Heterojunction Ambipolar Organic Transistors Fabricated by a Two‐Step Vacuum‐Deposition Process

Ambipolar organic field‐effect transistors (OFETs) are produced, based on organic heterojunctions fabricated by a two‐step vacuum‐deposition process. Copper phthalocyanine (CuPc) deposited at a high temperature (250 °C) acts as the first (p‐type component) layer, and hexadecafluorophthalocyaninatocopper (F₁₆CuPc) deposited at room temperature (25 °C) acts as the second (n‐type component) layer. A heterojunction with an interpenetrating network is obtained as the active layer for the OFETs. These heterojunction devices display significant ambipolar charge transport with symmetric electron and hole mobilities of the order of 10^–4 cm² V^–1 s^–1 in air. Conductive channels are at the interface between the F₁₆CuPc and CuPc domains in the interpenetrating networks. Electrons are transported in the F₁₆CuPc regions, and holes in the CuPc regions. The molecular arrangement in the heterojunction is well ordered, resulting in a balance of the two carrier densities responsible for the ambipolar electrical characteristics. The thin‐film morphology of the organic heterojunction with its interpenetrating network structure can be controlled well by the vacuum‐deposition process. The structure of interpenetrating networks is similar to that of the bulk heterojunction used in organic photovoltaic cells, therefore, it may be helpful in understanding the process of charge collection in organic photovoltaic cells.     

Cover Picture: An Organic Light‐Emitting Diode with Field‐Effect Electron Transport (Adv. Funct. Mater. 1/2008)

The cover shows an organic light‐emitting diode with remote metallic cathode, reported by Sarah Schols and co‐workers on p. 136. The metallic cathode is displaced from the light‐emission zone by one to several micrometers. The injected electrons accumulate at an organic heterojunction and are transported to the light‐emission zone by field‐effect. The achieved charge‐carrier mobility and in combination with reduced optical absorption losses because of the remoteness of the cathode may lead to applications as waveguide OLEDs and possibly a laser structure. (The result was obtained in the EU‐funded project “OLAS” IST‐ FP6‐015034.) We describe an organic light‐emitting diode (OLED) using field‐effect to transport electrons. The device is a hybrid between a diode and a field‐effect transistor. Compared to conventional OLEDs, the metallic cathode is displaced by one to several micrometers from the light‐emitting zone. This micrometer‐sized distance can be bridged by electrons with enhanced field‐effect mobility. The device is fabricated using poly(triarylamine) (PTAA) as the hole‐transport material, tris(8‐hydroxyquinoline) aluminum (Alq₃) doped with 4‐(dicyanomethylene)‐2‐methyl‐6‐(julolindin‐4‐yl‐vinyl)‐4H‐pyran (DCM₂) as the active light‐emitting layer, and N,N′‐ditridecylperylene‐3,4,9,10‐tetracarboxylic diimide (PTCDI‐C₁₃H₂₇), as the electron‐transport material. The obtained external quantum efficiencies are as high as for conventional OLEDs comprising the same materials. The quantum efficiencies of the new devices are remarkably independent of the current, up to current densities of more than 10 A cm^–2. In addition, the absence of a metallic cathode covering the light‐emission zone permits top‐emission and could reduce optical absorption losses in waveguide structures. These properties may be useful in the future for the fabrication of solid‐state high‐brightness organic light sources.     

Ultraviolet‐Light‐Induced Reversible and Stable Carrier Modulation in MoS2 Field‐Effect Transistors

The tuning of charge carrier concentrations in semiconductor is necessary in order to approach high performance of the electronic and optoelectronic devices. It is demonstrated that the charge‐carrier density of single‐layer (SL), bilayer (BL), and few‐layer (FL) MoS₂ nanosheets can be finely and reversibly tuned with N₂ and O₂ gas in the presence of deep‐ultraviolet (DUV) light. After exposure to N₂ gas in the presence of DUV light, the threshold voltages of SL, BL, and FL MoS₂ field‐effect transistors (FETs) shift towards negative gate voltages. The exposure to N₂ gas in the presence of DUV light notably improves the drain‐to‐source current, carrier density, and charge‐carrier mobility for SL, BL, and FL MoS₂ FETs. Subsequently, the same devices are exposed to O₂ gas in the presence of DUV light for different periods and the electrical characteristics are completely recovered after a certain time. The doping by using the combination of N₂ and O₂ gas with DUV light provides a stable, effective, and facile approach for improving the performance of MoS₂ electronic devices.     

Integration of a Rib Waveguide Distributed Feedback Structure into a Light‐Emitting Polymer Field‐Effect Transistor

Ambipolar light‐emitting organic field‐effect transistors (LEFETs) possess the ability to efficiently emit light due to charge recombination in the channel. Since the emission can be made to occur far from the metal electrodes, the LEFET structure has been proposed as a potential architecture for electrically pumped organic lasers. Here, a rib waveguide distributed feedback structure consisting of tantalum pentoxide (Ta₂O₅) integrated within the channel of a top gate/bottom contact LEFET based on poly(9,9‐dioctylfluorene‐alt‐benzothiadiazole) (F8BT) is demonstrated. The emitted light is coupled efficiently into the resonant mode of the DFB waveguide when the recombination zone of the LEFET is placed directly above the waveguide ridge. This architecture provides strong mode confinement in two dimensions. Mode simulations are used to optimize the dielectric thickness and gate electrode material. It is shown that electrode absorption losses within the device can be eliminated and that the lasing threshold for optical pumping of the LEFET structure with all electrodes (4.5 µJ cm^?2) is as low as that of reference devices without electrodes. These results enable quantitative judgement of the prospects for realizing an electrically pumped organic laser based on ambipolar LEFETs. The proposed device provides a powerful, low‐loss architecture for integrating high‐performance ambipolar organic semiconductor materials into electrically pumped lasing structures.     

Cover Picture: n‐Channel,Ambipolar, and p‐Channel Organic Heterojunction Transistors Fabricated with Various Film Morphologies (Adv. Funct. Mater. 3/2007)

Simultaneous introduction of short‐range repulsive interactions between dissimilar colloidal particles and attractive interactions between like particles provides a general new route to fabricating self‐organizing bipolar devices. By identifying combinations of conductive device materials between which short‐range repulsive forces exist in the presence of an intervening liquid, electrochemical junctions can be self‐formed, as reported by Chiang and co‐workers on p. 379. The relationship between the performance characteristics of organic field‐effect transistors (OFETs) with 2,5‐bis(4‐biphenylyl)bithiophene/copper hexadecafluorophthalocyanine (BP2T/F₁₆CuPc) heterojunctions and the thickness of the BP2T bottom layer is investigated. Three operating modes (n‐channel, ambipolar, and p‐channel) are obtained by varying the thickness of the organic semiconductor layer. The changes in operating mode are attributable to the morphology of the film and the heterojunction effect, which also leads to an evolution of the field‐effect mobility with increasing film thickness. In BP2T/F₁₆CuPc heterojunctions the mobile charge carriers accumulate at both sides of the heterojunction interface, with an accumulation layer thickness of ca. 10 nm. High field‐effect mobility values can be achieved in continuous and flat films that exhibit the heterojunction effect.     

n‐Channel,Ambipolar, and p‐Channel Organic Heterojunction Transistors Fabricated with Various Film Morphologies

The relationship between the performance characteristics of organic field‐effect transistors (OFETs) with 2,5‐bis(4‐biphenylyl)bithiophene/copper hexadecafluorophthalocyanine (BP2T/F₁₆CuPc) heterojunctions and the thickness of the BP2T bottom layer is investigated. Three operating modes (n‐channel, ambipolar, and p‐channel) are obtained by varying the thickness of the organic semiconductor layer. The changes in operating mode are attributable to the morphology of the film and the heterojunction effect, which also leads to an evolution of the field‐effect mobility with increasing film thickness. In BP2T/F₁₆CuPc heterojunctions the mobile charge carriers accumulate at both sides of the heterojunction interface, with an accumulation layer thickness of ca. 10 nm. High field‐effect mobility values can be achieved in continuous and flat films that exhibit the heterojunction effect.     

Solution‐Processed Small‐Molecule Bulk Heterojunction Ambipolar Transistors

Solution‐processed small‐molecule bulk heterojunction (BHJ) ambipolar organic thin‐film transistors are fabricated based on a combination of [2‐phenylbenzo[d,d']thieno[3,2‐b;4,5‐b']dithiophene (P‐BTDT) : 2‐(4‐n‐octylphenyl)benzo[d,d ']thieno[3,2‐b;4,5‐b']dithiophene (OP‐BTDT)] and C₆₀. Treating high electrical performance vacuum‐deposited P‐BTDT organic semiconductors with a newly developed solution‐processed organic semiconductor material, OP‐BTDT, in an optimized ratio yields a solution‐processed p‐channel organic semiconductor blend with carrier mobility as high as 0.65 cm² V^?1 s^?1. An optimized blending of P‐BTDT:OP‐BTDT with the n‐channel semiconductor, C₆₀, results in a BHJ ambipolar transistor with balanced carrier mobilities for holes and electrons of 0.03 and 0.02 cm² V^?1 s^?1, respectively. Furthermore, a complementary‐like inverter composed of two ambipolar thin‐film transistors is demonstrated, which achieves a gain of 115.     

High‐Performance,Phosphorescent, Top‐Emitting Organic Light‐Emitting Diodes with p–i–n Homojunctions

High‐performance, green, orange, and red top‐emitting organic light‐emitting diodes (TOLEDs) with p–i–n homojunction are demonstrated. An excellent ambipolar host, 2,5‐bis(2‐(9H‐carbazol‐9‐yl)phenyl)‐1,3,4‐oxadiazole (o‐CzOXD), which has good thermal and morphological stabilities, a high triplet energy level, and equally high electron and hole mobilities, is chosen as the organic host material for the homojunction devices. By electrical doping, the carrier injection and transporting characteristics are greatly improved. The optical structure is optimized in view of light emission of different colors to enhance the color purity and improve the view characte­ristics. As a result, high efficiency p–i–n homojunction TOLEDs with saturated intrinsic emission of the emitting materials and angular independence of the emission are realized. The performances of these p–i–n homojunction TOLEDs are even higher than the multi‐layer heterojunction bottom‐emitting devices using the same emitting layers.     

Emission Color Tuning in Ambipolar Organic Single‐Crystal Field‐Effect Transistors by Dye‐Doping

The effect of dye‐doping in ambipolar light‐emitting organic field‐effect transistors (LE‐OFETs) is investigated from the standpoint of the carrier mobilities and the electroluminescence (EL) characteristics under ambipolar operation. Dye‐doping of organic crystals permits not only tuning of the emission color but also significantly increases the efficiency of ambipolar LE‐OFETs. A rather high external EL quantum efficiency (～0.64%) of one order of magnitude higher than that of a pure p‐distyrylbenzene (P3V2) single crystal is obtained by tetracene doping. The doping of tetracene molecules into a host P3V2 crystal has almost no effect on the electron mobility and the dominant carrier recombination process in the tetracene‐doped P3V2 crystal involves direct carrier recombination on the tetracene molecules.     

Nanostructured Si/Organic Heterojunction Solar Cells with High Open‐Circuit Voltage via Improving Junction Quality

Nanostructured silicon (Si) can provide improved light harvest efficiencies in organic‐Si heterojunction solar cells due to its low light reflection ratio compared with planar one. However, the associated large surface/volume ratio of nanostructured Si suffers from serious surface recombination as well as poor adhesion with organics in organic‐Si heterojunction solar cells, which leads to an inferior open‐circuit voltage (V_oc). Here, we develop a simple and effective method to suppress charge recombination as well as enhancing adhesion force between nanostructured Si and organics by incorporating a silane chemical, namely 3‐glycidoxypropyltrimethoxydsilane (GOPS). GOPS can chemically graft onto nanostructured Si and improve the aqueous organic wetting properties, suppressing surface charge recombination velocity dramatically. In addition, this chemically grafted layer can enhance adhesion force between organics and Si. In such a way, a record V_oc of 640 mV associated with a power conversion efficiency of 14.1% is obtained for organic‐nanostructured Si heterojunction devices. These findings suggest a promising approach to low‐cost and simple fabrication for high‐performance organic‐Si solar cells.     

Solution‐Processed Zinc Oxide as High‐Performance Air‐Stable Electron Injector in Organic Ambipolar Light‐Emitting Field‐Effect Transistors

Electron injection from the source–drain electrodes limits the performance of many n‐type organic field‐effect transistors (OFETs), particularly those based on organic semiconductors with electron affinities less than 3.5 eV. Here, it is shown that modification of gold source–drain electrodes with an overlying solution‐deposited, patterned layer of an n‐type metal oxide such as zinc oxide (ZnO) provides an efficient electron‐injecting contact, which avoids the use of unstable low‐work‐function metals and is compatible with high‐resolution patterning techniques such as photolithography. Ambipolar light‐emitting field‐effect transistors (LEFETs) based on green‐light‐emitting poly(9,9‐dioctylfluorene‐alt‐benzothiadiazole) (F8BT) and blue‐light‐emitting poly(9,9‐dioctylfluorene) (F8) with electron‐injecting gold/ZnO and hole‐injecting gold electrodes show significantly lower electron threshold voltages and several orders of magnitude higher ambipolar currents, and hence light emission intensities, than devices with bare gold electrodes. Moreover, different solution‐deposited metal oxide injection layers are compared. By spin‐coating ZnO from a low‐temperature precursor, processing temperatures could be reduced to 150 °C. Ultraviolet photoemission spectroscopy (UPS) shows that the improvement in transistor performance is due to reduction of the electron injection barrier at the interface between the organic semiconductor and ZnO/Au compared to bare gold electrodes.     

Simultaneous Tenfold Brightness Enhancement and Emitted‐Light Spectral Tunability in Transparent Ambipolar Organic Light‐Emitting Transistor by Integration of High‐k Photonic Crystal

In organic light‐emitting transistors, the structural properties such as the in‐plane geometry and the lateral charge injection are the key elements that enable the monolithic integration of multiple electronic, optoelectronic, and photonic functions within the same device. Here, the realization of highly integrated multifunctional optoelectronic organic device is reported by introducing a high‐capacitance photonic crystal as a gate dielectric into a transparent single‐layer ambipolar organic light‐emitting transistor (OLET). By engineering the photonic crystal multistack and bandgap, it is showed that the integration of the photonic structure has a twofold effect on the optoelectronic performance of the device, i.e., i) to modulate the spectral profile and outcoupling of the emitted light and ii) to enhance the transistor source–drain current by a 25‐fold factor. Consequently, the photonic‐crystal‐integrated OLET shows an order of magnitude higher emitted power and brightness with respect to the corresponding polymer‐dielectric device, while presenting as‐designed electroluminescence spectral and spatial distribution. The results validate the efficacy of the proposed approach that is expected to unravel the technological potential for the realization of highly integrated optoelectronic smart systems based on organic light‐emitting transistors.     

Dicyanovinyl–Substituted Oligothiophenes: Structure‐Property Relationships and Application in Vacuum‐Processed Small Molecule Organic Solar Cells

Efficient synthesis of a series of terminally dicyanovinyl (DCV)‐substituted oligothiophenes, DCVnT 1–6, without solubilizing side chains synthesized via a novel convergent approach and their application as electron donors in vacuum‐processed m‐i‐p‐type planar and p‐i‐n‐type bulk heterojunction organic solar cells is described. Purification of the products via gradient sublimation yields thermally highly stable organic semiconducting materials in single crystalline quality which allows for X‐ray structure analysis. Important insights into the packing features and intermolecular interactions of these promising solar cell materials are provided. Optical absorption spectra and electrochemical properties of the oligomers are investigated and valuable structure–property relationships deduced. Photovoltaic devices incorporating DCVnTs 4–6 showed power conversion efficiencies up to 2.8% for planar and 5.2% for bulk heterojunction organic solar cells under full sun illumination (mismatch corrected simulated AM 1.5G sunlight). The 5.2% efficiency shown here represents one of the highest values ever reported for organic vacuum‐deposited single heterojunction solar cells.     

Solution Processable Monosubstituted Hexa‐Peri‐Hexabenzocoronene Self‐Assembling Dyes

Molecular organization behavior and visible light absorption ability are important factors for organic materials to be used in efficient bulk heterojunction solar cells applications. In this context, a series of monosubstituted fluorenyl hexa‐peri‐hexabenzocoronene (FHBC) are synthesized with the aim to combine the self‐association property of the FHBC unit with broadened light absorption of a small molecule organic dye, bisthienylbenzothiadiazole (TBT). Optical and electrochemical properties of the FHBC compounds vary according to their structures. Introduction of a TBT unit into the FHBC system broadens the absorption. All of the FHBC compounds show strong π–π intermolecular association in solution. X‐ray scattering measurements on thermally extruded filaments and thin films showed ordered alignment of these compounds in the solid state. In atomic force microscopy experiments, nanoscale phase separation is observed in thin films of FHBC and fullerene derivative blends. Solar cell devices with these compounds as donors are fabricated. FHBC compounds with the TBT unit show higher short circuit current while the high open circuit voltages are maintained. With C₆₀ derivative as acceptor, power conversion efficiency of 1.12% is achieved in the unoptimized solar cell devices under simulated solar irradiation. The efficiency was further improved to 1.64% when C₇₀ derivative was used as the acceptor.     

Solution Processable Fluorenyl Hexa‐peri‐hexabenzocoronenes in Organic Field‐Effect Transistors and Solar Cells

The organization of organic semiconductor molecules in the active layer of organic electronic devices has important consequences to overall device performance. This is due to the fact that molecular organization directly affects charge carrier mobility of the material. Organic field‐effect transistor (OFET) performance is driven by high charge carrier mobility while bulk heterojunction (BHJ) solar cells require balanced hole and electron transport. By investigating the properties and device performance of three structural variations of the fluorenyl hexa‐peri‐hexabenzocoronene (FHBC) material, the importance of molecular organization to device performance was highlighted. It is clear from ¹H NMR and 2D wide‐angle X‐ray scattering (2D WAXS) experiments that the sterically demanding 9,9‐dioctylfluorene groups are preventing π–π intermolecular contact in the hexakis‐substituted FHBC 4 . For bis‐substituted FHBC compounds 5 and 6 , π–π intermolecular contact was observed in solution and hexagonal columnar ordering was observed in solid state. Furthermore, in atomic force microscopy (AFM) experiments, nanoscale phase separation was observed in thin films of FHBC and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PC₆₁BM) blends. The differences in molecular and bulk structural features were found to correlate with OFET and BHJ solar cell performance. Poor OFET and BHJ solar cells devices were obtained for FHBC compound 4 while compounds 5 and 6 gave excellent devices. In particular, the field‐effect mobility of FHBC 6 , deposited by spin‐casting, reached 2.8 × 10^?3 cm² V^?1 s and a power conversion efficiency of 1.5% was recorded for the BHJ solar cell containing FHBC 6 and PC₆₁BM.     

White‐Light Emitting Diode Array of p+‐Si/Aligned n‐SnO2 Nanowires Heterojunctions

We report on the fabrication and optoelectronic properties of p‐n heterojunction arrays of p⁺‐type Si and aligned n‐type SnO₂ nanowires with high rectification ratios of >10⁴ at ±15 V. The electrical stability of the p‐n heterojunction devices was improved by coating the junction with poly(methylmethacrylate) to minimize the degradation of the interface layer at the junction. As a photodiode an enhanced UV photosensitivity higher than 10² was recorded under reverse bias. Using a large forward bias in the light‐emitting diode mode white light was emitted from the large‐scale heterojunction devices with at least three broad peaks in the visible range, which can be attributed to the interband transitions of the injected electrons or holes mediated by an interfacial SiO₂ layer with a contribution of trap‐level energies. These results indicate the high potential of Si/SnO₂ nanowires heterojunctions as optoelectronic devices with proper tuning of the recombination center at the junctions.     

Versatile,Benzimidazole/Amine‐Based Ambipolar Compounds for Electroluminescent Applications: Single‐Layer,Blue, Fluorescent OLEDs,Hosts for Single‐Layer,Phosphorescent OLEDs

A series of compounds containing arylamine and 1,2‐diphenyl‐1H‐benz[d]imidazole moieties are developed as ambipolar, blue‐emitting materials with tunable blue‐emitting wavelengths, tunable ambipolar carrier‐transport properties and tunable triplet energy gaps. These compounds possess several novel properties: (1) they emit in the blue region with high quantum yields; (2) they have high morphological stability and thermal stability; (3) they are capable of ambipolar carrier transport; (4) they possess tunable triplet energy gaps, suitable as hosts for yellow‐orange to green phosphors. The electron and hole mobilities of these compounds lie in the range of 0.68–144 × 10^?6 and 0.34–147 × 10^?6 cm² V^?1 s^?1, respectively. High‐performance, single‐layer, blue‐emitting, fluorescent organic light‐emitting diodes (OLEDs) are achieved with these ambipolar materials. High‐performance, single‐layer, phosphorescent OLEDs with yellow‐orange to green emission are also been demonstrated using these ambipolar materials, which have different triplet energy gaps as the host for yellow‐orange‐emitting to green‐emitting iridium complexes. When these ambipolar, blue‐emitting materials are lightly doped with a yellow‐orange‐emitting iridium complex, white organic light‐emitting diodes (WOLEDs) can be achieved, as well by the use of the incomplete energy transfer between the host and the dopant.     

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.     

Amino N‐Oxide Functionalized Conjugated Polymers and their Amino‐Functionalized Precursors: New Cathode Interlayers for High‐Performance Optoelectronic Devices

A series of amino N‐oxide functionalized polyfluorene homopolymers and copolymers (PNOs) are synthesized by oxidizing their amino functionalized precursor polymers (PNs) with hydrogen peroxide. Excellent solubility in polar solvents and good electron injection from high work‐function metals make PNOs good candidates for interfacial modification of solution processed multilayer polymer light‐emitting diodes (PLEDs) and polymer solar cells (PSCs). Both PNOs and PNs are used as cathode interlayers in PLEDs and PSCs. It is found that the resulting devices show much better performance than devices based on a bare Al cathode. The effect of side chain and main chain variations on the device performance is investigated. PNOs/Al cathode devices exhibit better performance than PNs/Al cathode devices. Moreover, devices incorporating polymers with para‐linkage of pyridinyl moieties exhibit better performance than those using polymers with meta‐linked counterparts. With a poly[(2,7‐(9,9‐bis(6‐(N,N‐diethylamino)‐hexyl N‐oxide)fluorene))‐alt‐(2,5‐pyridinyl)] (PF6NO25Py) cathode interlayer, the resulting device exhibits a luminance efficiency of 16.9 cd A^?1 and a power conversion efficiency of 6.9% for PLEDs and PSCs, respectively. These results indicate that PNOs are promising new cathode interlayers for modifying a range of 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.