移率最高为1.22×10-3cm2/(V·s),而漏电流仅为10-10A,总体性能优于单层SiO2器件.     

Electrically Tunable Surface Acoustic Wave Propagation at MHz Frequencies Based on Carbon Nanotube Thin-Film Transistors

Surface acoustic waves (SAWs) that propagate on the surface of a solid at MHz frequencies are widely used in sensing, communication, and acoustic tweezers. However, their properties are difficult to be tuned electrically, and current devices suffer from complicated configurations, complicated tuning mechanisms, or small ranges of tunability. Here a structure featuring a thin-film transistor configuration is proposed to achieve electrically tunable SAW propagation based on conductivity tuning. When a DC gate voltage is applied, the on-site conductivity of the piezoelectric substrate is modulated, which leads to velocity and amplitude tuning of SAWs. The use of carbon nanotubes and crystalline nanocellulose as the channel and gate materials results in high tuning capacity and low gate voltage requirement. The tunability is manifested by a 2.5% phase velocity tuning and near 10 dB on/off switching of the signals. The proposed device holds the potential for the next generation SAW-based devices.     

Solid-State Homojunction Electrochemical Transistors and Logic Gates on Plastic

Organic electrochemical transistors (OECTs) have attracted significant attention due to their unique ionic–electronic charge coupling, which holds promise for use in a variety of bioelectronics. However, the typical electronic components of OECTs, such as the rigid metal electrodes and aqueous electrolytes, have limited their application in solid-state bioelectronics that requires design flexibility and a variety of form factors. Here, the fabrication of a solid-state homojunction OECT consisting of a pristine polymer semiconductor channel, doped polymer semiconductor electrodes, and a solid electrolyte is demonstrated. This structure combines the photo-crosslinking of all of the electronic OECT components with the selective doping of the polymer semiconductor. Three Lewis acids (gold (III) chloride (AuCl₃), iron (III) chloride (FeCl₃), and copper (II) chloride (CuCl₂) ) are utilized as dopants for the metallization of the polymer semiconductor. The AuCl₃-doped polymer semiconductor with an electrical conductivity of ≈100 S cm⁻¹ is successfully employed as the source, drain, and gate electrodes for the OECT, which exhibited a high carrier mobility of 3.4 cm² V⁻¹ s⁻¹ and excellent mechanical stability, with negligible degradation in device performance after 5000 cycles of folding at a radius of 0.1 mm. Homojunction OECTs are then successfully assembled to produce NOT, NAND, and NOR logic gates.     

Analysis of the Annealing Budget of Metal Oxide Thin-Film Transistors Prepared by an Aqueous Blade-Coating Process

Metal oxide (MO) semiconductors are widely used in electronic devices due to their high optical transmittance and promising electrical performance. This work describes the advancement toward an eco-friendly, streamlined method for preparing thin-film transistors (TFTs) via a pure water-solution blade-coating process with focus on a low thermal budget. Low temperature and rapid annealing of triple-coated indium oxide thin-film transistors (3C-TFTs) and indium oxide/zinc oxide/indium oxide thin-film transistors (IZI-TFTs) on a 300 nm SiO₂ gate dielectric at 300 °C for only 60 s yields devices with an average field effect mobility of 10.7 and 13.8 cm² V⁻¹ s⁻¹, respectively. The devices show an excellent on/off ratio (>10⁶), and a threshold voltage close to 0 V when measured in air. Flexible MO-TFTs on polyimide substrates with AlO_x dielectrics fabricated by rapid annealing treatment can achieve a remarkable mobility of over 10 cm² V⁻¹ s⁻¹ at low operating voltage. When using a longer post-coating annealing period of 20 min, high-performance 3C-TFTs (over 18 cm² V⁻¹ s⁻¹) and IZI-TFTs (over 38 cm² V⁻¹ s⁻¹) using MO semiconductor layers annealed at 300 °C are achieved.     

基于垂直结构的有机薄膜晶体管

介绍了基于垂直结构的有机薄膜晶体管的器件结构、工作原理以及相关的研究进展。通过对垂直结构的有机薄膜晶体管的特性分析,探讨了采用这种结构的有机薄膜晶体管驱动有机发光二极管的可行性。此项研究为发展新型全有机的柔性显示器提供了新的思路。     

An Intrinsically Stretchable High‐Performance Polymer Semiconductor with Low Crystallinity

For wearable and implantable electronics applications, developing intrinsically stretchable polymer semiconductor is advantageous, especially in the manufacturing of large‐area and high‐density devices. A major challenge is to simultaneously achieve good electrical and mechanical properties for these semiconductor devices. While crystalline domains are generally needed to achieve high mobility, amorphous domains are necessary to impart stretchability. Recent progresses in the design of high‐performance donor–acceptor polymers that exhibit low degrees of energetic disorder, while having a high fraction of amorphous domains, appear promising for polymer semiconductors. Here, a low crystalline, i.e., near‐amorphous, indacenodithiophene‐co‐benzothiadiazole (IDTBT) polymer and a semicrystalline thieno[3,2‐b]thiophene‐diketopyrrolopyrrole (DPPTT) are compared, for mechanical properties and electrical performance under strain. It is observed that IDTBT is able to achieve both a high modulus and high fracture strain, and to preserve electrical functionality under high strain. Next, fully stretchable transistors are fabricated using the IDTBT polymer and observed mobility ≈0.6 cm² V^?1 s^?1 at 100% strain along stretching direction. In addition, the morphological evolution of the stretched IDTBT films is investigated by polarized UV–vis and grazing‐incidence X‐ray diffraction to elucidate the molecular origins of high ductility. In summary, the near‐amorphous IDTBT polymer signifies a promising direction regarding molecular design principles toward intrinsically stretchable high‐performance polymer semiconductor.     

A Review of Vertical Organic Transistors

Powerful electronic devices require performant short‐channel transistors. For organic electronics, though, promising low‐cost and flexible electronic circuits, high processing costs for short channel devices are not acceptable. In this regard, vertical organic transistors (VOTs) are an attractive alternative, and in fact, today they reach the highest transition frequency (40 MHz) and the highest footprint current density (>1 MA cm^?2) among all organic transistors. Here, all VOT concepts are reviewed, while discussing device physics, integration approaches, and highlighting the recent developments. The upcoming challenges for the VOT technology are also presented with a guideline for further developments.     

Gradual Controlling the Work Function of Metal Electrodes by Solution‐Processed Mixed Interlayers for Ambipolar Polymer Field‐Effect Transistors and Circuits

In this paper, a technique using mixed transition‐metal oxides as contact interlayers to modulate both the electron‐ and hole‐injections in ambipolar organic field‐effect transistors (OFETs) is presented. The cesium carbonate (Cs₂CO₃) and vanadium pentoixide (V₂O₅) are found to greatly and independently improve the charge injection properties for electrons and holes in the ambipolar OFETs using organic semiconductor of diketopyrrolopyrrolethieno[3,2‐b]thiophene copolymer (DPPT‐TT) and contact electrodes of molybdenum (Mo). When Cs₂CO₃ and V₂O₅ are blended at various mixing ratios, they are observed to very finely and constantly regulate the Mo's work function from ?4.2 eV to ?4.8 eV, leading to high electron‐ and hole‐mobilities as high as 2.6 and 2.98 cm² V^?1 s^?1, respectively. The most remarkable finding is that the device characteristics and device performance can be gradually controlled by adjusting the composition of mixed‐oxide interlayers, which is highly desired for such applications as complementary circuitry that requires well matched n‐channel and p‐channel device operations. Therefore, such simple interface engineering in conjunction with utilization of ambipolar semiconductors can truly enable the promising low‐cost and soft organic electronics for extensive applications.     

Low-voltage organic transistors with steep subthreshold slope fabricated on commercially available paper

Organic thin-film transistors were fabricated directly on the surface of commercially available cleanroom paper using the vacuum-deposited small-molecule semiconductor dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (DNTT). A thin, high-capacitance gate dielectric that allows the TFTs to be operated with low voltages of 2 V was employed. The TFTs have a charge-carrier mobility of 1.6 cm²/Vs, an on/off current ratio of 10⁶, and a subthreshold slope of 90 mV/decade. In addition, the TFTs also display a very large differential output resistance, which is an important requirement for applications in analog circuits and active-matrix displays.     

Photo-Patternable Stretchable Semi-Interpenetrating Polymer Semiconductor Network Using Thiol–Ene Chemistry for Field-Effect Transistors

Stretchable polymer semiconductors are an essential component for skin-inspired electronics. However, the lack of scalable patterning capability of stretchable polymer semiconductors limits the development of stretchable electronics. To address this issue, photo-curable stretchable polymer blends consisting of a high-mobility donor–acceptor conjugated polymer and an elastic rubber through thiol–ene chemistry are developed. The thiol–ene reaction can selectively cross-link the rubber with alkene or vinyl groups without damaging the electronic properties of the conjugated polymer. The conjugated polymer chains embedded in the elastic polymer matrix induce a semi-interpenetrating polymer network (SIPN). The thiol–ene-cross-linked network provides great solvent resistance and enhances stretchability for the embedded conjugated polymer. The well-defined patterned film with a feature size of ≈10 µm can be obtained using UV light at 365 nm through conventional photolithography processes. Furthermore, the SIPN-based transistors show increased mobilities from 0.61 to 1.18 cm² V⁻¹ s⁻¹ when applying the strain from 0% to 100%. Moreover, the hole mobility can still maintain at 0.87 cm² V⁻¹ s⁻¹ after 1000 strain-and-release cycles at the strain of 25%. This study sheds light on the molecular design of photo-curable polymer semiconductors for the mass production of stretchable circuits.     

Printed Neuromorphic Devices Based on Printed Carbon Nanotube Thin‐Film Transistors

Hardware implementation of artificial synapse/neuron by electronic/ionic hybrid devices is of great interest for brain‐inspired neuromorphic systems. At the same time, printed electronics have received considerable interest in recent years. Here, printed dual‐gate carbon‐nanotube thin‐film transistors with very high saturation field‐effect mobility (≈269 cm² V^?1 s^–1) are proposed for artificial synapse application. Some important synaptic behaviors including paired‐pulse facilitation (PPF), and signal filtering characteristics are successfully emulated in such printed artificial synapses. The PPF index can be modulated by spike width and spike interval of presynaptic impulse voltages. The results present a printable approach to fabricate artificial synaptic devices for neuromorphic systems.