Photoresponsive Transistors Based on Lead‐Free Perovskite and Carbon Nanotubes

Lead‐free perovskite materials are exhibiting bright application prospects in photodetectors (PDs) owing to their low toxicity compared with traditional lead perovskites. Unfortunately, their photoelectric performance is constrained by the relatively low charge conductivity and poor stability. In this work, photoresponsive transistors based on stable lead‐free bismuth perovskites CsBi₃I₁₀ and single‐walled carbon nanotubes (SWCNTs) are first reported. The SWCNTs significantly strengthen the dissociation and transportation of the photogenerated charge carriers, which lead to dramatically improved photoresponsivity, while a decent I_light/I_dark ratio over 10² can be maintained with gate modulation. The devices exhibit high photoresponsivity (6.0 × 10⁴ A W^?1), photodetectivity (2.46 × 10¹⁴ jones), and external quantum efficiency (1.66 × 10⁵%), which are among the best reported results in lead‐free perovskite PDs. Furthermore, the excellent stability over many other lead‐free perovskite PDs is demonstrated over 500 h of testing. More interestingly, the device also shows the application potential as a light‐stimulated synapse and its synaptic behaviors are demonstrated. In summary, the lead‐free bismuth perovskite‐based hybrid phototransistors with multifunctional performance of photodetection and light‐stimulated synapse are first demonstrated in this work.     

High‐Performance SiC Nanobelt Photodetectors with Long‐Term Stability Against 300 °C up to 180 Days

In the present work, high‐performance photodetectors (PDs) based on a single B‐doped 3C‐SiC nanobelt, which are synthesized via catalyst‐free pyrolysis of polymeric precursors of polysilazane, are reported. The as‐built PDs have a high responsivity and external quantum efficiency of 6.37 × 10⁵ A · W^?1 and 2.0 × 10⁸% under 405 nm light with a power density of 0.14 mW · cm^?2 at 5 V, respectively. The detectivity of the PDs is measured to be of 6.86 × 10¹⁴ Jones. Moreover, the B‐doped 3C‐SiC nanobelt PDs exhibit a long‐term stability against 300 °C up to 180 days, suggesting their promising applications to be served under harsh conditions.     

High‐Mobility n‐Type Organic Transistors Based on a Crystallized Diketopyrrolopyrrole Derivative

A new high‐performing small molecule n‐channel semiconductor based on diketopyrrolopyrrole (DPP), 2,2′‐(5,5′‐(2,5‐bis(2‐ethylhexyl)‐3,6‐dioxo‐2,3,5,6‐tetrahydropyrrolo[3,4‐c]pyrrole‐1,4‐diyl)bis(thiophene‐5,2‐diyl))bis(methan‐1‐yl‐1‐ylidene)dimalononitrile (DPP‐T‐DCV), is successfully synthesized. The frontier molecular orbitals in this designed structure are elaborately tuned by introducing a strong electron‐accepting functionality (dicyanovinyl). The well‐defined lamellar structures of the crystals display a uniform terrace step height corresponding to a molecular monolayer in the solid‐state. As a result of this tuning and the remarkable crystallinity derived from the conformational planarity, organic field‐effect transistors (OFETs) based on dense‐packed solution‐processed single‐crystals of DPP‐T‐DCV exhibit an electron mobility (μ_e) up to 0.96 cm² V^?1 s^?1, one of the highest values yet obtained for DPP derivative‐based n‐channel OFETs. Polycrystalline OFETs show promise (with an μ_e up to 0.64 cm² V^?1 s^?1) for practical utility in organic device applications.     

Response Enhancement of Self‐Powered Visible‐Blind UV Photodetectors by Nanostructured Heterointerface Engineering

The development of efficient photodetectors (PDs) for ultraviolet (UV) light is of great importance for many applications. In this paper, a novel approach is proposed for boosting the performances of self‐powered PDs. Visible‐blind UV‐A PDs are built by combining a mesoporous TiO₂ layer with a Spiro‐OMeTAD layer. The nanostructured heterointerface is engineered by inserting a self‐assembled layer of organic modifiers. By choosing 4‐nitrobenzoic acid (NBA), the responsivity is boosted by 70% compared to the pristine devices. It achieves 64 mA W^?1 at 0 V bias, 380 nm, and 1 mW cm^?2. The PD displays a very high sensitivity (>10⁴), a fast response time (<3 ms), a high stability, and repeatability. 4‐chlorobenzoic acid, 4‐methoxy benzoic acid, 4‐nitro benzoic acid, and β‐alanine surface modifiers are studied by a combined experimental and theoretical approach. Their dipole moment is calculated. Their presence induces a step in the vacuum energy and the formed dipole field dramatically affects the charge transfer and then the photocurrent/photoresponse of the device. The higher responsivity of the NBA‐modified PD is thus explained by the better and faster electron charge transfer toward the electrical contact on TiO₂.     

Mixed‐Valence‐Driven Quasi‐1D SnIISnIVS3 with Highly Polarization‐Sensitive UV–vis–NIR Photoresponse

Mixed‐valence states can bring unexpected unique phenomena, especially novel anisotropic physics, due to structural asymmetry, which originate from the discrepant distribution of atoms with different valence. This study reports an unexploited mixed‐valence‐driven quasi‐1D Sn^IISn^IVS₃ crystal, which exhibits widely and distinctively anisotropic polarized‐light absorption reaching ≈3.4 from the deep ultraviolet to near‐infrared region (250–850 nm). The fabricated polarization‐sensitive photodetectors based on highly air‐stable Sn^IISn^IVS₃ nanowires display strong linear dichroism among the UV–vis–NIR spectrum with responsivity exceeding ≈150 A W^?1. Furthermore, the devices are further constructed onto a flexible polyethylene terephthalate (PET) substrate and the photoresponse remains roughly unchanged after repeated bending. This work based on novel mixed‐valence‐driven quasi‐1D ternary sulfide Sn^IISn^IVS₃ excites interest in low‐symmetry semiconductors for developing broadly spectral polarization‐sensitive photodetectors with environmental stability and mechanical flexibility.     

Flexible Near‐Infrared Plastic Phototransistors with Conjugated Polymer Gate‐Sensing Layers

Flexible near‐infrared (NIR) light‐sensing detectors are strongly required in the fast‐growing flexible electronics era, because they can serve as a vision system like eyes in various innovative applications including humanoid robots. Recently, keen interest has been paid to organic phototransistors due to their unique signal amplification and active matrix driving features over organic photodiodes. However, conventional NIR‐sensing organic phototransistors suffer from the limited use of organic materials because the channel layers play a dual role in both charge transport and sensing so that organic semiconducting materials with reasonably high charge mobility can be applied only. Here, it is demonstrated that a conjugated polymer, poly[{2,5‐bis‐(2‐ethylhexyl)‐3,6‐bis‐(thien‐2‐yl)‐pyrrolo[3,4‐c]pyrrole‐1,4‐diyl}‐co‐{2,2′‐(2,1,3‐benzothiadiazole)]‐5,5′‐diyl}] (PEHTPPD‐BT), which exhibits no transistor performance as a channel layer, can stably detect a NIR light (up to 1000 nm) as a gate‐sensing layer (GSL) when it is placed between gate‐insulating layers and gate electrodes. The flexible array (10 × 10) detectors with the PEHTPPD‐BT GSLs could effectively sense NIR light without visible light interference by applying visible light cut films.     

Printed,Flexible, Organic Nano‐Floating‐Gate Memory: Effects of Metal Nanoparticles and Blocking Dielectrics on Memory Characteristics

The effects of using a blocking dielectric layer and metal nanoparticles (NPs) as charge‐trapping sites on the characteristics of organic nano‐floating‐gate memory (NFGM) devices are investigated. High‐performance NFGM devices are fabricated using the n‐type polymer semiconductor, poly{[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)} (P(NDI2OD‐T2)), and various metal NPs. These NPs are embedded within bilayers of various polymer dielectrics (polystyrene (PS)/poly(4‐vinyl phenol) (PVP) and PS/poly(methyl methacrylate) (PMMA)). The P(NDI2OD‐T2) organic field‐effect transistor (OFET)‐based NFGM devices exhibit high electron mobilities (0.4–0.5 cm² V^?1 s^?1) and reliable non‐volatile memory characteristics, which include a wide memory window (≈52 V), a high on/off‐current ratio (I_on/I_off ≈ 10⁵), and a long extrapolated retention time (>10⁷ s), depending on the choice of the blocking dielectric (PVP or PMMA) and the metal (Au, Ag, Cu, or Al) NPs. The best memory characteristics are achieved in the ones fabricated using PMMA and Au or Ag NPs. The NFGM devices with PMMA and spatially well‐distributed Cu NPs show quasi‐permanent retention characteristics. An inkjet‐printed flexible P(NDI2OD‐T2) 256‐bit transistor memory array (16 × 16 transistors) with Au‐NPs on a polyethylene naphthalate substrate is also fabricated. These memory devices in array exhibit a high I_on/I_off (≈10^{4 ± 0.85}), wide memory window (≈43.5 V ± 8.3 V), and a high degree of reliability.     

High‐Performance Flexible Broadband Photodetector Based on Organolead Halide Perovskite

Organolead halide perovskites have attracted extensive attentions as light harvesting materials for solar cells recently, because of its high charge‐carrier mobilities, high photoconversion efficiencies, low energy cost, ease of deposition, and so on. Herein, with CH₃NH₃PbI₃ film deposited on flexible ITO coated substrate, the first organolead halide perovskite based broadband photodetector is demonstrated. The organolead halide perovskite photodetector is sensitive to a broadband wavelength from the ultraviolet light to entire visible light, showing a photo‐responsivity of 3.49 A W^?1, 0.0367 A W^?1, an external quantum efficiency of 1.19×10³%, 5.84% at 365 nm and 780 nm with a voltage bias of 3 V, respectively. Additionally, the as‐fabricated photodetector exhibit excellent flexibility and robustness with no obvious variation of photocurrent after bending for several times. The organolead halide perovskite photodetector with high sensitivity, high speed and broad spectrum photoresponse is promising for further practical applications. And this platform creates new opportunities for the development of low‐cost, solution‐processed and high‐efficiency photodetectors.     

Phototransistors with Negative or Ambipolar Photoresponse Based on As‐Grown Heterostructures of Single‐Walled Carbon Nanotube and MoS2

A facile synthesis method for the heterostructures of single‐walled carbon nanotubes (SWCNTs) and few‐layer MoS₂ is reported. The heterostructures are realized by in situ chemical vapor deposition of MoS₂ on individual SWCNTs. Field effect transistors based on the heterostructures display different transfer characteristics depending on the formation of MoS₂ conduction channels along SWCNTs. Under light illumination, negative photoresponse originating from charge transfer from MoS₂ to SWCNT is observed while positive photoresponse is observed in MoS₂ conduction channels, leading to ambipolar photoresponse in devices with both SWCNT and MoS₂ channels. The heterostructure phototransistor, for negative photoresponse, exhibits high responsivity (100–1000 AW^?1) at low bias voltages (0.1 V) in the visible spectrum (500–700 nm) by combining high mobility conduction channel (SWCNT) with efficient light absorber (MoS₂).     

Poly(diketopyrrolopyrrole‐benzothiadiazole) with Ambipolarity Approaching 100% Equivalency

As a characteristic feature of conventional conjugated polymers, it has been generally agreed that conjugated polymers exhibit either high hole transport property (p‐type) or high electron transport property (n‐type). Although ambipolar properties have been demonstrated from specially designed conjugated polymers, only a few examples have exhibited ambipolar transport properties under limited conditions. Furthermore, there is, as yet, no example with ‘equivalent’ hole and electron transport properties. We describe the realization of an equivalent ambipolar organic field‐effect transistor (FET) by using a single‐component visible–near infrared absorbing diketopyrrolopyrrole (DPP)‐benzothiadiazole (BTZ) copolymer, namely poly[3,6‐dithiene‐2‐yl‐2,5‐di(2‐decyltetradecyl)‐pyrrolo[3,4‐c]pyrrole‐1,4‐dione‐5’,5’’‐diyl‐alt‐benzo‐2,1, 3‐thiadiazol‐4,7‐diyl] ( PDTDPP‐alt‐BTZ ). PDTDPP‐alt‐BTZ shows not only ideally balanced charge carrier mobilities for both electrons (?_e = 0.09 cm²V^?1s^?1) and holes (?_h = 0.1 cm²V^?1s^?1) but also its inverter constructed with the combination of two identical ambipolar FETs exhibits a gain of ～35 that is much higher than usually obtained values for unipolar logic.     

High‐Performance Near‐IR Photodetector Using Low‐Bandgap MA0.5FA0.5Pb0.5Sn0.5I3 Perovskite

Photodetectors with ultrafast response are explored using inorganic/organic hybrid perovskites. High responsivity and fast optoelectronic response are achieved due to the exceptional semiconducting properties of perovskite materials. However, most of the perovskite‐based photodetectors exploited to date are centered on Pb‐based perovskites, which only afford spectral response across the visible spectrum. This study demonstrates a high‐performance near‐IR (NIR) photodetector using a stable low‐bandgap Sn‐containing perovskite, (CH₃NH₃)_0.5(NH₂CHNH₂)_0.5Pb_0.5Sn_0.5I₃ (MA_0.5FA_0.5Pb_0.5Sn_0.5I₃), which is processed with an antioxidant additive, ascorbic acid (AA). The addition of AA effectively strengthens the stability of Sn‐containing perovskite against oxygen, thereby significantly inhibiting the leakage current. Consequently, the derived photodetector shows high responsivity with a detectivity of over 10¹² Jones ranging from 800 to 970 nm. Such low‐cost, solution processable NIR photodetectors with high performance show promising potential for future optoelectronic applications.     

High‐Performance All‐Polymer Photoresponse Devices Based on Acceptor–Acceptor Conjugated Polymers

Three acceptor–acceptor (A–A) type conjugated polymers based on isoindigo and naphthalene diimide/perylene diimide are designed and synthesized to study the effects of building blocks and alkyl chains on the polymer properties and performance of all‐polymer photoresponse devices. Variation of the building blocks and alkyl chains can influence the thermal, optical, and electrochemical properties of the polymers, as indicated by thermogravimetric analysis, differential scanning calorimetry, UV–vis, cyclic voltammetry, and density functional theory calculations. Based on the A–A type conjugated polymers, the most efficient all‐polymer photovoltaic cells are achieved with an efficiency of 2.68%, and the first all‐polymer photodetectors are constructed with high responsivity (0.12 A W^?1) and detectivity (1.2 × 10¹² Jones), comparable to those of the best fullerene based organic photodetectors and inorganic photodetectors. Photoluminescence spectra, charge transport properties, and morphology of blend films are investigated to elucidate the influence of polymeric structures on device performances. This contribution demonstrates a strategy of systematically tuning the polymeric structures to achieve high performance all‐polymer photoresponse devices.     

Highly Sensitive Low‐Bandgap Perovskite Photodetectors with Response from Ultraviolet to the Near‐Infrared Region

It is a great challenge to obtain broadband response perovskite photodetectors (PPDs) due to the relatively large bandgaps of the most used methylammonium lead halide perovskites. The response range of the reported PPDs is limited in the ultraviolet–visible range. Here, highly sensitive PPDs are successfully fabricated with low bandgap (≈1.25 eV) (FASnI₃)_0.6(MAPbI₃)_0.4 perovskite as active layers, exhibiting a broadband response from 300 to 1000 nm. The performance of the PPDs can be optimized by adjusting the thicknesses of the perovskite and C₆₀ layers. The optimized PPDs with 1000 nm thick perovskite layer and 70 nm thick C₆₀ layer exhibit an almost flat external quantum efficiency (EQE) spectrum from 350 to 900 nm with EQE larger than 65% under ?0.2 V bias. Meanwhile, the optimized PPDs also exhibit suppressed dark current of 3.9 nA, high responsivity (R ) of over 0.4 A W^?1, high specific detectivity (D* ) of over 10¹² Jones in the near‐infrared region under ?0.2 V. Such highly sensitive broadband response PPDs, which can work well as self‐powered conditions, offer great potential applications in multicolor light detection.     

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

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

High Gain Solution-Processed Carbon-Free BiSI Chalcohalide Thin Film Photodetectors

Chalcohalide semiconductors are an emergent class of materials for optoelectronics. Here, the first work on BiSI chalcohalide thin film photodetectors (PDs) is presented. An entirely new method for the fabrication of bismuth chalcohalide thin films (BiOI and BiSI) is developed. This method circumvents the use of any ligands or counter ions during fabrication and provides highly pure thin films free of carbon residues and other contaminants. When integrated into lithographically patterned lateral PDs these BiSI thin films show outstanding performances and high stability. The direct ≈1.55 eV bandgap of BiSI perfectly accommodates optical sensing over the full visible spectrum. The responsivity (R) of the BiSI PDs reaches 62.1 A W⁻¹, which is the best value reported to date across chalcohalide materials of any type. The BiSI PDs display remarkable sensitivity to low light levels, supporting a broad operational detectivity ≈10¹² Jones over four decades in light intensity, with a peak specific detectivity (D*) of 2.01 × 10¹³ Jones. The dynamics of photocurrent generation are demonstrated to be dominated by photoconductive gain. These results cement BiSI as an exciting candidate for high performance photodetector applications and encourage ongoing work in BiSX (X = Cl, Br, I) materials for optoelectronics.     

Doping Dependent In‐Plane and Cross‐Plane Thermoelectric Performance of Thin n‐Type Polymer P(NDI2OD‐T2) Films

Thermoelectric generators pose a promising approach in renewable energies as they can convert waste heat into electricity. In order to build high efficiency devices, suitable thermoelectric materials, both n‐ and p‐type, are needed. Here, the n‐type high‐mobility polymer poly[N,N′‐bis(2‐octyldodecyl)naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene) (P(NDI2OD‐T2)) is focused upon. Via solution doping with 4‐(1,3‐dimethyl‐2,3‐dihydro‐1H‐benzoimidazol‐2‐yl)‐N,N‐diphenylaniline (N‐DPBI), a maximum power factor of (1.84 ± 0.13) µW K^?2 m^?1 is achieved in an in‐plane geometry for 5 wt% dopant concentration. Additionally, UV–vis spectroscopy and grazing‐incidence wide‐angle X‐ray scattering are applied to elucidate the mechanisms of the doping process and to explain the discrepancy in thermoelectric performance depending on the charge carriers being either transported in‐plane or cross‐plane. Morphological changes are found such that the crystallites, built‐up by extended polymer chains interacting via lamellar and π–π stacking, re‐arrange from face‐ to edge‐on orientation upon doping. At high doping concentrations, dopant molecules disturb the crystallinity of the polymer, hindering charge transport and leading to a decreased power factor at high dopant concentrations. These observations explain why an intermediate doping concentration of N‐DPBI leads to an optimized thermoelectric performance of P(NDI2OD‐T2) in an in‐plane geometry as compared to the cross‐plane case.     

Spraying Perovskite Intermediate Enabling Inch-Scale Microwire Film Fabrication for Integration Compatible Efficient-Photodetectors Array

Metal halide perovskite microwires (MWs) have emerged as promising photoactive materials for highly efficient photodetectors (PDs). However, large-scale MWs film fabrication is still a formidable challenge for achieving integration compatible perovskite PDs arrays, owing to precipitation and structure crushing of MWs during deposition and annealing. Herein, a strategy of fabrication of inch-scale perovskite MWs films is presented by depositing perovskite intermediate suspension through spray-coating, which addresses the trade-off present between the high flatness of MWs film and its large-scale fabrication. The single crystalline perovskite MWs weave a film with high enough flatness rendering narrow performance distribution of high efficiency on the 7 × 7 PDs arrays. The formamidinium lead iodide (FAPbI₃) PDs arrays show average responsivity and detectivity of (1.60 ± 0.46) A W⁻¹ and (1.49 ± 0.50) × 10¹² Jones. The methanaminium lead iodide (MAPbI₃) PDs arrays show average responsivity and detectivity of (0.065 ± 0.046) A W⁻¹ and (2.54 ± 0.77) × 10¹¹ Jones. The champion PDs based on FAPbI₃ MWs film and MAPbI₃ MWs film show detectivity of 1.26 × 10¹³ and 9.67 × 10¹¹ Jones, which are much higher than that of corresponding polycrystalline films and located on the top ranking of similar devices.     

High Performance Ternary Organic Phototransistors with Photoresponse up to 2600 nm at Room Temperature

Infrared (IR) photodetection is important for light communications, military, agriculture, and related fields. Organic transistors are investigated as photodetectors. However, due to their large band gap, most organic transistors can only respond to ultraviolet and visible light. Here high performance IR phototransistors with ternary semiconductors of organic donor/acceptor complex and semiconducting single-walled carbon nanotubes (SWCNTs), without deep cooling requirements are developed. Due to both the ultralow intermolecular electronic transition energy of the complex and charge transport properties of SWCNTs, the phototransistor realizes broadband photodetection with photoresponse up to 2600 nm. Moreover, it exhibits outstanding performance under 2000 nm light with photoresponsivity of 2.75 × 10⁶ A W⁻¹, detectivity of 3.12 × 10¹⁴ Jones, external quantum efficiency over 10⁸%, and high I_photo/I_dark ratio of 6.8 × 10⁵. The device exhibits decent photoresponse to IR light even under ultra-weak light intensity of 100 nW cm⁻². The response of the phototransistor to blackbody irradiation is demonstrated, which is rarely reported for organic phototransistors. Interestingly, under visible light, the device can also be employed as synaptic devices, and important basic functions are realized. This strategy provides a new guide for developing high performance IR optoelectronics based on organic transistors.     

Ultrafast Responsive Non‐Volatile Flash Photomemory via Spatially Addressable Perovskite/Block Copolymer Composite Film

The exotic photophysical properties of organic–inorganic hybrid perovskite with long exciton lifetimes and small binding energy have appeared as promising front‐runners for next‐generation non‐volatile flash photomemory. However, the long photo‐programming time of photomemory limits its application on light‐fidelity (Li‐Fi), which requires high storage capacity and short programming times. Herein, the spatially addressable perovskite in polystyrene‐block‐poly(ethylene oxide) (PS‐b‐PEO)/perovskite composite film as an photoactive floating gate is demonstrated to elucidate the effect of morphology on the photo‐responsive characteristics of photomemory. The chelation between lead ion and PEO segment promotes the anti‐solvent functionalities of the perovskite/PS‐b‐PEO composite film, thus allowing the solution‐processable poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) to act as the active channel. Through manipulating the interfacial area between perovskite and P3HT, fast photo‐induced charge transfer rate of 0.056 ns^?1, high charge transfer efficiency of 89%, ON/OFF current ratio of 10⁴, and extremely low programming time of 5 ms can be achieved. This solution‐processable and fast photo‐programmable non‐volatile flash photomemory can trigger the practical application on Li‐Fi.     

Rational Design of Perylenediimide‐Substituted Triphenylethylene to Electron Transporting Aggregation‐Induced Emission Luminogens (AIEgens) with High Mobility and Near‐Infrared Emission

Organic materials with both high electron mobility and strong solid‐state emission are rare although for their importance to advanced organic optoelectronics. In this paper, triphenylethylenes with varying number of perylenediimide (PDI) unit (TriPE‐nPDIs, n = 1?3) are synthesized and their optical and charge‐transporting properties are systematically investigated. All the molecules exhibit strong solid‐stated near infrared (NIR) emission and some of them exhibit aggregation‐enhanced emission characteristics. Organic field‐effect transistors (OFETs) using TriPE‐nPDIs are fabricated. TriPE‐3PDI shows the best performance with maximum quantum yield of ≈30% and optimized electron mobility of over 0.01 cm² V^?1 s^?1, which are the highest values among aggregation‐induced emission luminogens with NIR emissions reported so far. Photophysical property investigation and theoretical calculation indicate that the molecular conformation plays an important role on the optical properties of TriPE‐nPDI, while the result from film microstructure study reveals that the film crystallinity influences greatly their OFET device performance.