Dual Optoelectronic Organic Field-Effect Device: Combination of Electroluminescence and Photosensitivity.

Merging the functionality of an organic field-effect transistor (OFET) with either a light emission or a photoelectric effect can increase the efficiency of displays or photosensing devices. In this work, we show that an organic semiconductor enables a multifunctional OFET combining electroluminescence (EL) and a photoelectric effect. Specifically, our computational and experimental investigations of a six-ring thiophene-phenylene co-oligomer (TPCO) revealed that this material is promising for OFETs, light-emitting, and photoelectric devices because of the large oscillator strength of the lowest-energy singlet transition, efficient luminescence, pronounced delocalization of the excited state, and balanced charge transport. The fabricated OFETs showed a photoelectric response for wavelengths shorter than 530 nm and simultaneously EL in the transistor channel, with a maximum at ~570 nm. The devices demonstrated an EL external quantum efficiency (EQE) of ~1.4% and a photoelectric responsivity of ~0.7 A W-1, which are among the best values reported for state-of-the-art organic light-emitting transistors and phototransistors, respectively. We anticipate that our results will stimulate the design of efficient materials for multifunctional organic optoelectronic devices and expand the potential applications of organic (opto)electronics.

Multifunctional Deformable Organic Semiconductor Single Crystals.

We report the first organic semiconductor crystal with a unique combination of properties that can be used as a multifunctional optoelectronic device. Mechanically flexible single crystals of 9,10-bis(phenylethynyl)anthracene (BPEA) can function as a phototransistor, photoswitch, and an optical waveguide. The material can exist as two structurally different solid phases, with single crystals of one of the phases being elastic at room temperature while those of the other are brittle and become plastic at higher temperature. The output and transfer characteristics of the devices were characterized by measuring the generation and temporal response of the switching of the photogenerated current. The current-voltage characteristics of both phases exhibit linearity and symmetry about the positive and negative voltages. The crystals transmit light in the telecommunications range with significantly low optical loss for an organic crystalline material.

Investigating the Thermal Stability of Organic Thin-Film Transistors and Phototransistors Based on [1]-Benzothieno-[3,2-b]-[1]-benzothiophene Dimeric Derivatives.

Two new highly thermally stable [1]benzothieno[3,2-b][1]benzothiophene (BTBT) dimeric derivatives, namely 1,4-bis([1]benzothieno[3,2-b][1]benzothiophene-2-yl)benzene (BTBT-Ph-BTBT) and 4,4'-bis([1]benzothieno[3,2-b][1]benzothiophene-2-yl)-1,1'-biphenyl (BTBT-DPh-BTBT), were synthesized by combining two simple fragment structures. Compared to the monomer compound 2-phenyl[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT, µmax =3.4×10-2  cm2 V-1 s-1 ), the organic thin-film transistors (OTFTs) based on BTBT-Ph-BTBT and BTBT-DPh-BTBT showed significantly higher mobility (up to 2.5 and 3.6 cm2 V-1 s-1 for BTBT-Ph-BTBT and BTBT-DPh-BTBT, respectively). The mobility of OTFTs based on BTBT-Ph-BTBT was kept at a high value (2.4×10-1  cm2 V-1 s-1 ) after the devices were thermally annealed at 350 °C. Furthermore, the organic phototransistors (OPTs) based on BTBT-Ph-BTBT and BTBT-DPh-BTBT displayed high photosensitivities in a range of 250-400 nm with a low intensity, making these materials potentially applicable for sensitive optoelectronic devices.

Axially Chiral Organic Semiconductors for Visible-Blind UV-Selective Circularly Polarized Light Detection.

Technologies that detect circularly polarized light (CPL), particularly in the UV region, have significant potential for various applications, including bioimaging and optical communication. However, a major challenge in directly sensing CPL arises from the conflicting requirements of planar structures for efficient charge transport and distorted structures for effective interaction with CPL. Here, a novel design of an axially chiral n-type organic semiconductor is presented to surmount the challenge, in which a binaphthyl group results in a high dissymmetry factor at the molecular level, while maintaining excellent electron-transporting characteristics through the naphthalene diimide group. Experimental and computational methods reveal different stacking behaviors in homochiral and heterochiral assemblies, yielding different structures: Nanowires and nanoparticles, respectively. Especially, the homochiral assemblies exhibit effective π-π stacking between naphthalene diimides despite axial chirality. Thus, phototransistors fabricated using enantiomers exhibit a high maximum electron mobility of 0.22 cm2 V-1 s-1 and a detectivity of 3.9 × 1012 Jones, alongside the CPL distinguishing ability with a dissymmetry factor of responsivity of 0.05. Furthermore, the material possesses a wide bandgap, contributing to its excellent visible-blind UV-selective detection. These findings highlight the new strategy for compact CPL detectors, coupled with the demonstration of less-explored n-type and UV region phototransistors.

Colorless Near-Infrared Absorbing Dyes Based on B-N Fused Donor-Acceptor-Donor π-Conjugated Molecules for Organic Phototransistors.

The introduction of a colorless function to organic electronic devices allows responses to light in the near-infrared (NIR) region and is expected to broaden the applications of these devices. However, the development of a colorless NIR dye remains a challenge due to the lack of a rational molecular design for controlling electronic transitions. In this study, to suppress the π-π* transitions in the visible region, polycyclic donor-acceptor-donor π-conjugated molecules with boron bridges (Py-FNTz-B and IP-FNTz-B) are designed and synthesized, which contain pyrrole or indenopyrrole as donor units with fluorinated naphthobisthiadiazole (FNTz) as an acceptor unit. The pyrrole end-capped Py-FNTz-B shows an absorption band in the NIR region without distinct visible-light absorption, which has led to the establishment of colorless characteristics. The indenopyrrole end-capped IP-FNTz-B shows a narrow optical energy gap of 0.87 eV in films. Time-resolved microwave conductance and field-effect transistors demonstrate the semiconducting characteristics of these molecules, and Py-FNTz-B-based devices function as NIR phototransistors. Theoretical analyses indicate that the combination of a polyene-like electronic structure with orbital symmetry is important to obtain NIR wavelength-selective absorption. This study suggests that a molecular design based on electronic structures can be effective in the development of colorless NIR-absorbing dyes for organic electronics.

Conjugated Polymer Heteroatom Engineering Enables High Detectivity Symmetric Ambipolar Phototransistors.

Solution-processed high-performing ambipolar organic phototransistors (OPTs) can enable low-cost integrated circuits. Here, a heteroatom engineering approach to modify the electron affinity of a low band gap diketopyrrolopyrole (DPP) co-polymer, resulting in well-balanced charge transport, a more preferential edge-on orientation and higher crystallinity, is demonstrated. Changing the comonomer heteroatom from sulfur (benzothiadiazole (BT)) to oxygen (benzooxadiazole (BO)) leads to an increased electron affinity and introduces higher ambipolarity. Organic thin film transistors fabricated from the novel PDPP-BO exhibit charge carrier mobility of 0.6 and 0.3 cm2 Vs⁻1 for electrons and holes, respectively. Due to the high sensitivity of the PDPP-based material and the balanced transport in PDPP-BO, its application as an NIR detector in an OPT architecture is presented. By maintaining a high on/off ratio (9 × 104), ambipolar OPTs are shown with photoresponsivity of 69 and 99 A W⁻1 and specific detectivity of 8 × 107 for the p-type operation and 4 × 109 Jones for the n-type regime. The high symmetric NIR-ambipolar OPTs are also evaluated as ambipolar photo-inverters, and show a 46% gain enhancement under illumination.

Highly Stretchable and Oriented Wafer-Scale Semiconductor Films for Organic Phototransistor Arrays.

Stretchable organic phototransistor arrays have potential applications in artificial visual systems due to their capacity to perceive ultraweak light across a broad spectrum. Ensuring uniform mechanical and electrical performance of individual devices within these arrays requires semiconductor films with large-area scale, well-defined orientation, and stretchability. However, the progress of stretchable phototransistors is primarily impeded by their limited electrical properties and photodetection capabilities. Herein, wafer-scale and well-oriented semiconductor films were successfully prepared using a solution shearing process. The electrical properties and photodetection capabilities were optimized by improving the polymer chain alignment. Furthermore, a stretchable 10 × 10 transistor array with high device uniformity was fabricated, demonstrating excellent mechanical robustness and photosensitive imaging ability. These arrays based on highly stretchable and well-oriented wafer-scale semiconductor films have great application potential in the field of electronic eye and artificial visual systems.

Overcoming the Unfavorable Effects of "Boltzmann Tyranny:" Ultra-Low Subthreshold Swing in Organic Phototransistors via One-Transistor-One-Memristor Architecture.

Organic phototransistors (OPTs), as photosensitive organic field-effect transistors (OFETs), have gained significant attention due to their pivotal roles in imaging, optical communication, and night vision. However, their performance is fundamentally limited by the Boltzmann distribution of charge carriers, which constrains the average subthreshold swing (SSave) to a minimum of 60 mV/decade at room temperature. In this study, an innovative one-transistor-one-memristor (1T1R) architecture is proposed to overcome the Boltzmann limit in conventional OFETs. By replacing the source electrode in an OFET with a memristor, the 1T1R device exploits the memristor's sharp resistance state transitions to achieve an ultra-low SSave of 18 mV/decade. Consequently, the 1T1R devices demonstrate remarkable sensitivity to photo illumination, with a high specific detectivity of 3.9 × 109 cm W-1Hz1/2, outperforming conventional OPTs (4.9 × 104 cm W-1Hz1/2) by more than four orders of magnitude. The 1T1R architecture presents a potentially universal solution for overcoming the detrimental effects of "Boltzmann tyranny," setting the stage for the development of ultra-low SSave devices in various optoelectronic applications.

Nanographene-Based Heterojunctions for High-Performance Organic Phototransistor Memory Devices.

Organic phototransistors can enable many important applications such as nonvolatile memory, artificial synapses, and photodetectors in next-generation optical communication and wearable electronics. However, it is still a challenge to achieve a big memory window (threshold voltage response ∆Vth ) for phototransistors. Here, a nanographene-based heterojunction phototransistor memory with large ∆Vth responses is reported. Exposure to low intensity light (25.7 µW cm-2 ) for 1 s yields a memory window of 35 V, and the threshold voltage shift is found to be larger than 140 V under continuous light illumination. The device exhibits both good photosensitivity (3.6 × 105 ) and memory properties including long retention time (>1.5 × 105  s), large hysteresis (45.35 V), and high endurance for voltage-erasing and light-programming. These findings demonstrate the high application potential of nanographenes in the field of optoelectronics. In addition, the working principle of these hybrid nanographene-organic structured heterojunction phototransistor memory devices is described which provides new insight into the design of high-performance organic phototransistor devices.

Improving Photosensitivity and Transparency in Organic Phototransistor with Blending Insulating Polymers.

Organic phototransistors exhibit great promise for use in a wide range of technological applications due to their flexibility, low cost, and low-temperature processability. However, their low transparency due to visible light absorption has hindered their adoption in next-generation transparent electronics. For this reason, the present study sought to develop a highly sensitive organic phototransistor with greater transparency and significantly higher light sensitivity in the visible and UVA regions without deterioration in its electrical properties. An organic blended thin-film transistor (TFT) fabricated from the blend of an organic semiconductor and an insulating polymer demonstrated improved electrical properties in the dark and a higher current under light irradiation even though its transmittance was higher. The device exhibited a transmittance of 87.28% and a photosensitivity of 7049.96 in the visible light region that were 4.37% and 980 times higher than those of the single-semiconductor-based device. The carrier mobility of the device blended with the insulating polymer was improved and greatly amplified under light irradiation. It is believed that the insulating polymer facilitated the crystallization of the organic semiconductor, thus promoting the flow of photogenerated excitons and improving the photocurrent. Overall, the proposed TFT offers excellent low-temperature processability and has the potential to be employed in a range of transparent electronic applications.

Modulating the Alkylation Position on Terminal Thiophene Ring of Naphtho[2,3-b:6,7-b'] Bithieno[2,3-d] Thiophene (NBTT) for High-Performance Organic Optoelectronic Devices.

Several thiophene terminated thienoacenes with high mobilities in organic thin-film transistors (OTFTs) have been reported; however, the structure-property relationship of thiophene terminated thienoacenes was unclear, especially the impact of α or ß position substitution of terminal thiophene ring on molecular packing and physicochemical properties. Here, we report the synthesis and characterization of a six-ring-fused naphtho[2,3-b:6,7-b'] bithieno[2,3-d] thiophene (NBTT) and its derivatives 2,8-dioctyl-naphtho[2,3-b:6,7-b'] bithieno [2,3-d] thiophene (2,8-C8NBTT) and 3,9-dioctyl-naphtho[2,3-b:6,7-b'] bithieno [2,3-d] thiophene (3,9-C8NBTT). It is found that the alkylation on terminal thiophene ring can effectively tune the molecular stacking from a cofacial herringbone stacking mode (NBTT) to layer-by-layer packing (2,8-C8NBTT and 3,9-C8NBTT). Impressively, a hopping to "band-like" charge transport mechanism evolution of vacuum deposited films is realized by modulating the alkylation position on the terminal thiophene rings. As a result, the OTFTs based on 2,8-C8NBTT characterized by a "band-like" transport presents the highest mobility of 3.58 cm2 V-1 s-1 together with a remarkably high current on/off ratio around 109. Furthermore, organic phototransistors (OPTs) based on 2,8-C8NBTT thin film also exhibits higher photosensitivity (P) of 2.0 × 108, photoresponsivity (R) of 3.3 × 103 A W-1, and detectivity (D*) of 1.3 × 1016 Jones than those based on NBTT and 3,9-C8NBTT.

Negative Phototransistors with Ultrahigh Sensitivity and Weak-Light Detection Based on 1D/2D Molecular Crystal p-n Heterojunctions and their Application in Light Encoders.

Anomalous negative phototransistors in which the channel current decreases under light illumination hold potential to generate novel and multifunctional optoelectronic applications. Although a variety of design strategies have been developed to construct such devices, NPTs still suffer from far lower device performance compared to well-developed positive phototransistors (PPTs). In this work, a novel 1D/2D molecular crystal p-n heterojunction, in which p-type 1D molecular crystal (1DMC) arrays are embedded into n-type 2D molecular crystals (2DMCs), is developed to produce ultrasensitive NPTs. The p-type 1DMC arrays act as light-absorbing layers to induce p-doping of n-type 2DMCs through charge transfer under illumination, resulting in ineffective gate control and significant negative photoresponses. As a result, the NPTs show remarkable performances in photoresponsivity (P) (1.9 × 108 ) and detectivity (D*) (1.7 × 1017 Jones), greatly outperforming previously reported NPTs, which are one of the highest values among all organic phototransistors. Moreover, the device exhibits intriguing characteristics undiscovered in PPTs, including precise control of the threshold voltage by controlling light signals and ultrasensitive detection of weak light. As a proof-of-concept, the NTPs are demonstrated as light encoders that can encrypt electrical signals by light. These findings represent a milestone for negative phototransistors, and pave the way for the development of future novel optoelectronic applications.

Organic Single Crystals with High Photoluminescence Quantum Yields Close to 100% and High Mobility for Optoelectronic Devices.

Organic single crystals with excellent optical and electrical properties are critical for the development of organic optoelectronics. Herein, two compounds 9,10-bis([N,N-diphenyl]-4'-phenylethynyl)anthracene (TPA-An) and 9,10-bis([1',3'-diphenyl]-5'-phenylethynyl)anthracene (TBA-An) are synthesized by introducing two different luminescent groups, triphenylamine and 1,3-diphenylbenzene, at the 9,10 positions of anthracene via triple bond connection. Single crystals based on TPA-An and TBA-An with a ribbon morphology obtained through the slow solvent-evaporation method exhibit high photoluminescence quantum yields (PLQYs) of 98% and 99% at room temperature, and remarkable hole mobilities of 0.45 and 0.15 cm2 V-1 s-1 in single-crystal organic field-effect transistors (SC-OFETs). Furthermore, UV phototransistors based on the two single crystals obtain photosensitivities of 1.03 × 103 and 3.45 × 104 , ultrahigh photoresponsivities of 7.19 × 105 and 1.50 × 105 A W-1 , and the detectivities exceeding 1.40 × 1016 and 1.60 × 1017 Jones.

Organic UV-Sensitive Phototransistors Based on Distriphenylamineethynylpyrene Derivatives with Ultra-High Detectivity Approaching 1018.

Organic photodetectors with UV-sensitivity are of great potential for various optoelectronic applications. Integration of high charge carrier mobility, long exciton diffusion length as well as unique UV-sensitivity for active materials is crucial for construction of UV-sensitive devices with high performance, however, very few organic semiconductors can integrate these properties simultaneously. Herein, two novel organic semiconductors containing large steric hindrance triphenylamine groups, 1,6-distriphenylamineethynylpyrene (1,6-DTEP) and 2,7-distriphenylamineethynylpyrene (2,7-DTEP) are designed and synthesized. It demonstrates that the single crystals of both 1,6-DTEP and 2,7-DTEP exhibit superior integrated optoelectronic properties of high charge carrier mobility, unique UV absorption, high photoluminescence quantum yields as well as small exciton binding energies. Organic phototransistors constructed using 1,6-DTEP and 2,7-DTEP single crystals show ultrasensitive performance with ultra-high photoresponsivity of 2.86 × 106 and 1.04 × 105 A W-1 , detectivity (D*) of above 1.49 × 1018 and 5.28 × 1016 Jones under 370 nm light illumination, respectively. It indicates the great potential of 1,6-DTEP and 2,7-DTEP-based phototransistors for organic UV-photodetector applications and also provides a new design strategy to develop series of better performance UV photoelectric organic materials for related research in organic optoelectronics.

Near-Infrared Organic Phototransistors with Polymeric Channel/Dielectric/Sensing Triple Layers.

A new type of near-infrared (NIR)-sensing organic phototransistor (OPTR) was designed and fabricated by employing a channel/dielectric/sensing (CDS) triple layer structure. The CDS structures were prepared by inserting poly(methyl methacrylate) (PMMA) dielectric layers (DLs) between poly(3-hexylthiophene) (P3HT) channel layers and poly[{2,5-bis-(2-octyldodecyl)-3,6-bis-(thien-2-yl)-pyrrolo[3,4-c]pyrrole-1,4-diyl}-co-{2,2'-(2,1,3-benzothiadiazole)-5,5'-diyl}] (PODTPPD-BT) top sensing layers. Two different thicknesses of PMMA DLs (20 nm and 50 nm) were applied to understand the effect of DL thickness on the sensing performance of devices. Results showed that the NIR-OPTRs with the CDS structures were operated in a typical n-channel mode with a hole mobility of ca. 0.7~3.2 × 10-4 cm2/Vs in the dark and delivered gradually increased photocurrents upon illumination with an NIR light (905 nm). As the NIR light intensity increased, the threshold voltage was noticeably shifted, and the resulting transfer curves showed a saturation tendency in terms of curve shape. The operation of the NIR-OPTRs with the CDS structures was explained by the sensing mechanism that the excitons generated in the PODTPPD-BT top sensing layers could induce charges (holes) in the P3HT channel layers via the PMMA DLs. The optically modulated and reflected NIR light could be successfully detected by the present NIR-OPTRs with the CDS structures.

High-Performance Low-Voltage Flexible Photodetector Arrays Based on All-Solid-State Organic Electrochemical Transistors for Photosensing and Imaging.

The identifying characteristic of an organic electrochemical transistor (OECT) is the coupling between ionic and electronic charges within the entire volume of the channel. In this work, by taking advantage of the volumetric nature of the OECTs' response, a novel flexible photodetector is reported for the first time based on all-solid-state OECT with an excellent responsivity of up to 6.7 × 106 A/W, detectivity as high as 3.6 × 1013 Jones, and a fast response of ∼0.13 s in the visible range, which are superior to those of the majority of the reported organic phototransistors (OPTs) based on field-effect transistors (FETs) and even better than those of FET-based phototransistors with two-dimensional (MoS2 and graphene) and perovskite materials. The high performance of the devices was ascribed to the combination of the higher carrier mobility of poly(3,4-ethylenedioxythiophene) doped with poly(styrene sulfonate) (PEDOT:PSS) as a channel and the volumetric nature of the OECTs' response, and the charge density of the volumetric channel was efficiently modulated by incident light compared to FETs. Moreover, OECT-based OPTs with quantum dots (CdSe/ZnS) as a light sensitizer were characterized under ultraviolet light, and they exhibited excellent photosensitivity, which further verified the superiority of OECT for phototransistors. Furthermore, a flexible image sensor was fabricated for the first time by integrating flexible OECTs-OPTs into a 10 × 10 array, which can clearly identify the target image under a bending state, indicating the great potential of OECTs-OPTs in the application of low-power, ultrasensitive flexible photodetectors and imaging technology.

A "Phase Separation" Molecular Design Strategy Towards Large-Area 2D Molecular Crystals.

2D molecular crystals (2DMCs) have attracted considerable attention because of their unique optoelectronic properties and potential applications. Taking advantage of the solution processability of organic semiconductors, solution self-assembly is considered an effective way to grow large-area 2DMCs. However, this route is largely blocked because a precise molecular design towards 2DMCs is missing and little is known about the relationship between 2D solution self-assembly and molecular structure. A "phase separation" molecular design strategy towards 2DMCs is proposed and layer-by-layer growth of millimeter-sized monolayer or few-layer 2DMCs is realized. High-performance organic phototransistors are constructed based on the 2DMCs with unprecedented photosensitivity (2.58 × 107 ), high responsivity (1.91 × 104 A W-1 ), and high detectivity (4.93 × 1015 Jones). This "phase separation" molecular design strategy provides a guide for the design and synthesis of novel organic semiconductors that self-assemble into large-area 2DMCs for advanced organic (opto)electronics.

Organic-Single-Crystal Vertical Field-Effect Transistors and Phototransistors.

Organic vertical field-effect transistors (VFETs) have attracted significant attention over the past years due to their unique characteristics of high output currents, low operation voltages, high working frequency, and promising high-density integration for circuits. However, most currently reported VFETs demonstrate poor performance, e.g., with low on/off ratio and current density. Here, the first organic-single-crystal vertical field-effect transistors (SC-VFETs) and phototransistors are constructed from 2,6-diphenyl anthracene (DPA) through a modified method. The devices exhibit high on/off ratio of 106 and a high current density of 100 mA cm-2 under a small voltage of -5 V, which are proved to be one of the best performances for organic VFETs. Furthermore, superior photoresponse performance with photoresponsivity of 110 A W-1 and detectivity of 1013 Jones is obtained under light illumination for vertical phototransistors. These results confirm the control of the intrinsic Schottky barrier height at the graphene-DPA junction along with good interfacial contact effectively suppressing the dark current to realize a large on/off ratio and high light detectivity. This vertical integration of graphene with organic single crystals via simple, effective fabrication processes opens up new opportunities to realize high-performance integrated organic vertical electronic and optoelectronic devices.

Flexible Organic/Inorganic Hybrid Near-Infrared Photoplethysmogram Sensor for Cardiovascular Monitoring.

Wearable photoplethysmogram (PPG) sensors offer convenient and informative measurements for evaluating daily physiological states of individuals. In this work, epidermal and flexible near-infrared (NIR) PPG sensors integrating a low-power, high-sensitivity organic phototransistor (OPT) with a high-efficiency inorganic light-emitting diode are developed. By exploiting an organic bulk heterojunction active layer and a bilayer gate dielectric design, a low voltage (<3 V) operated OPT with NIR responsivity as high as 3.5 × 105 A W-1 and noise equivalent power of 1.2 × 10-15 W Hz-1/2 is achieved, greatly surpassing commercial available silicon-based photodetectors. In addition, the ultrathin encapsulation structure renders the device highly flexible and allows transfer printing of the device directly onto human skin. It is demonstrated that the epidermal/flexible PPG sensors are capable of continuously monitoring heart rate variability and precisely tracking the changes of pulse pressure at different postures of human subjects with the aid of electrocardiogram monitoring, exhibiting more reliable performance than commercial PPG sensors while consuming less power. The study suggests that the hybrid PPG sensor design may provide a promising solution for low-power, real-time physiological monitoring.