High Tg Cyclic Olefin Copolymer Gate Dielectrics for N,N′‐Ditridecyl Perylene Diimide Based Field‐Effect Transistors: Improving Performance and Stability with Thermal Treatment

A novel application of ethylene‐norbornene cyclic olefin copolymers (COC) as gate dielectric layers in organic field‐effect transistors (OFETs) that require thermal annealing as a strategy for improving the OFET performance and stability is reported. The thermally‐treated N,N′‐ditridecyl perylene diimide (PTCDI‐C13)‐based n‐type FETs using a COC/SiO₂ gate dielectric show remarkably enhanced atmospheric performance and stability. The COC gate dielectric layer displays a hydrophobic surface (water contact angle = 95° ± 1°) and high thermal stability (glass transition temperature = 181 °C) without producing crosslinking. After thermal annealing, the crystallinity improves and the grain size of PTCDI‐C13 domains grown on the COC/SiO₂ gate dielectric increases significantly. The resulting n‐type FETs exhibit high atmospheric field‐effect mobilities, up to 0.90 cm² V^?1 s^?1 in the 20 V saturation regime and long‐term stability with respect to H₂O/O₂ degradation, hysteresis, or sweep‐stress over 110 days. By integrating the n‐type FETs with p‐type pentacene‐based FETs in a single device, high performance organic complementary inverters that exhibit high gain (exceeding 45 in ambient air) are realized.     

Organic Electronics: High Tg Cyclic Olefin Copolymer Gate Dielectrics for N,N′‐Ditridecyl Perylene Diimide Based Field‐Effect Transistors: Improving Performance and Stability with Thermal Treatment (Adv. Funct. Mater. 16/2010)

A novel application of ethylene‐norbornene cyclic olefin copolymers (COC) as gate dielectric layers in organic field‐effect transistors (OFETs) that require thermal annealing as a strategy for improving the OFET performance and stability is reported. The thermally‐treated N,N′‐ditridecyl perylene diimide (PTCDI‐C13)‐based n‐type FETs using a COC/SiO₂ gate dielectric show remarkably enhanced atmospheric performance and stability. The COC gate dielectric layer displays a hydrophobic surface (water contact angle = 95° ± 1°) and high thermal stability (glass transition temperature = 181 °C) without producing crosslinking. After thermal annealing, the crystallinity improves and the grain size of PTCDI‐C13 domains grown on the COC/SiO₂ gate dielectric increases significantly. The resulting n‐type FETs exhibit high atmospheric field‐effect mobilities, up to 0.90 cm² V^?1 s^?1 in the 20 V saturation regime and long‐term stability with respect to H₂O/O₂ degradation, hysteresis, or sweep‐stress over 110 days. By integrating the n‐type FETs with p‐type pentacene‐based FETs in a single device, high performance organic complementary inverters that exhibit high gain (exceeding 45 in ambient air) are realized.     

Laminated Modulation of Tricritical Ferroelectrics Exhibiting Highly Enhanced Dielectric Permittivity and Temperature Stability

Ferroelectric materials with large dielectric response and high temperature‐stability have found significant applications in advanced electronics and electrical power/storage equipment. The effective approaches explored up to now mainly focus on improving dielectric response by employing the phase instability caused by the ferroelectric transition. Nevertheless, one inherent shortcoming is that the enhancement of dielectric permittivity is at the expense of the deterioration of its temperature stability. Here, a strategy that successfully achieves both enhanced dielectric response as well as excellent temperature reliability (with ε_r ≈ 2 × 10⁴ from 30 to 85 °C) by designing a laminated structure of tricritical ferroelectrics (LTF) with successive Curie temperatures is proposed. Moreover, the improvement in dielectric performance triggers the temperature‐stable energy‐storage performance as well as electrocaloric property in LTF specimens. Further microstructure investigation and phase‐field modeling reveal that these remarkable properties of laminated layers originate from the successive occurrence of tricritical transition with a nanodomain structure in a wide temperature range. The findings may shed a new light on developing advanced ferroelectrics with high performance and thermal reliability.     

Polylactic acid as a biodegradable material for all-solution-processed organic electronic devices

In this paper we report on the fabrication of spin-coated biodegradable polylactic acid (PLA) thin films to be used as substrates for the realisation of all-solution-processed organic electronic devices. The full mechanical and electrical characterisation of these substrates shows that they exhibit good mechanical and dielectric properties and are therefore suitable for the fabrication of disposable electronics. To demonstrate practically the functionality of such PLA thin films, organic electronic devices were realised on the top of them, exclusively by means of solution-process fabrication techniques and in particular inkjet-printing. Also, a photonic curing procedure is here presented as a means for sintering the conductive inks without heating up the PLA substrates. Two types of organic transistors were fabricated on the top of PLA: organic field-effect transistors (OFETs), where the PLA film was used not only as a substrate but also as the gate dielectric, and all-inkjet-printed organic electrochemical transistors (OECTs). The second typology of transistors exhibited one of the highest transconductance reported so far in the literature (up to 2.75 mS). This study opens an avenue for the fabrication of disposable, low-cost organic electronic devices.     

Stretchable,Transparent, and Thermally Stable Triboelectric Nanogenerators Based on Solvent‐Free Ion‐Conducting Elastomer Electrodes

The development of stretchable/soft electronics requires power sources that can match their stretchability. In this study, a highly stretchable, transparent, and environmentally stable triboelectric nanogenerator with ionic conductor electrodes (iTENG) is reported. The ion‐conducting elastomer (ICE) electrode, together with a dielectric elastomer electrification layer, allows the ICE‐iTENG to achieve a stretchability of 1036% and transmittance of 91.5%. Most importantly, the ICE is liquid solvent‐free and thermally stable up to 335 °C, avoiding the dehydration‐induced performance degradation of commonly used hydrogels. The ICE‐iTENG shows no decrease in electrical output even after storing at 100 °C for 15 h. Biomechanical motion energies are demonstrated to be harvested by the ICE‐iTENG for powering wearable electronics intermittently without extra power sources. An ICE‐iTENG‐based pressure sensor is also developed with sensitivity up to 2.87 kPa^?1. The stretchable ICE‐iTENG overcomes the strain‐induced performance degradation using percolated electrical conductors and liquid evaporation‐induced degradation using ion‐conducting hydrogels/ionogels, suggesting great promising applications in soft/stretchable electronics under a relatively wider temperature range.     

Super‐ and Ultrathin Organic Field‐Effect Transistors: from Flexibility to Super‐ and Ultraflexibility

Physically flexible electronics offer a wide range of benefits, including the development of next‐generation consumer electronics and healthcare products. The advancement of physical flexibility, typically achieved by the reduction of the total device thickness, including substrates and encapsulation layers, shows great promise for skin‐laminated electronics. Organic electronics—devices relying on carbon‐based materials—offer many advantages over their inorganic counterparts, including the following: significantly lower fabrication temperatures resulting in alternative fabrication techniques, including inkjet and roll‐to‐roll printing, enabling low‐cost and large‐area fabrication; biocompatibility; and spectacular physical flexibility. This article presents a review, spanning the last two decades, of organic field‐effect transistors with the total thickness of just a few microns as well as devices demonstrated in this decade with a total thickness of few hundred of nanometers. A handful of demonstrations of other organic electronic thin film devices are also presented.     

Stretchable and Heat‐Resistant Protein‐Based Electronic Skin for Human Thermoregulation

Silk protein is one of the a promising materials for on‐skin and implantable electronic devices due to its biodegradability and biocompatibility. However, its intrinsic brittleness as well as poor thermal stability limits its applications. In this work, robust and heat‐resistant silk fibroin composite membranes (SFCMs) are synthesized by mesoscopic doping of regenerated silk fibroin (SF) via the strong interactions between SF and polyurethane. Surprisingly, the obtained SFCMs can endure the tensile test (>200%) and thermal treatment (up to 160 °C). Attributed to these advantages, traditional micromachining techniques, such as inkjet printing, can be carried out to print flexible circuits on such protein substrate. Based on this, Ag nanofibers (NFs) and Pt NFs networks are successfully constructed on both sides of the SFCMs to function as heaters and temperature sensors, respectively. Furthermore, the integrated protein‐based electronic skin (PBES) exhibits high thermal stability and temperature sensitivity (0.205% °C^?1). Heating and temperature distribution detection are realized by array‐type PBES, contributing to potential applications in dredging of the blood vessel for alleviating arthritis. This PBES is also inflammation‐free and air‐permeable so that it can directly be laminated onto human skin for long‐term thermal management.     

Flexible,Conformal Organic Synaptic Transistors on Elastomer for Biomedical Applications

Bioelectronics in synaptic transistors for future biomedical applications, such as implanted treatments and human–machine interfaces, must be flexible with good mechanical compatibility with biological tissues. The rigid nature and high deposition temperature in conventional inorganic synaptic transistors restrict the development of flexible, conformal synaptic devices. Here, the dinaphtho[2,3‐b:2′,3′‐f]thieno[3,2‐b]‐thiophene organic synaptic transistor on elastic polydimethylsiloxane is demonstrated to avoid these limitations. The unique advantages of organic materials in low Young's modulus and low temperature process enable seamless adherence of organic synaptic transistors on arbitrary‐shaped objects. On 3D curved surfaces, the essential synaptic functions, such as potentiation/depression, short/long‐term synaptic plasticity, and spike voltage–dependent plasticity, are successfully realized. The time‐dependent surface potential characterization reveals the slow polarization of dipoles in the dielectric is responsible for hysteresis and synaptic behaviors. This work represents that organic materials offer a potential platform to realize the flexible, conformal synaptic transistors for the development of wearable and implantable artificial neuromorphic systems.     

Polyelectrolyte Dielectrics for Flexible Low‐Voltage Organic Thin‐Film Transistors in Highly Sensitive Pressure Sensing

Organic thin‐film transistors (OTFTs) can provide an effective platform to develop flexible pressure sensors in wearable electronics due to their good signal amplification function. However, it is particularly difficult to realize OTFT‐based pressure sensors with both low‐voltage operation and high sensitivity. Here, controllable polyelectrolyte composites based on poly(ethylene glycol) (PEG) and polyacrylic acid (PAA) are developed as a type of high‐capacitance dielectrics for flexible OTFTs and ultrasensitive pressure sensors with sub‐1 V operation. Flexible OTFTs using the PAA:PEG dielectrics show good universality and greatly enhanced electrical performance under a much smaller operating voltage of ?0.7 V than those with a pristine PAA dielectric. The low‐voltage OTFTs also exhibit excellent flexibility and bending stability under various bending radii and long cycles. Flexible OTFT‐based pressure sensors with low‐voltage operation and superhigh sensitivity are demonstrated by using a suspended semiconductor/dielectric/gate structure in combination with the PAA:PEG dielectric. The sensors deliver a record high sensitivity of 452.7 kPa^?1 under a low‐voltage of ?0.7 V, and excellent operating stability over 5000 cycles. The OTFT sensors can be built into a wearable sensor array for spatial pressure mapping, which shows a bright potential in flexible electronics such as wearable devices and smart skins.     

Highly Robust Flexible Ferroelectric Field Effect Transistors Operable at High Temperature with Low‐Power Consumption

Flexible ferroelectric field effect transistors (FeFETs) with multiple functionalities and tunable properties are attractive for low power sensing, nonvolatile data storage, as well as emerging memristor applications such as artificial synapses, though the state‐of‐art flexible FeFETs based on organic materials possess low polarization, large coercivity, and high operating voltage, and suffer from poor thermal stability. Here, developed is an all‐inorganic flexible FeFET based on epitaxial Pb(Zr_0.1Ti_0.9)O₃/ZnO heterostructure on a mica substrate, which not only operates under a small voltage (±6 V) and thus consumes low power with an excellent on/off ratio of 10⁴ as well as retention characteristics, but also shows robust FeFET performance under large bending deformation (4 mm), extended bending cycling (500 cycles), and high temperature operation at 200 °C. Importantly, the FeFET characteristics depend on temperature, but not on temperature history, critical for operation under repeated thermal loading. The excellent mechanical flexibility and functional robustness of the flexible FeFET originate from the unique van der Waals bonded layer structure of mica, facilitating a small bending radius yet modest strain. This work demonstrates the great promise of mica as a universal platform to integrate complicated functional devices for flexible electronics, especially under harsh environment.     

Low‐Temperature,Nontoxic Water‐Induced Metal‐Oxide Thin Films and Their Application in Thin‐Film Transistors

Here, a simple, nontoxic, and inexpensive “water‐inducement” technique for the fabrication of oxide thin films at low annealing temperatures is reported. For water‐induced (WI) precursor solution, the solvent is composed of water without additional organic additives and catalysts. The thermogravimetric analysis indicates that the annealing temperature can be lowered by prolonging the annealing time. A systematic study is carried out to reveal the annealing condition dependence on the performance of the thin‐film transistors (TFTs). The WI indium‐zinc oxide (IZO) TFT integrated on SiO₂ dielectric, annealed at 300 °C for 2 h, exhibits a saturation mobility of 3.35 cm² V^?1 s^?1 and an on‐to‐off current ratio of ≈10⁸. Interestingly, through prolonging the annealing time to 4 h, the electrical parameters of IZO TFTs annealed at 230 °C are comparable with the TFTs annealed at 300 °C. Finally, fully WI IZO TFT based on YO_x dielectric is integrated and investigated. This TFT device can be regarded as “green electronics” in a true sense, because no organic‐related additives are used during the whole device fabrication process. The as‐fabricated IZO/YO_x TFT exhibits excellent electron transport characteristics with low operating voltage (≈1.5 V), small subthreshold swing voltage of 65 mV dec^?1 and the mobility in excess of 25 cm² V^?1 s^?1.     

Transparent Photo‐Stable Complementary Inverter with an Organic/Inorganic Nanohybrid Dielectric Layer

Transparent electronics has been one of the key terminologies forecasting the ubiquitous technology era. Several researchers have thus extensively developed transparent oxide‐based thin‐film transistors (TFTs) on glass and plastic substrates. However, work in transparent electronics has been limited mostly to high‐voltage devices operating at more than a few tens of volts, and has mainly focused on transparent display drivers. Low‐voltage logic devices, such as transparent complementary inverters, operating in an electrically stable and photo‐stable manner, are now very necessary to practically realize transparent electronics. Electrically stable dielectrics with high strength and high capacitance must also be proposed to support this mission, and simultaneously these dielectrics must be compatible with both n‐ and p‐channel TFTs in device fabrication. Here, a nanohybrid dielectric layer that is composed of multiple units of inorganic oxide and organic self‐assembled monolayer is proposel to support a transparent complementary TFT inverter operating at 3 V.     

Temperature‐Memory Effect of Copolyesterurethanes and their Application Potential in Minimally Invasive Medical Technologies

Minimally invasive surgery often requires devices that can change their geometry or shape when placed inside the body. Here, the potential of thermoplastic temperature‐memory polymers (TMP) for the design of intelligent devices, which can be programmed by the clinician to individually adapt their shifting geometry and their response temperature T_sw to the patient's needs, is explored. Poly(ω‐pentadecalactone) as hard segments and poly(?‐caprolactone) segments acting as crystallizable controlling units for the temperature‐memory effect (TME) are chosen to form multiblock copolymers PDLCL. These components are selected according to their thermal properties and their good biocompatibility. Response temperatures obtained under stress‐free and constant strain recovery can be systematically adjusted by variation of the deformation temperature in a temperature range from 32 °C to 65 °C, which is the relevant temperature range for medical applications. The working principle of TMP based instruments for minimally invasive surgical procedures is successfully demonstrated using three temperature‐memory catheter concepts: individually programmable TM‐catheter, an in‐situ programmable TM‐catheter, and an intelligent drainage catheter for gastroenterology.     

Room‐Temperature Printing of Organic Thin‐Film Transistors with π‐Junction Gold Nanoparticles

Printing semiconductor devices under ambient atmospheric conditions is a promising method for the large‐area, low‐cost fabrication of flexible electronic products. However, processes conducted at temperatures greater than 150 °C are typically used for printed electronics, which prevents the use of common flexible substrates because of the distortion caused by heat. The present report describes a method for the room‐temperature printing of electronics, which allows thin‐film electronic devices to be printed at room temperature without the application of heat. The development of π‐junction gold nanoparticles as the electrode material permits the room‐temperature deposition of a conductive metal layer. Room‐temperature patterning methods are also developed for the Au ink electrodes and an active organic semiconductor layer, which enables the fabrication of organic thin‐film transistors through room‐temperature printing. The transistor devices printed at room temperature exhibit average field‐effect mobilities of 7.9 and 2.5 cm² V^?1 s^?1 on plastic and paper substrates, respectively. These results suggest that this fabrication method is very promising as a core technology for low‐cost and high‐performance printed electronics.     

High‐Mobility and Low Turn‐On Voltage n‐Channel OTFTs Based on a Solution‐Processable Derivative of Naphthalene Bisimide

In organic electronics solution‐processable n‐channel field‐effect transistors (FETs) matching the parameters of the best p‐channel FETs are needed. Progress toward the fabrication of such devices is strongly impeded by a limited number of suitable organic semiconductors as well as by the lack of processing techniques that enable strict control of the supramolecular organization in the deposited layer. Here, the use of N,N′‐bis(4‐n‐butylphenyl)‐1,4,5,8‐naphthalenetetracarboxylic‐1,4:5,8‐bisimide (NBI‐4‐n‐BuPh) for fabrication of n‐channel FETs is described. The unidirectionally oriented crystalline layers of NBI‐4‐n‐BuPh are obtained by the zone‐casting method under ambient conditions. Due to the bottom‐contact, top‐gate configuration used, the gate dielectric, Parylene C, also acts as a protective layer. This, together with a sufficiently low LUMO level of NBI‐4‐n‐BuPh allows the fabrication and operation of these novel n‐channel transistors under ambient conditions. The high order of the NBI‐4‐n‐BuPh molecules in the zone‐cast layer and high purity of the gate dielectric yield good performance of the transistors.     

Low‐Temperature‐Processed Printed Metal Oxide Transistors Based on Pure Aqueous Inks

Additive patterning of transparent conducting metal oxides at low temperatures is a critical step in realizing low‐cost transparent electronics for display technology and photovoltaics. In this work, inkjet‐printed metal oxide transistors based on pure aqueous chemistries are presented. These inks readily convert to functional thin films at lower processing temperatures (T ≤ 250 °C) relative to organic solvent‐based oxide inks, facilitating the fabrication of high‐performance transistors with both inkjet‐printed transparent electrodes of aluminum‐doped cadmium oxide (ACO) and semiconductor (InO_x ). The intrinsic fluid properties of these water‐based solutions enable the printing of fine features with coffee‐ring free line profiles and smoother line edges than those formed from organic solvent‐based inks. The influence of low‐temperature annealing on the optical, electrical, and crystallographic properties of the ACO electrodes is investigated, as well as the role of aluminum doping in improving these properties. Finally, the all‐aqueous‐printed thin film transistors (TFTs) with inkjet‐patterned semiconductor (InO_x ) and source/drain (ACO) layers are characterized, which show ideal low contact resistance (R _c < 160 Ω cm) and competitive transistor performance (µ _lin up to 19 cm² V^?1 s^?1, Subthreshold Slope (SS) ≤150 mV dec^?1) with only low‐temperature processing (T ≤ 250 °C).     

Flexible Low‐Power Operative Organic Source‐Gated Transistors

Low‐voltage operation and fast switching ability are necessary for wearable electronic devices. Recently, electrolyte dielectric materials have been widely used to decrease driving voltages; however, they often exhibit unwanted doping effects and power dissipation problems. Here, a method for dramatically lowering driving voltages is reported in organic electronics via source‐gated transistor (SGT) structures. SGTs are fabricated by evaporating asymmetric metals with different work functions for the source and drain electrodes. Versatile organic semiconductor‐based SGTs demonstrate a significantly lower drain voltage (<10 V) for the saturation regime compared to that of typical field‐effect transistors with the same dielectric layer (>80 V). Furthermore, coating reduced Pyronin B (rPyB) onto n‐type SGTs decreases the threshold voltage from 51.2 to 0.1 eV and improves air‐stability, exhibiting a maintained electron mobility (>90%) for 40 d. The air‐stability is due to both the energetic and kinetic factors, including a decreased lowest unoccupied molecular orbital level of the n‐type semiconductor after doping and covering the active layer with rPyB. Finally, flexible SGTs are fabricated on a Parylene‐C substrate that shows highly stable operation in a bending test. The results demonstrate a promising technology for low‐power, flexible electronic devices via electrode engineering.     

Design of Engineered Elastomeric Substrate for Stretchable Active Devices and Sensors

In the field of flexible electronics, emerging applications require biocompatible and unobtrusive devices, which can withstand different modes of mechanical deformation and achieve low complexity in the fabrication process. Here, the fabrication of a mesa‐shaped elastomeric substrate, supporting thin‐film transistors (TFTs) and logic circuits (inverters), is reported. High‐relief structures are designed to minimize the strain experienced by the electronics, which are fabricated directly on the pillars' surface. In this design configuration, devices based on amorphous indium‐gallium‐zinc‐oxide can withstand different modes of deformation. Bending, stretching, and twisting experiments up to 6 mm radius, 20% uniaxial strain, and 180° global twisting, respectively, are performed to show stable electrical performance of the TFTs. Similarly, a fully integrated digital inverter is tested while stretched up to 20% elongation. As a proof of the versatility of mesa‐shaped geometry, a biocompatible and stretchable sensor for temperature mapping is also realized. Using pectin, which is a temperature‐sensitive material present in plant cells, the response of the sensor shows current modulation from 13 to 28 °C and functionality up to 15% strain. These results demonstrate the performance of highly flexible electronics for a broad variety of applications, including smart skin and health monitoring.     

Highly Thermal Stable and Efficient Organic Photovoltaic Cells with Crosslinked Networks Appending Open‐Cage Fullerenes as Additives

Highly thermal stable organic bulk heterojunction (OBHJ) photovoltaic cells are demonstrated with crosslinkable open‐cage fullerenes ( COF ) as additives in the active layer. Partial incorporation of COF , ≈10–15 wt% with weight ratio of P3HT: PC₆₁BM = 1:0.9, builds up three‐dimensional local borders upon heating treatment at 150 °C for 10 min. This process induces crosslinking chemical reaction through activating the styryl moiety in COF and reduces phase aggregation rates of fullerenes materials. Supported by statistics of devices degradation data analysis and optical microscopy study, the devices with COF show longer lifetime with keeping their efficiency (t = 144 h) under accelerated heating test at 150 °C, while PCE of normal devices without COF drop dramatically. These results demonstrate that the thermally crosslinkable COF is an excellent additive for highly thermal stable and durable OPVs applications.     

Thermally Stable Hole‐Transporting Materials Based upon a Fluorene Core

We report a new class of diamine hole‐transporting materials (HTMs) based upon a fluorene core. Using a fluorene core, rather than a biphenyl group, leads to enhanced thermal stability, as evidenced by glass‐transition (T_g) temperatures as high as 161 °C for N,N′‐iminostilbenyl‐4,4′‐fluorene (ISF). The fluorene‐based HTMs have lower ionization potentials (I_p) than their biphenyl analogs, which leads to more efficient injection of holes from the indium tin oxide (ITO) anode, and higher quantum efficiencies. Devices prepared with fluorene‐based HTMs were operated under thermal stress. The failure of an organic light‐emitting diode (OLED) under thermal stress has a direct correlation with the thermal stability of the HTM that is in contact with the ITO anode. OLEDs based on ISF are stable to over 140 °C.