Beyond Conventional Enhancements: Self-Organization of a Buffer Material on Tin Oxide as a Game-Changer for Improving the Performance of Inverted Organic Solar Cells.

Inverted organic solar cells (OSCs) have garnered significant interest due to their remarkable stability. In this study, the efficiency and stability of inverted OSCs are enhanced via the in situ self-organization (SO) of an interfacial modification material Phen-NaDPO onto tin oxide (SnO2). During the device fabrication, Phen-NaDPO is spin-coated with the active materials all together on SnO2. Driven by the interactions with SnO2 and the thermodynamic forces due to its high surface energy and the convection flow, Phen-NaDPO spontaneously migrates to the SnO2 interface, resulting in the formation of an in situ modification layer on SnO2. This self-organization of Phen-NaDPO not only effectively reduces the work function of SnO2, but also enhances the ordered molecular stacking and manipulates the vertical morphology of the active layer, which suppress the surface trap-assisted recombination and minimize the charge extraction. As a result, the SO devices based on PM6:Y6 exhibit significantly improved photovoltaic performance with an enhanced power conversion efficiency of 17.62%. Moreover, the stability of the SO device is also improved. Furthermore, the SO ternary devices based on PM6:D18:L8-BO achieved an impressive PCE of 18.87%, standing as one of the highest values for single-junction inverted organic solar cells to date.

Highly Stretchable Conjugated Polymer/Elastomer Blend Films with Sandwich Structure.

The physical blending of high-mobility conjugated polymers with ductile elastomers provides a simple way to realize high-performance stretchable films. However, how to control the morphology of the conjugated polymer and elastomer blend film and its response to mechanical fracture processes during stretching are not well understood. Herein, a sandwich structure is constructed in the blend film based on a conjugated polymer poly[(5-fluoro-2,1,3-benzothiadiazole-4,7-diyl)(4,4-dihexadecyl-4H-cyclopenta[2,1-b:3,4-b″]dithiophene-2,6-diyl)(6-fluoro-2,1,3-benzothiadiazole-4,7-diyl)(4,4-dihexadecyl-4H-cyclopenta[2,1-b:3,4-b″]dithiophene-2,6-diyl)] (PCDTFBT) and an elastomer polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (SEBS). The sandwich structure is composed of a PCDTFBT:SEBS mixed layer laminated with a PCDTFBT-rich layer at both the top and bottom surfaces. During stretching, the external strain energy can be effectively dissipated by the deformation of the crystalline PCDTFBT domains and amorphous SEBS phases and the recrystallization of the PCDTFBT chains. This endows the blend film with excellent ductility, with a large crack onset strain exceeding 1100%, and minimized the electrical degradation of the blend film at a large strain. This study indicates that the electrical and mechanical performance of conjugated polymer/elastomer blend films can be improved by manipulating their microstructure.

Binary All-polymer Solar Cells with a Perhalogenated-Thiophene-Based Solid Additive Surpass 18 % Efficiency.

Morphological control of all-polymer blends is quintessential yet challenging in fabricating high-performance organic solar cells. Recently, solid additives (SAs) have been approved to be capable in tuning the morphology of polymer: small-molecule blends improving the performance and stability of devices. Herein, three perhalogenated thiophenes, which are 3,4-dibromo-2,5-diiodothiophene (SA-T1), 2,5-dibromo-3,4-diiodothiophene (SA-T2), and 2,3-dibromo-4,5-diiodothiophene (SA-T3), were adopted as SAs to optimize the performance of all-polymer organic solar cells (APSCs). For the blend of PM6 and PY-IT, benefitting from the intermolecular interactions between perhalogenated thiophenes and polymers, the molecular packing properties could be finely regulated after introducing these SAs. In situ UV/Vis measurement revealed that these SAs could assist morphological character evolution in the all-polymer blend, leading to their optimal morphologies. Compared to the as-cast device of PM6 : PY-IT, all SA-treated binary devices displayed enhanced power conversion efficiencies of 17.4-18.3 % with obviously elevated short-circuit current densities and fill factors. To our knowledge, the PCE of 18.3 % for SA-T1-treated binary ranks the highest among all binary APSCs to date. Meanwhile, the universality of SA-T1 in other all-polymer blends is demonstrated with unanimously improved device performance. This work provide a new pathway in realizing high-performance APSCs.

Isomeric Dimer Acceptors for Stable Organic Solar Cells with over 19% Efficiency.

The strategy of isomerization is known for its simple yet effective role in optimizing molecular configuration and enhancing the power conversion efficiency (PCE) of organic solar cells (OSCs). However, the impact of isomerization on the design of dimer acceptors has been rarely investigated, and the relationship between the chemical structure and optoelectronic property remains unclear. In this study, we designed and synthesized two dimer acceptor isomers named D-TPh and D-TN, which differ in the positional arrangement of their end capping groups. Compared to D-TN, D-TPh exhibited enhanced backbone planarity, elevated lowest unoccupied molecular orbital energy level, and more ordered molecular stacking. Consequently, the OSC device based on PM6:D-TPh achieved a PCE of 19.05%, higher than that (PCE = 18.42%) of the device based on PM6:D-TN. Large-area PM6:D-TPh devices (1 cm²) yielded a PCE of 18.0%. More importantly, the extrapolated T80 lifetime of the PM6:D-TPh device is over 2800 h with MPP tracking under continuous one-sun illumination. These results suggest that isomerization strategy is an effective way to optimize the molecular configuration of dimer acceptors for the fabrication of high-efficiency and stable OSCs.

Non-halogenated Solvent-Processed Organic Solar Cells with Approaching 20 % Efficiency and Improved Photostability.

The development of high-efficiency organic solar cells (OSCs) processed from non-halogenated solvents is crucially important for their scale-up industry production. However, owing to the difficulty of regulating molecular aggregation, there is a huge efficiency gap between non-halogenated and halogenated solvent processed OSCs. Herein, we fabricate o-xylene processed OSCs with approaching 20 % efficiency by incorporating a trimeric guest acceptor named Tri-V into the PM6:L8-BO-X host blend. The incorporation of Tri-V effectively restricts the excessive aggregation of L8-BO-X, regulates the molecular packing and optimizes the phase-separation morphology, which leads to mitigated trap density states, reduced energy loss and suppressed charge recombination. Consequently, the PM6:L8-BO-X:Tri-V-based device achieves an efficiency of 19.82 %, representing the highest efficiency for non-halogenated solvent-processed OSCs reported to date. Noticeably, with the addition of Tri-V, the ternary device shows an improved photostability than binary PM6:L8-BO-X-based device, and maintains 80 % of the initial efficiency after continuous illumination for 1380 h. This work provides a feasible approach for fabricating high-efficiency, stable, eco-friendly OSCs, and sheds new light on the large-scale industrial production of OSCs.

Asymmetrified Benzothiadiazole-Based Solid Additives Enable All-Polymer Solar Cells with Efficiency Over 19.

Disordered polymer chain entanglements within all-polymer blends limit the formation of optimal donor-acceptor phase separation. Therefore, developing effective methods to regulate morphology evolution is crucial for achieving optimal morphological features in all-polymer organic solar cells (APSCs). In this study, two isomers, 4,5-difluorobenzo-c-1,2,5-thiadiazole (SF-1) and 5,6-difluorobenzo-c-1,2,5-thiadiazole (SF-2), were designed as solid additives based on the widely-used electron-deficient benzothiadiazole unit in nonfullerene acceptors. The incorporation of SF-1 or SF-2 into PM6:PY-DT blend induces stronger molecular packing via molecular interaction, leading to the formation of continuous interpenetrated networks with suitable phase-separation and vertical distribution. Furthermore, after treatment with SF-1 and SF-2, the exciton diffusion lengths for PY-DT films are extended to over 40 nm, favoring exciton diffusion and charge transport. The asymmetrical SF-2, characterized by an enhanced dipole moment, increases the power conversion efficiency (PCE) of PM6:PY-DT-based device to 18.83% due to stronger electrostatic interactions. Moreover, a ternary device strategy boosts the PCE of SF-2-treated APSC to over 19%. This work not only demonstrates one of the best performances of APSCs but also offers an effective approach to manipulate the morphology of all-polymer blends using rational-designed solid additives.

Highly Durable Inverted Inorganic Perovskite/Organic Tandem Solar Cells Enabled by Multifunctional Additives.

Inverted perovskite/organic tandem solar cells (P/O TSCs) suffer from poor long-term device stability due to halide segregation in organic-inorganic hybrid wide-bandgap (WBG) perovskites, which hinders their practical deployment. Therefore, developing all-inorganic WBG perovskites for incorporation into P/O TSCs is a promising strategy because of their superior stability under continuous illumination. However, these inorganic WBG perovskites also face some critical issues, including rapid crystallization, phase instability, and large energy loss, etc. To tackle these issues, two multifunctional additives based on 9,10-anthraquinone-2-sulfonic acid (AQS) are developed to regulate the perovskite crystallization by mediating the intermediate phases and suppress the halide segregation through the redox-shuttle effect. By coupling with organic cations having the desirable functional groups and dipole moments, these additives can effectively passivate the defects and adjust the alignment of interface energy levels. Consequently, a record Voc approaching 1.3 V with high power conversion efficiency (PCE) of 18.59% could be achieved in a 1.78 eV bandgap single-junction inverted all-inorganic PSC. More importantly, the P/O TSC derived from this cell demonstrates a T90 lifetime of 1000 h under continuous operation, presenting the most stable P/O TSCs reported so far.

End Group Effect of Asymmetric Benzodithiophene-Based Donor with Liquid-Crystal State for Small-Molecule Binary Solar Cell.

Liquid-crystal small molecule donor (LC-SMD) is a new type organic semiconductor, which is attractive not only for the easy synthesis and purification, well-defined chemical structures, etc., but also for the LC state that makes the crystallinity and aggregation state of molecules adjustable. Here, one new LC-SMD (a-BTR-H4) is synthesized with 1D alkoxyl and 2D thiophene-alkylthiol side-chained benzo[1,2-b:4,5-b']dithiophene core, trithiophene π-bridge, and 3-(2-ethylhexyl) rhodanine end group. a-BTR-H4 shows low LC transition temperature, 117 °C, however, counterpart material (a-BTR-H5) with the same main structure but 3-ethyl rhodanine terminal group does not show LC properties. Although a-BTR-H4/H5 show similar Ultraviolet-visible absorption spectrum and energy levels, a-BTR-H4 affords relatively high photovoltaic performances due to favorable blend morphology produced by the consistent annealing temperature of Y6-based accepters and liquid crystal temperature of donors. Preliminary results indicate that a-BTR-H4 gains a power conversion efficiency (PCE) of 11.36% for Y6-based devices, which is ascribed to better light harvest as well as balanced carrier generation and transport, while a-BTR-H5 obtains 7.57% PCE. Therefore, some materials with unique nematic LC phase have great application potential in organic electronics, and further work to utilize a-BTR-H4 for high-performance device is underway.

Improving Charge Injection at Gold/Conjugated Polymer Contacts by Polymer Insulator-Assisted Annealing for Transistors.

The poor chemical miscibility between metal and organic materials usually leads to both structural and energetic mismatches at gold/organic interfaces, and thereby, high contact resistance of organic electronic devices. This study shows that the contact resistance of organic field-effect transistors is significantly reduced by one order of magnitude, by reforming the contact interface between gold electrodes and conjugated polymers upon a polymer insulator-assisted thermal annealing. Upon an optimized solution process, the conjugated polymer is homogenously distributed within the amorphous polymer insulator matrix with relatively low glass transition temperature, and thus, even a moderate annealing temperature can induce sufficient motion of conjugated polymer chains to simultaneously adjust the polymer orientation and improve the packing of gold atoms. Consequently, gold/conjugated polymer contact is reorganized after annealing, which improves both charge transport from bulk gold to interface and charge injection from gold into conjugated polymers. This method, with appropriate insulator matrix, is effective for improving the injection of both holes and electrons, and widely applicable for many unipolar and ambipolar conjugated polymers to optimize the device performance and simultaneously increase the optical transparency (over 80%). A frequency doubler and a phase modulator are demonstrated, respectively, using the ambipolar transistors with optimized charge injection properties.

All-Small-Molecule Organic Solar Cells with Efficiency Approaching 16% and FF over 80.

Molecule engineering has been demonstrated as a valid strategy to adjust the active layer morphology in all-small-molecule organic solar cells (ASM-OSCs). In this work, two non-fullerene acceptors (NFAs), FO-2Cl and FO-EH-2Cl, with different alkyl side chains are reported and applied in ASC-OSCs. Compared with FO-2Cl, FO-EH-2Cl is designed by replacing the octyl alkyl chains with branched iso-octyl alkyl chains, leading to an enhanced molecular packing, crystallinity, and redshifted absorption. With a small molecule BSFTR as donor, the device of BSFTR:FO-EH-2Cl obtains a better morphology and achieves a higher power conversion efficiency (PCE) of 15.78% with a notable fill factor (FF) of 80.44% than that of the FO-2Cl-based device with a PCE of 15.27% and FF of 78.41%. To the authors' knowledge, the FF of 80.44% is the highest value in ASM-OSCs. These results demonstrate a good example of fine-tuning the molecular structure to achieve suitable active layer morphology with promising performance for ASM-OSCs, which can provide valuable insight into material design for high-efficiency ASM-OSCs.

Interfacial Effect on Dielectric Properties of Self-Assembled Polythiourea-Based Copolymers for Ultrahigh Energy Storage.

Polymer dielectrics are highly desirable in capacitor applications due to their low cost, high stability, and reliability. However, there still remains a lack of feasible methods to prepare polymer dielectrics with high energy density and low dielectric loss, which severely hampers the development of compact and efficient power electronics. Here, an amphiphilic block copolymer, polythiourea-b-polydimethylsiloxane (PTU-b-PDMS), with an extraordinarily high energy density of 29.8 J cm-3 and a low loss is synthesized via polyaddition polymerization. This is highly relevant to the block molecule conformation in the interfacial region of the self-assembled PTU-b-PDMS. The block molecule in the interface adopts an extended conformation when the PTU forms nanodots, whereas the block molecule adopts a coiled conformation when the PTU forms nanostrands. The observation and characterization have proved that the coiled block molecule in the interfacial region can simultaneously induce extra strong charge trapping sites and dipolar polarization. It substantially improves the breakdown strength from 652 to 1166 MV m-1 , while maintaining a high dielectric constant of 5 and a low loss of <0.01. This work offers unprecedented structural insights into the conformation-induced interfacial effect and enables rational design of self-assembled copolymers to boost their dielectric properties and energy density.

Achieving over 18 % Efficiency Organic Solar Cell Enabled by a ZnO-Based Hybrid Electron Transport Layer with an Operational Lifetime up to 5†Years.

Although organic solar cells (OSCs) have delivered an impressive power conversion efficiency (PCE) of over 19 %, most of them demonstrated rather limited stability. So far, there are hardly any effective and universal strategies to improve stability of state-of-the-art OSCs. Herein, we developed a hybrid electron-transport layer (ETL) in inverted OSCs using ZnO and a new modifying agent (NMA), and significantly improved the stability and PCEs for all the tested devices. In particular, when applied in the D18 : N3 system, its inverted OSC exhibits so far the highest PCE (18.20 %) among inverted single-junction OSCs, demonstrating an extrapolated T80 lifetime of 7572 h (equivalent to 5 years under outdoor exposure). This is the first report with T80 over 5000 h among OSCs with over 18 % PCE. Furthermore, a high PCE of 16.12 % can be realized even in a large-area device (1 cm2 ). This hybrid ETL strategy provides a strong stimulus for highly prospective commercialization of OSCs.

Effect of Isomerization on High-Performance Nonfullerene Electron Acceptors.

We design and synthesize two isomeric fused-ring electron acceptors, FNIC1 and FNIC2, which have the same end-groups and side-chains, but isomeric fused-nine-ring cores. Subtle changes in the two isomers influence their electronic, optical, charge-transport, and morphological properties. As compared with FNIC1, FNIC2 film exhibits a red-shifted absorption peak at 794 nm (752 nm for FNIC1), larger electron affinity of 4.00 eV (3.92 eV for FNIC1), smaller ionization energy of 5.56 eV (5.61 eV for FNIC1), and higher electron mobility of 1.7 × 10-3 cm2 V-1 s-1 (1.2 × 10-3 cm2 V-1 s-1 for FNIC1). The as-cast organic solar cells based on PTB7-Th:FNIC2 blends exhibit a power conversion efficiency (PCE) of 13.0%, which is significantly higher than that of PTB7-Th:FNIC1-based devices (10.3%). Semitransparent devices based on PTB7-Th:FNIC2 blends exhibit PCEs varying from 9.51% to 11.6% at different average visible transmittance (AVT, 20.3- 13.6%), significantly higher than those of PTB7-Th:FNIC1-based devices (7.58-9.14% with AVT of 20.2- 14.7%).

Terpolymer Containing a meta-Octyloxy-phenyl-Modified Dithieno[3,2-f:2',3'-h]quinoxaline Unit Enabling Efficient Organic Solar Cells.

With the rapid development of small-molecule electron acceptors, polymer electron donors are becoming more important than ever in organic photovoltaics, and there is still room for the currently available high-performance polymer donors. To further develop polymer donors with finely tunable structures to achieve better photovoltaic performances, random ternary copolymerization is a useful technique. Herein, by incorporating a new electron-withdrawing segment 2,3-bis(3-octyloxyphenyl)dithieno[3,2-f:2',3'-h]quinoxaline derivative (C12T-TQ) to PM6, a series of terpolymers were synthesized. It is worth noting that the introduction of the C12T-TQ unit can deepen the highest occupied molecular orbital energy levels of the resultant polymers. In addition, the polymer Z6 with a 10% C12T-TQ ratio possesses the highest film absorption coefficient (9.86 × 104 cm-1) among the four polymers. When blended with Y6, it exhibited superior miscibility and mutual crystallinity enhancement between Z6 and Y6, suppressed recombination, better exciton separation and charge collection characteristics, and faster hole transfer in the D-A interface. Consequently, the device of Z6:Y6 successfully achieved enhanced photovoltaic parameters and yielded an efficiency of 17.01%, higher than the 16.18% of the PM6:Y6 device, demonstrating the effectiveness of the meta-octyloxy-phenyl-modified dithieno[3,2-f:2',3'-h]quinoxaline moiety to build promising terpolymer donors for high-performance organic solar cells.

High-Performance PM6:Y6-Based Ternary Solar Cells with Enhanced Open Circuit Voltage and Balanced Mobilities via Doping a Wide-Band-Gap Amorphous Acceptor.

Great progress has been made in organic solar cells (OSCs) in recent years, especially after the report of the highly efficient small-molecule electron acceptor Y6. However, the relatively low open circuit voltage (VOC) and unbalanced charge mobilities remain two issues that need to be resolved for further improvement in the performance of OSCs. Herein, a wide-band-gap amorphous acceptor IO-4Cl, which possessed a shallower lowest unoccupied molecular orbital (LUMO) energy level than Y6, was introduced into the PM6:Y6 binary system to construct a ternary device. The mechanism study revealed that the introduced IO-4Cl was alloyed with Y6 to prevent the overaggregation of Y6 and offer dual channels for effective hole transportation, resulting in balanced hole and electron mobilities. Taking these advantages, an enhanced VOC of 0.894 V and an improved fill factor of 75.58% were achieved in the optimized PM6:Y6:IO-4Cl-based ternary device, yielding a promising power conversion efficiency (PCE) of 17.49%, which surpassed the 16.72% efficiency of the PM6:Y6 binary device. This work provides an alternative solution to balance the charge mobilities of PM6:Y6-based devices by incorporating an amorphous high-performance LUMO A-D-A small molecule as the third compound.

Boosting the Efficiency of Perovskite/Organic Tandem Solar Cells via Enhanced Near-Infrared Absorption and Minimized Energy Losses.

The compatibility of perovskite and organic photovoltaic materials in solution processing provides a significant advantage in the fabrication of high-efficiency perovskite/organic tandem solar cells. However, additional recombination losses can occur during exciton dissociation in organic materials, leading to energy losses in the near-infrared region of tandem devices. Consequently, a ternary organic rear subcell is designed containing two narrow-bandgap non-fullerene acceptors to enhance the absorption of near-infrared light. Simultaneously, a unique diffusion-controlled growth technique is adopted to optimize the morphology of the ternary active layer, thereby improving exciton dissociation efficiency. This innovation not only broadens the absorption range of near-infrared light but also facilitates the generation and effective dissociation of excitons. Owing to these technological improvements, the power conversion efficiency (PCE) of organic solar cells increased to 19.2%. Furthermore, a wide-bandgap perovskite front subcell is integrated with a narrow-bandgap organic rear subcell to develop a perovskite/organic tandem solar cell. Owing to the reduction in near-infrared energy loss, the PCE of this tandem device significantly improved, reaching 24.5%.

Over 18% Efficiency Ternary Organic Solar Cells with 300 nm Thick Active Layer Enabled by an Oligomeric Acceptor.

The development of high-efficiency thickness-insensitive organic solar cells (OSCs) is crucially important for the mass production of solar panels. However, increasing the active layer thickness usually induces a substantial loss in efficiency. Herein, a ternary strategy in which an oligomer DY-TF is incorporated into PM6:L8-BO system as a guest component is adopted to break this dilemma. The S···F intramolecular noncovalent interactions in the backbone endow DY-TF with a high planarity. Upon the addition of DY-TF, the crystallinity of the blend is effectively improved, leading to increased charge carrier mobility, which is highly desirable in the fabrication of thick-film devices. As a result, thin-film PM6:L8-BO:DY-TF-based device (110 nm) shows a power conversion efficiency (PCE) of 19.13%. Impressively, when the active layer thickness increases to 300 nm, an efficiency of 18.23% (certified as 17.8%) is achieved, representing the highest efficiency reported for 300 nm thick OSCs thus far. Additionally, blade-coated thick device (300 nm) delivers a promising PCE of 17.38%. This work brings new insights into the construction of efficient OSCs with high thickness tolerance, showing great potential for roll-to-roll printing of large-area solar cells.

Solid Additive Dual-Regulates Spectral Response Enabling High-Performance Semitransparent Organic Solar Cells.

Semi-transparent organic solar cells (ST-OSCs) possess significant potential for applications in vehicles and buildings due to their distinctive visual transparency. Conventional device engineering strategies are typically used to optimize photon selection and utilization at the expense of power conversion efficiency (PCE); moreover, the fixed spectral utilization range always imposes an unsatisfactory upper limit to its light utilization efficiency (LUE). Herein, a novel solid additive named 1,3-diphenoxybenzene (DB) is employed to dual-regulate donor/acceptor molecular aggregation and crystallinity, which effectively broadens the spectral response of ST-OSCs in near-infrared region. Besides, more visible light is allowed to pass through the devices, which enables ST-OSCs to possess satisfactory photocurrent and high average visible transmittance (AVT) simultaneously. Consequently, the optimal ST-OSC based on PP2+DB/BTP-eC9+DB achieves a superior LUE of 4.77%, representing the highest value within AVT range of 40-50%, which also correlates with the formation of multi-scale phase-separated morphology. Such results indicate that the ST-OSCs can simultaneously meet the requirements for minimum commercial efficiency and plant photosynthesis when integrated with the roofs of agricultural greenhouses. This work emphasizes the significance of additives to tune the spectral response in ST-OSCs, and charts the way for organic photovoltaics in economically sustainable agricultural development.

Eliminating the Burn-in Loss of Efficiency in Organic Solar Cells by Applying Dimer Acceptors as Supramolecular Stabilizers.

The meta-stable active layer morphology of organic solar cells (OSCs) is identified as the main cause of the rapid burn-in loss of power conversion efficiency (PCE) during long-term device operation. However, effective strategies to eliminate the associated loss mechanisms from the initial stage of device operation are still lacking, especially for high-efficiency material systems. Herein, the introduction of molecularly engineered dimer acceptors with adjustable thermal transition properties into the active layer of OSCs to serve as supramolecular stabilizers for regulating the thermal transitions and optimizing the crystallization of the absorber composites is reported. By establishing intimate π-π interactions with small-molecule acceptors, these stabilizers can effectively reduce the trap-state density (Nt) in the devices to achieve excellent PCEs over 19%. More importantly, the low Nt associated with an initially optimized morphology can be maintained under external stresses to significantly reduce the PCE burn-in loss in devices. This research reveals a judicious approach to improving OPV stability by establishing a comprehensive correlation between material properties, active-layer morphology, and device performance, for developing burn-in-free OSCs.

Electro-Optically Configurable Synaptic Transistors With Cluster-Induced Photoactive Dielectric Layer for Visual Simulation and Biomotor Stimuli.

The integration of visual simulation and biorehabilitation devices promises great applications for sustainable electronics, on-demand integration and neuroscience. However, achieving a multifunctional synergistic biomimetic system with tunable optoelectronic properties at the individual device level remains a challenge. Here, an electro-optically configurable transistor employing conjugated-polymer as semiconductor layer and an insulating polymer (poly(1,8-octanediol-co-citrate) (POC)) with clusterization-triggered photoactive properties as dielectric layer is shown. These devices realize adeptly transition from electrical to optical synapses, featuring multiwavelength and multilevel optical synaptic memory properties exceeding 3 bits. Utilizing enhanced optical memory, the images learning and memory function for visual simulation are achieved. Benefiting from rapid electrical response akin to biological muscle activation, increased actuation occurs under increased stimulus frequency of gate voltage. Additionally, the transistor on POC substrate can be effectively degraded in NaOH solution due to degradation of POC. Pioneeringly, the electro-optically configurability stems from light absorption and photoluminescence of the aggregation cluster in POC layer after 200 °C annealing. The enhancement of optical synaptic plasticity and integration of motion-activation functions within a single device opens new avenues at the intersection of optoelectronics, synaptic computing, and bioengineering.