Printable and Flexible Phototransistors Based on Blend of Organic Semiconductor and Biopolymer

Printable and flexible organic phototransistors (OPTs) make comprehensive requirements for the organic semiconductors (OSCs), including high photosensitivity, decent transistor characteristics, appropriate solution viscosity, and good film flexibility. It has been challenging to obtain such semiconductors. Here, we demonstrated that by taking advantage of the interfacial charge effect, printable and flexible OPTs with high performance can be successfully fabricated through simply blending common OSCs with polymers. Using 2,7‐dioctyl[1]benzothieno[3,2‐b][1]benzothiophene and an insulating biopolymer polylactide, OPTs with blended and layered structure are both fabricated and investigated. The photoresponses of the OPTs can be modulated by gate voltage over 1000 times, and their responsivities are measured up to 400 A W^?1. As compared to the layered OPTs, the blended ones exhibit higher photocurrent to dark current ratio (up to 10⁵) and better light detection limit (lower than 0.02 mW cm^?2). The improvements are attributed to larger interfacial area and more intensive charge trapping effect. The flexible OPTs are further fabricated by inkjet printing the blended solution. This work presents OPTs with comprehensive advantages including low cost, enhanced photosensitivity, great flexibility, and printability, which are realized by simply blending common OSC with polymer, and thus provide an inspiration for the design of novel organic electronics.     

High‐Sensitivity Floating‐Gate Phototransistors Based on WS2 and MoS2

In recent years, 2D layered materials have been considered as promising photon absorption channel media for next‐generation phototransistors due to their atomic thickness, easily tailored single‐crystal van der Waals heterostructures, ultrafast optoelectronic characteristics, and broadband photon absorption. However, the photosensitivity obtained from such devices, even under a large bias voltage, is still unsatisfactory until now. In this paper, high‐sensitivity phototransistors based on WS₂ and MoS₂ are proposed, designed, and fabricated with gold nanoparticles (AuNPs) embedded in the gate dielectric. These AuNPs, located between the tunneling and blocking dielectric, are found to enable efficient electron trapping in order to strongly suppress dark current. Ultralow dark current (10^?11 A), high photoresponsivity (1090 A W^?1), and high detectivity (3.5 × 10¹¹ Jones) are obtained for the WS₂ devices under a low source/drain and a zero gate voltage at a wavelength of 520 nm. These results demonstrate that the floating‐gate memory structure is an effective configuration to achieve high‐performance 2D electronic/optoelectronic devices.     

High‐Performance Phototransistors Based on Single‐Crystalline n‐Channel Organic Nanowires and Photogenerated Charge‐Carrier Behaviors

The photoelectronic characteristics of single‐crystalline nanowire organic phototransistors (NW‐OPTs) are studied using a high‐performance n‐channel organic semiconductor, N,N′‐bis(2‐phenylethyl)‐perylene‐3,4:9,10‐tetracarboxylic diimide (BPE‐PTCDI), as the photoactive layer. The optoelectronic performances of the NW‐OPTs are analyzed by way of their current–voltage (I–V) characteristics on irradiation at different wavelengths, and comparison with corresponding thin‐film organic phototransistors (OPTs). Significant enhancement in the charge‐carrier mobility of NW‐OPTs is observed upon light irradiation as compared with when performed in the dark. A mobility enhancement is observed when the incident optical power density increases and the wavelength of the light source matches the light‐absorption range of the photoactive material. The photoswitching ratio is strongly dependent upon the incident optical power density, whereas the photoresponsivity is more dependent on matching the light‐source wavelength with the maximum absorption range of the photoactive material. BPE‐PTCDI NW‐OPTs exhibit much higher external quantum efficiency (EQE) values (≈7900 times larger) than thin‐film OPTs, with a maximum EQE of 263 000%. This is attributed to the intrinsically defect‐free single‐crystalline nature of the BPE‐PTCDI NWs. In addition, an approach is devised to analyze the charge‐transport behaviors using charge accumulation/release rates from deep traps under on/off switching of external light sources.     

High‐Performance Thermally Stable Organic Phototransistors Based on PSeTPTI/PC61BM for Visible and Ultraviolet Photodetection

Phototransistors are three‐terminal photodetectors which usually have higher photosensitivity than photodiodes due to the presence of gate electrode. In this report, organic phototransistors (OPTs) based on a donor material, namely, poly{2,5‐selenophene‐alt‐2,8‐(4,10‐bis(2‐hexyldecyl))thieno[2′,3′:5,6]­pyrido[3,4‐g]thieno[3,2‐c]isoquinoline‐5,11(4H,10H)‐dione} (PSeTPTI), are fabricated and intensively studied. As unipolar p‐type organic semiconductor usually has plenty of electron traps in the bulk to impede electron transporting, most of photogenerated electrons will fill the traps in PSeTPTI and this process can prolong the response time. By introducing [6,6]‐phenyl C₆₁ butyric acid methyl ester on top, the p–n heterojunction can produce most of the photocurrent and eliminates the influence from the process of trapping electrons. This mechanism improves the photoresponsivity and response speed. Since ultraviolet (UV) detection is very important in some fields including military, aerospace, and biology, the OPTs are characterized under UV illumination besides the visible light and they present high sensitivity. Furthermore, organic semiconductors often have bad stability in harsh conditions and meanwhile some devices need to work in these environments. At high temperature even up to 200 °C, our OPTs can work normally and show very high stability, indicating the potential of the devices in applications of high‐temperature environments.     

Highly photosensitive thienoacene single crystal microplate transistors via optimized dielectric

High photosensitivity and high photocurrent gain have been obtained based on dielectric optimized dinaphtho[3,4-d:3′,4′-d′]benzo[1,2-b:4,5-b′]dithiophene (Ph5T2) single crystal microplate transistors. In our experiments, the PMMA dielectric device shows the best operational stability without hysteresis effect. Based on such an optimized device, the photoelectric properties of the Ph5T2 single crystal microplates have been studied for the first time. The Ph5T2 phototransistor has the high photosensitivity at 21 mA W⁻¹ and the extremely high photocurrent gain (I_light/I_dark) at 6.8 × 10⁵. The photocurrent gain is higher than that of the most reported organic phototransistors (OPTs), and is in a class with the highest photocurrent gain for the reported values so far. This confirms that Ph5T2 is a photosensitive material and shows it promising potential in photoswitches and phototransistors.     

High‐Performance,Air‐Stable,Top‐Gate,p‐Channel WSe2 Field‐Effect Transistor with Fluoropolymer Buffer Layer

High‐performance, air‐stable, p‐channel WSe₂ top‐gate field‐effect transistors (FETs) using a bilayer gate dielectric composed of high‐ and low‐k dielectrics are reported. Using only a high‐k Al₂O₃ as the top‐gate dielectric generally degrades the electrical properties of p‐channel WSe₂, therefore, a thin fluoropolymer (Cytop) as a buffer layer to protect the 2D channel from high‐k oxide forming is deposited. As a result, a top‐gate‐patterned 2D WSe₂ FET is realized. The top‐gate p‐channel WSe₂ FET demonstrates a high hole mobility of 100 cm²_­ V^?1 s^?1 and a I_ON/I_OFF ratio > 10⁷ at low gate voltages (V_GS ca. ?4 V) and a drain voltage (V_DS) of ?1 V on a glass substrate. Furthermore, the top‐gate FET shows a very good stability in ambient air with a relative humidity of 45% for 7 days after device fabrication. Our approach of creating a high‐k oxide/low‐k organic bilayer dielectric is advantageous over single‐layer high‐k dielectrics for top‐gate p‐channel WSe₂ FETs, which will lead the way toward future electronic nanodevices and their integration.     

Flexible organic phototransistors based on a combination of printing methods

Highly photosensitive organic phototransistors (OPTs) are successfully demonstrated on a flexible substrate using all-solution process as well as a combination of printing methods which consist of roll-to-plate reverse offset printing (ROP), inkjet printing and bar coating. Excellent electrical switching characteristics are obtained from heterogeneous interfacial properties of the reverse-offset-printed silver nanoparticle electrode and the inkjet-printed p-channel polymeric semiconductor. In particular, the OPTs exhibit remarkably photosensitivity with a photo-to-dark current ratio exceeding 5 orders. This optoelectronic properties of the combinational printed OPTs are theoretically and experimentally studied, and found the comparable tendency. In addition, excellent mechanical stability is observed with up to 0.5% of strain applied to the OPTs. Hence, by manufactured with a combination of various graphic art printing methods such as roll-to-plate ROP, inkjet printing, and bar coating, these devices are very promising candidates for large-area and low-cost printed and flexible optoelectronics applications.     

Self‐Assembled,Millimeter‐Sized TIPS‐Pentacene Spherulites Grown on Partially Crosslinked Polymer Gate Dielectric

Here, a highly crystalline and self‐assembled 6,13‐bis(triisopropylsilylethynyl) pentacene (TIPS‐Pentacene) thin films formed by simple spin‐coating for the fabrication of high‐performance solution‐processed organic field‐effect transistors (OFETs) are reported. Rather than using semiconducting organic small‐molecule–insulating polymer blends for an active layer of an organic transistor, TIPS‐Pentacene organic semiconductor is separately self‐assembled on partially crosslinked poly‐4‐vinylphenol:poly(melamine‐co‐formaldehyde) (PVP:PMF) gate dielectric, which results in a vertically segregated semiconductor‐dielectric film with millimeter‐sized spherulite‐crystalline morphology of TIPS‐Pentacene. The structural and electrical properties of TIPS‐Pentacene/PVP:PMF films have been studied using a combination of polarized optical microscopy, atomic force microscopy, 2D‐grazing incidence wide‐angle X‐ray scattering, and secondary ion mass spectrometry. It is finally demonstrated a high‐performance OFETs with a maximum hole mobility of 3.40 cm² V^?1 s^?1 which is, to the best of our knowledge, one of the highest mobility values for TIPS‐Pentacene OFETs fabricated using a conventional solution process. It is expected that this new deposition method would be applicable to other small molecular semiconductor–curable polymer gate dielectric systems for high‐performance organic electronic applications.     

Controllable Shifts in Threshold Voltage of Top‐Gate Polymer Field‐Effect Transistors for Applications in Organic Nano Floating Gate Memory

Organic field‐effect transistor (FET) memory is an emerging technology with the potential to realize light‐weight, low‐cost, flexible charge storage media. Here, solution‐processed poly[9,9‐dioctylfluorenyl‐2,7‐diyl]‐co‐(bithiophene)] (F8T2) nano floating gate memory (NFGM) with a top‐gate/bottom‐contact device configuration is reported. A reversible shift in the threshold voltage (V_Th) and reliable memory characteristics was achieved by the incorporation of thin Au nanoparticles (NPs) as charge storage sites for negative charges (electrons) at the interface between polystyrene and cross‐linked poly(4‐vinylphenol). The F8T2 NFGM showed relatively high field‐effect mobility (µ_FET) (0.02 cm² V^?1 s^?1) for an amorphous semiconducting polymer with a large memory window (ca. 30 V), a high on/off ratio (more than 10⁴) during writing and erasing with an operation voltage of 80 V of gate bias in a relatively short timescale (less than 1 s), and a retention time of a few hours. This top‐gated polymer NFGM could be used as an organic transistor memory element for organic flash memory.     

High‐Performance Organic Heterojunction Phototransistors Based on Highly Ordered Copper Phthalocyanine/para‐Sexiphenyl Thin Films

High‐performance organic heterojunction phototransistors are fabricated using highly ordered copper phthalocyanine (CuPc) and para ‐sexiphenyl (p ‐6P) thin films. The p ‐6P thin film plays an important role on the performance of CuPc/p ‐6P heterojunction phototransistors. It acts as a molecular template layer to induce the growth of highly ordered CuPc thin film, which dramatically improves the charge transport and decreases the grain boundaries. On the other hand, the p ‐6P thin film can form an effective heterojunction with CuPc thin film, which is greatly helpful to enhance the light absorption and photogenerated carriers. Under 365 nm ultraviolet light irradiation, the ratio of photocurrent and dark current and photoresponsivity of CuPc/p ‐6P heterojunction phototransistors reaches to about 2.2 × 10⁴ and 4.3 × 10² A W^?1, respectively, which are much larger than that of CuPc phototransistors of about 2.7 × 10² and 7.3 A W^?1, respectively. A detailed study carried out with current sensing atomic force microscopy proves that the photocurrent is predominately produced inside the highly ordered CuPc/p ‐6P heterojunction grains, while the photocurrent produced at the boundaries between grains can be neglected. The research provides a good method for fabricating high‐performance organic phototransistors using a combination of molecular template growth and organic heterojunction.     

Highly Stretchable,High‐Mobility,Free‐Standing All‐Organic Transistors Modulated by Solid‐State Elastomer Electrolytes

Highly stretchable, high‐mobility, and free‐standing coplanar‐type all‐organic transistors based on deformable solid‐state elastomer electrolytes are demonstrated using ionic thermoplastic polyurethane (i‐TPU), thereby showing high reliability under mechanical stimuli as well as low‐voltage operation. Unlike conventional ionic dielectrics, the i‐TPU electrolyte prepared herein has remarkable characteristics, i.e., a large specific capacitance of 5.5 µF cm^?2, despite the low weight ratio (20 wt%) of the ionic liquid, high transparency, and even stretchability. These i‐TPU‐based organic transistors exhibit a mobility as high as 7.9 cm² V^?1 s^?1, high bendability (R_c, radius of curvature: 7.2 mm), and good stretchability (60% tensile strain). Moreover, they are suitable for low‐voltage operation (V_DS = ?1.0 V, V_GS = ?2.5 V). In addition, the electrical characteristics such as mobility, on‐current, and threshold voltage are maintained even in the concave and convex bending state (bending tensile strain of ≈3.4%), respectively. Finally, free‐standing, fully stretchable, and semi‐transparent coplanar‐type all‐organic transistors can be fabricated by introducing a poly(3,4‐ethylenedioxythiophene):polystyrene sulfonic acid layer as source/drain and gate electrodes, thus achieving low‐voltage operation (V_DS = ?1.5 V, V_GS = ?2.5 V) and an even higher mobility of up to 17.8 cm² V^?1 s^?1. Moreover, these devices withstand stretching up to 80% tensile strain.     

High Responsivity Phototransistors Based on Few‐Layer ReS2 for Weak Signal Detection

2D transition metal dichalcogenides are emerging with tremendous potential in many optoelectronic applications due to their strong light–matter interactions. To fully explore their potential in photoconductive detectors, high responsivity is required. Here, high responsivity phototransistors based on few‐layer rhenium disulfide (ReS₂) are presented. Depending on the back gate voltage, source drain bias and incident optical light intensity, the maximum attainable photoresponsivity can reach as high as 88 600 A W^?1, which is a record value compared to other individual 2D materials with similar device structures and two orders of magnitude higher than that of monolayer MoS₂. Such high photoresponsivity is attributed to the increased light absorption as well as the gain enhancement due to the existence of trap states in the few‐layer ReS₂ flakes. It further enables the detection of weak signals, as successfully demonstrated with weak light sources including a lighter and limited fluorescent lighting. Our studies underscore ReS₂ as a promising material for future sensitive optoelectronic applications.     

Effects of the Ionic Currents in Electrolyte‐gated Organic Field‐Effect Transistors

Polyelectrolytes are promising materials as gate dielectrics in organic field‐effect transistors (OFETs). Upon gate bias, their polarization induces an ionic charging current, which generates a large double layer capacitor (10–500 µF cm^?2) at the semiconductor/electrolyte interface. The resulting transistor operates at low voltages (<1 V) and its conducting channel is formed in ～50 µs. The effect of ionic currents on the performance of the OFETs is investigated by varying the relative humidity of the device ambience. Within defined humidity levels and potential values, the water electrolysis is negligible and the OFETs performances are optimum.     

High‐Performance UV–Vis–NIR Phototransistors Based on Single‐Crystalline Organic Semiconductor–Gold Hybrid Nanomaterials

Hybrid materials in optoelectronic devices can generate new functionality or provide synergistic effects that enhance the properties of each component. Here, high‐performance phototransistors with broad spectral responsivity in UV–vis–near‐infrared (NIR) regions, using gold nanorods (Au NRs)‐decorated n‐type organic semiconductor and N ,N ′‐bis(2‐phenylethyl)‐perylene‐3,4:9,10‐tetracarboxylic diimide (BPE‐PTCDI) nanowires (NWs) are reported. By way of the synergistic effect of the excellent photo‐conducting characteristics of single‐crystalline BPE‐PTCDI NW and the light scattering and localized surface plasmon resonances (LSPR) of Au NRs, the hybrid system provides new photo‐detectivity in the NIR spectral region. In the UV–vis region, hybrid nanomaterial‐based phototransistors exhibit significantly enhanced photo‐responsive properties with a photo‐responsivity (R ) of 7.70 × 10⁵ A W^?1 and external quantum efficiency (EQE) of 1.42 × 10⁸% at the minimum light intensity of 2.5 µW cm^?2, which are at least tenfold greater than those of pristine BPE‐PTCDI NW‐based ones and comparable to those of high‐performance inorganic material‐based devices. While a pristine BPE‐PTCDI NW‐based photodetector is insensitive to the NIR spectral region, the hybrid NW‐based phototransistor shows an R of 10.7 A W^?1 and EQE of 1.35 × 10³% under 980 nm wavelength‐NIR illumination. This work demonstrates a viable approach to high‐performance photo‐detecting systems with broad spectral responsivity.     

Highly-sensitive solution-processed 2,8-difluoro-5,11-bis(triethylsilylethynyl) anthradithiophene (diF-TESADT) phototransistors for optical sensing applications

A highly-sensitive organic phototransistor, based on solution-processed 2,8-difluoro-5,11-bis(triethylsilylethynyl) anthradithiophene (diF-TESADT) was fabricated and investigated for an optical sensing element. The phototransistor based on thin crystalline grains of diF-TESADT exhibited a significant threshold voltage (V_TH) shift under a white light illumination in which the response time was estimated to be <0.5 s and a current modulation greater than 10⁶. It was found that the V_TH shift can be further enlarged by an additional gate bias, achieving very high light responsivity >10³ A/W at 0.17 mW/cm² and I_PH/I_DARK ratio higher than 10⁶. Also, by applying an erase gate bias, fast recovering of V_TH to the initial position was possible. This phenomenon can be ascribed to the trapping and de-trapping of photo-generated carriers at the organic channel/dielectric interface, while the amount of trapped carriers can be also modulated simultaneously by the gate bias. This investigation identifies that the solution-processed diF-TESADT phototransistors can be used for large-area and low-cost optical sensors and memory applications. In particular, it can be claimed that performance improvement by a gate bias represents a universal method applicable to the organic phototransistors.     

Solution-processed low-voltage organic phototransistors based on an anthradithiophene molecular solid

Low-voltage organic phototransistors (OPTs) are attractive candidates for optoelectronic applications such as photodetectors and memory devices. Here we describe a solution-processed low-voltage organic phototransistor based on a triethylgermylethynyl-substituted anthradithiophene (diF-TEG ADT). Two kinds of dielectric materials were used: 80-nm-thick potassium alumina (PA) and 300-nm-thick thermally grown SiO₂. To investigate its application in a moist environment, the performance at different humidities was characterized. Results showed that the device was very stable in high humidity. A major change in drain current (I_DS) was observed when connecting or disconnecting the gate electrode to the device. This feature may motivate the application of diF-TEG ADT-based phototransistors as multistage photo-controlled memory devices.     

Non‐Lithographic Fabrication of All‐2D α‐MoTe2 Dual Gate Transistors

As one of the emerging new transition‐metal dichalcogenides materials, molybdenum ditelluride (α‐MoTe₂) is attracting much attention due to its optical and electrical properties. This study fabricates all‐2D MoTe₂‐based field effect transistors (FETs) on glass, using thin hexagonal boron nitride and thin graphene in consideration of good dielectric/channel interface and source/drain contacts, respectively. Distinguished from previous works, in this study, all 2D FETs with α‐MoTe₂ nanoflakes are dual‐gated for driving higher current. Moreover, for the present 2D dual gate FET fabrications on glass, all thermal annealing and lithography processes are intentionally exempted for fully non‐lithographic method using only van der Waal's forces. The dual‐gate MoTe₂ FET displays quite a high hole and electron mobility over ≈20 cm² V^?1 s^?1 along with ON/OFF ratio of ≈10⁵ in maximum as an ambipolar FET and also demonstrates high drain current of a few tens‐to‐hundred μA at a low operation voltage. It appears promising enough to drive organic light emitting diode pixels and NOR logic functions on glass.     

Diketopyrrolopyrrole‐Based Conjugated Polymers Synthesized via Direct Arylation Polycondensation for High Mobility Pure n‐Channel Organic Field‐Effect Transistors

High‐performance unipolar n‐type conjugated polymers (CPs) are critical for the development of organic electronics. In the current paper, four “weak donor–strong acceptor” n‐type CPs based on pyridine flanked diketopyrrolopyrrole (PyDPP), namely PPyDPP1‐4FBT, PPyDPP2‐4FBT, PPyDPP1‐4FTVT, and PPyDPP2‐4FTVT, are synthesized via direct arylation polycondensation by using 3,3′,4,4′‐tetrafluoro‐2,2′‐bithiophene (4FBT) or (E)‐1,2‐bis(3,4‐difluorothien‐2‐yl)ethene (4FTVT) as weak donor unit. All four polymers exhibit low‐lying highest occupied molecular orbital (≈ ?5.90 eV) and lowest unoccupied molecular orbital energy levels (≈ ?3.70 eV). Top‐gate/bottom‐contact organic field‐effect transistors based on all four polymers display unipolar n‐channel characteristics with electron mobility (µ_e) above 1 cm² V^?1 s^?1 in air, and presented linear |I_SD|^1/2 ?V_GS plots and weak dependence of the extracted moblity on gate voltage (V_GS), indicative of the reliability of the extracted mobility values. Importantly, the devices based on PPyDPP1‐4FBT and PPyDPP2‐4FBT show a pure unipolar n‐channel transistor behavior as revealed by the typical unipolar n‐channel output characteristics and clear off‐regimes in transfer characteristics. Attributed to its high crystallinity and favorable thin film morphology, PPyDPP2‐4FBT shows the highest µ_e of 2.45 cm² V^?1 s^?1, which is among the highest for unipolar n‐type CPs reported to date. This is also the first report for DPP based pure n‐type CPs with µ_e greater than 1 cm² V^?1 s^?1.     

Highly sensitive near infrared organic phototransistors based on conjugated polymer nanowire networks

Highly sensitive near-infrared (NIR) organic phototransistors (OPTs) were fabricated using nanowire network based on a narrow bandgap donor-acceptor (D-A) polymer as the photoactive channel. The D-A polymer nanowire network-based NIR-OPTs exhibit high responsivity of ∼246 A/W under an NIR illumination source (850 nm) with a light intensity of ∼0.1 mW/cm². This value is over one order of magnitude higher than that of the structurally identical planar D-A polymer thin film OPTs. The high performance of the nanowire network-based phototransistors is attributed to the excellent hole transport ability, reduced density of the structural defects in the polymer nanowires, and improved contact at the channel layer/electrode interfaces. The high sensitivity and low cost solution-fabrication process render this OPT technology appealing and practically viable for application in large area NIR sensors.     

High‐Mobility Air‐Stable Naphthalene Diimide‐Based Copolymer Containing Extended π‐Conjugation for n‐Channel Organic Field Effect Transistors

A high‐performance naphthalene diimide (NDI)‐based conjugated polymer for use as the active layer of n‐channel organic field‐effect transistors (OFETs) is reported. The solution‐processable n‐channel polymer is systematically designed and synthesized with an alternating structure of long alkyl substituted‐NDI and thienylene–vinylene–thienylene units (PNDI‐TVT). The material has a well‐controlled molecular structure with an extended π‐conjugated backbone, with no increase in the LUMO level, achieving a high mobility and highly ambient stable n‐type OFET. The top‐gate, bottom‐contact device shows remarkably high electron charge‐carrier mobility of up to 1.8 cm² V^?1 s^?1 (I_on/I_off = 10⁶) with the commonly used polymer dielectric, poly(methyl methacrylate) (PMMA). Moreover, PNDI‐TVT OFETs exhibit excellent air and operation stability. Such high device performance is attributed to improved π–π intermolecular interactions owing to the extended π‐conjugation, apart from the improved crystallinity and highly interdigitated lamellar structure caused by the extended π–π backbone and long alkyl groups.