All-organic stretchable broadband light self-adaptive-synaptic transistor based on donor-receptor-elastomer ternary hybrid reticular self-assembled photosensitive active layer and preparation method of all-organic stretchable broadband light self-adaptive-synaptic transistor

Abstract

The invention provides an all-organic stretchable broadband light self-adaption-synapse transistor based on a donor-receptor-elastomer ternary hybrid net-shaped self-assembly photosensitive active layer and a preparation method of the all-organic stretchable broadband light self-adaption-synapse transistor. The all-organic stretchable phototransistor is constructed by an all-organic stretchable phototransistor with a bottom gate top contact structure, and a hybrid photosensitive active layer is optimized through the blending proportion, the pre-aggregation form and the self-assembly morphology of related polymers. The full-organic stretchable broadband light self-adaption-synaptic transistor prepared by the invention has excellent field effect characteristics, broadband photoelectric response performance and high tensile strain capacity; and meanwhile, the device has a synaptic behavior simulation function and an adjustable bionic visual self-adaptive function. According to the invention, the blank of an all-organic system in the construction of a stretchable adaptive transistor device is filled, the application prospect of a nerve-like device is widened, and a feasible strategy is provided for the fields of wearable photoelectric devices, eye prostheses, cranial nerve-like calculation, bionic visual networks and the like in the future.

Description

Technical Field

[0001] This invention belongs to the field of wearable and skin-like optoelectronic device technology, specifically relating to a method for regulating the self-assembly of a donor-receptor-elastomer ternary hybrid photosensitive active film. It mainly involves the preparation of a ternary hybrid photosensitive active layer with a mesh-like morphology, and the fabrication method of an all-organic stretchable broadband photoadaptive-synaptic transistor based on the photosensitive active layer. Ultimately, it realizes excellent neuro-like optoelectronic functions, including photodetection, photoadaptation, and photosynapsis. Background Technology

[0002] With the rapid development of biomimetic intelligence, human-computer interaction, and the Internet of Things, intrinsically stretchable neuromorphic optoelectronics, characterized by wearability, efficient neural computing, and multifunctional simulation, has become a promising emerging field attracting significant attention from both academia and industry. ((a) Yang, X. et al.) Nat. Mater. 2019, 18, 510-517; (b) Wang, W., et al. Nat Electron . 2021, 4, 143-50;(c) Zhong, D. et al. Nature (2024, 627, 313–320.) Organically stretchable neuromorphic devices based on phototransistors possess high efficiency in recognition, memory, computation, and low crosstalk, thus enabling optical event-driven operation and multi-task parallel processing. They exhibit unique advantages in the simulation and development of visual neural systems, such as neural network learning and environmental adaptation. However, constructing intrinsically stretchable optically adaptive devices still faces significant challenges, such as the development and design of stretchable photosensitive materials and the structural simplification of stretchable phototransistors. (Wang, C. et al.) Wearable Electronics. 2024, 1, 41-52.) Photosensitive organic semiconductor materials are key to the development of stretchable optoelectronic devices. Currently, common high-performance photosensitive layers mainly rely on inorganic materials such as perovskite, molybdenum disulfide, and lead sulfide. These materials typically suffer from high brittleness, low stability, rough interfaces, and complex fabrication processes. Organic semiconductor materials, on the other hand, possess advantages such as intrinsic flexibility and biocompatibility, and their molecular structure can be tuned to achieve precise sensing and conversion of photoelectric signals under highly flexural conditions. However, designing stretchable photosensitive materials with wide response, high stability, and durability, and introducing defect states without affecting photosensitivity to construct neuromorphic functions, remains a pressing challenge. Furthermore, complex device structures also hinder the development of highly integrated, large-area uniform, and high-quality neural network circuits. ((a)Liao, F. et al.) Nat. Electron.2022,5, 84–91; (b) He, Z. et al. Nat. Electron. (2021, 4, 522–529.) Therefore, the development of high-performance neuromorphic photosensitive materials, simplified device structures, and multifunctional integration technologies is of great research significance for further broadening the application of functionalized electronic skin in next-generation neuromorphic computing, artificial vision, and neuroprosthetics. Summary of the Invention

[0003] In view of the shortcomings of the existing research, one object of the present invention is to prepare an all-organic thin film donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer with intrinsic stretchability, easy integration, high photosensitivity, high carrier mobility and controllable defects by controlling the blending ratio of donor-acceptor polymer and polar elastomer polymer, pre-aggregation morphology and thin film network self-assembly morphology.

[0004] Another objective of this invention is to provide an all-organic stretchable broadband photoadaptive-synaptic transistor based on a donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer and its fabrication method. This transistor exhibits high mobility (>0.2 cm⁻¹). 2 V -1 s -1 High light-to-dark current ratio (>10) 4 High tensile strain (>100%), excellent synaptic behavior simulation (double-pulse facilitated behavior, short-range plasticity (STM), long-range plasticity (LTM), and biomimetic visual adaptive function with a wide wavelength range (ultraviolet, visible and near-infrared light) (light intensity and grating voltage dependent light and dark adaptation).

[0005] The all-organic stretchable broadband optical adaptive-synaptic transistor provided by this invention has a bottom-gate top-contact structure. Its structure, from bottom to top, includes: a stretchable substrate, a stretchable composite gate electrode, a stretchable hybrid dielectric layer, a stretchable polymer donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer, and a stretchable source electrode and a stretchable drain electrode on the same plane. The stretchable source / drain electrode covers the stretchable polymer donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer.

[0006] The optical adaptive range of the all-organic stretchable broadband optical adaptive-synaptic transistor includes visible light and near-infrared light.

[0007] In the all-organic stretchable broadband optical adaptive-synaptic transistor, the stretchable composite gate electrode is prepared by combining poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT:PSS) and carbon nanotube or silver nanowire materials; wherein the stretchable composite gate electrode is composed of a poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT:PSS) layer and a carbon nanotube or silver nanowire material layer, wherein the thickness of the poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT:PSS) layer is 50-100 nm; the thickness of the carbon nanotube or silver nanowire material layer can be 50-100 nm. The stretchable source electrode and the stretchable drain electrode are made of carbon nanotube material or silver nanowire material; The poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT:PSS) is designated as PH 1000. The carbon nanotube material is a single-walled carbon nanotube, including any one of the following types: P2-SWNT, P3-SWNT, P5-SWNT, P8-SWNT, and P9-SWNT. The silver nanowire material is any one of GS-SNW-20, GS-SNW-25, GS-SNW-30 and GS-SNW-40; In the all-organic stretchable broadband optical adaptive-synaptic transistor, the stretchable hybrid dielectric layer is made of a blend of elastomeric polymer and carbon quantum dots; The elastomer polymer is selected from any one of polydimethylsiloxane (PDMS), hydrogenated styrene-butadiene block copolymer (SEBS), polyurethane elastomer (PU), styrene-butadiene rubber (SBS), and natural rubber (NR). The carbon quantum dots are characterized by being uncharged, having high dielectric properties, and having a narrow particle size of 1-5 nm. The mass ratio of the elastomer polymer and carbon quantum dots can be 100:0.5 to 100:10, specifically 100:1.5 to 100:5, and more specifically 100:3.5 or 100:5. The thickness of the stretchable hybrid dielectric layer can be 1300-2500 nm, specifically 1600-1900 nm.

[0008] In the all-organic stretchable broadband optical adaptive-synaptic transistor, the stretchable polymer donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer is prepared based on a ternary hybrid system of elastomer polymer and conjugated polymer donor and acceptor materials, and the blending ratio, pre-aggregation morphology and network self-assembly morphology of the three polymers of donor, acceptor and elastomer are controlled. The elastomer polymer is polyurethane elastomer (PU). The donor conjugated polymer is any one of poly(2,5-bis(2-octyldodecyl)-3,6-bis(thiophen-2-yl)dionepyrrole[3,4-c]pyrrole-1,4-dione-alt-thiophene[3,2-b]thiophene) (DPPT-TT), poly(2,5-bis(3-alkylthiophen-2-yl)thiophene[3,2-b]thiophene) (PBTTT), poly(tetrathiopheneacetic acid dionepyrrole) (PTDPPTFT4), polyisoindigodithiophene (PII2T), and poly(3-hexylthiophene) (P3HT); The acceptor conjugated polymers are poly(2,7-bis(2-octyldodecyl)benzo[LMN][3,8]o-diazaphenanthroline-1,3,6,8(2H,7H)-tetraone-4,9-diyl)([2,2']dithienyl-5,5'-diyl) (N2200), poly[(2,2'-((2Z,2'Z)-((12,13-bis(2-octyldodecyl)-3,9-dicepyl-12,13-dihydro[1,2,5]thiadiazo[3,4e]thieno[2”, 3”: [4',5']thieno[2,3':4,5]thieno[3,2-b]-indole-2,10-diyl)bis(methylethylidene))bis(3-oxo-2,3-dihydro-1H-indene-2,1-diethylene))diamonic acid-alt-2,5-thiophene)] (PYT) and peryleneimide-bithiophene (PDI-2T); The mass ratio of the donor conjugated polymer to the acceptor conjugated polymer can be 0.8:1.2 to 1.2:0.8, specifically 1:1; The mass ratio of the donor-acceptor conjugated polymer to the elastomer polymer can be 1:9 to 9:1, specifically 3:7 to 7:3; The thickness of the stretchable polymer donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer can be 30-100 nm, specifically 50-70 nm.

[0009] The network self-assembly morphology is achieved by controlling the blending ratio and pre-aggregation morphology of the three polymers: donor, acceptor, and elastomer. In the all-organic stretchable broadband optical adaptive-synaptic transistor, the stretchable substrate is made of any of the elastomeric polymers used in the stretchable hybrid dielectric layer; The thickness of the stretchable substrate can be 100 µm to 2 mm, specifically 0.6-1 mm.

[0010] The method for fabricating the above-mentioned all-organic stretchable broadband optical adaptive-synaptic transistor provided by the present invention includes the following steps: (1) The stretchable substrate, the stretchable composite gate electrode, the stretchable hybrid dielectric layer, the stretchable polymer donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer, the stretchable source electrode and the stretchable drain electrode are respectively fabricated on a substrate with a self-assembled molecular layer. (2) Use tweezers to transfer the stretchable substrate from the substrate with the self-assembled molecular layer, and then cover the stretchable composite gate electrode from one side; transfer the stretchable composite gate electrode to the stretchable substrate by thermal bonding-transfer method; then use the same method and steps to sequentially transfer the stretchable hybrid dielectric layer, the stretchable polymer donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer, and the stretchable source electrode and the stretchable drain electrode located on the same plane from the self-assembled monolayer substrate or the substrate with the elastomer film to the stretchable composite gate electrode, so as to obtain the all-organic stretchable broadband photoadaptive-synaptic transistor based on the stretchable polymer ternary hybrid network self-assembled photosensitive active layer.

[0011] In step 1) of the above method, the substrate is selected from any one of silicon wafers, glass, ceramics and quartz; The substrate is ultrasonically cleaned sequentially with detergent, deionized water, acetone and ethanol, dried with a nitrogen gun, and then subjected to vacuum oxygen plasma treatment to obtain a clean substrate. The conditions for ultrasonic cleaning are: ultrasonic power of 10-100 watts, ultrasonic time of 1-30 minutes, and ultrasonic frequency of 10-100 kilohertz. The conditions for the vacuum oxygen plasma treatment are: treatment time of 1-30 minutes.

[0012] The substrate with the self-assembled molecular layer is prepared by heating or immersing the clean substrate in a solution under vacuum conditions with any one of octadecyltrimethoxysilane, octadecyltrichlorosilane, octadecyltrichlorosilane, and phenyltrichlorosilane. The conditions for the vacuum heating treatment are: vacuum degree of 0.1 Pascal, heating temperature of 50~150°C, and heating time of 1~5 hours. The conditions for immersion treatment in the solution are as follows: any one of n-hexane, n-heptane, isohexane, and cyclohexane is used as the solvent; the volume ratio of the octadecyltrimethoxysilane, octadecyltrichlorosilane, octadecyltrichlorosilane, or phenyltrichlorosilane to the n-hexane, n-heptane, isohexane, or cyclohexane is 1:200-1:1000, and the immersion time is 0.1-3 hours.

[0013] In step 2) of the above method, the stretchable substrate, the stretchable hybrid dielectric layer, and the stretchable polymer donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer are all prepared by solution deposition. The solution deposition method is any one of drop coating, spin coating, blade coating, roller coating, brush coating, and stretch coating; The solvent used in the solution deposition method is any one of toluene, xylene, chlorobenzene, dichlorobenzene, methane, chloroform, dichloromethane, n-hexane, or cyclohexane; The solution concentration of the stretchable substrate is 100-300 mg / mL; The solution concentration of the stretchable hybrid dielectric layer is 50-100 mg / mL; The solution concentration of the stretchable polymer donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer is 5-20 mg / mL, specifically 10 mg / mL.

[0014] In the above preparation steps, the poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT:PSS) layer of the stretchable composite gate electrode is prepared by solution deposition. The thickness of the poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT:PSS) layer in the stretchable composite gate electrode is 50-100 nm. The carbon nanotube layer or silver nanowire layer of the stretchable source electrode, the stretchable drain electrode, and the stretchable composite gate electrode are all prepared by spraying. The solvent used is any one of water, ethanol, isopropanol, or a mixture thereof; The spraying conditions are as follows: substrate temperature is 60-120 °C, distance between spray gun nozzle and substrate is 5-12 cm, spraying rate is 0.3-3 mL / min, and spraying volume is 1-3 mL.

[0015] To ensure the high resolution of the stretchable composite gate electrode, the stretchable source electrode, and the stretchable drain electrode, a substrate with a self-assembled molecular layer is placed between a strong magnet and a patterned nickel or iron mask. The heat bonding process is carried out in a vacuum drying oven; The conditions for heat bonding are: vacuum degree of 0.1~3 Pascals, temperature of 30~80 °C, and heat treatment time of 0.1~1 hour.

[0016] The application of the aforementioned all-organic stretchable broadband optical adaptive-synaptic transistor in the fabrication of neural-like devices also falls within the scope of protection of this invention.

[0017] The all-organic stretchable broadband optical adaptive-synaptic transistor can be used in future wearable optoelectronic devices, prosthetic eyes and limbs, brain-like neural computing, and bionic visual networks.

[0018] The beneficial effects of this invention are as follows: This invention discloses an all-organic stretchable broadband photoadaptive-synaptic transistor based on a donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer and its fabrication method. It is constructed from an all-organic stretchable phototransistor with a bottom-gate top-contact structure, and a stretchable polymer ternary hybrid photosensitive active layer is obtained by controlling the blending ratio of the donor and acceptor polymers and the elastomer polymer, the pre-aggregation morphology, and the network self-assembly morphology. The all-organic stretchable broadband photoadaptive-synaptic transistor fabricated by this invention exhibits excellent field-effect characteristics, superior broadband photoelectric response performance, and high tensile strain capability; it also possesses excellent synaptic behavior simulation capabilities and tunable biomimetic visual adaptive functions. This invention simplifies the complex structure of current neural-like devices by introducing controllable defects into the photosensitive heterojunction active layer, fills the gap in the construction of stretchable adaptive transistor devices using all-organic systems, broadens the application prospects of all-organic stretchable neural-like devices, and provides a practical strategy for future wearable optoelectronic devices, prosthetic eyes and limbs, brain-like neural computing, and biomimetic visual networks. Attached Figure Description

[0019] Figure 1 This is a schematic diagram of the structure of the all-organic stretchable broadband photoadaptive-synaptic transistor based on a donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer of the present invention.

[0020] Figure 2 Atomic force microscopy (AFM) images of the donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer thin film prepared in Example 1 of this invention, and AFM images of the thin films prepared in Examples 2 and 3, and Comparative Example 1, respectively, showing the hybridization ratio, pre-aggregation morphology, and lack of elastomer modulation. Figure 2 Image a in Example 1 is an atomic force microscope image. Figure 2 Image b in Example 2 is an atomic force microscope image; Figure 2 c is an atomic force microscope image of Example 3; Figure 2 In the middle, d is an atomic force microscope image of Comparative Example 1.

[0021] Figure 3 The UV-Vis absorption spectra of the donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer film prepared in Example 1 of the present invention and the donor-acceptor binary hybrid photosensitive active layer film of Comparative Example 1 are shown.

[0022] Figure 4The graphs show the characteristic transfer curves of the all-organic stretchable broadband optically adaptive synaptic transistors prepared in Examples 1, 2, and 3 of this invention under strong light illumination at a wavelength of 808 nm. Figure 4 In the figure, 'a' represents the characteristic transfer curve of Example 1; Figure 4 In Figure b, the characteristic transfer curve of Example 2 is shown. Figure 4 c represents the characteristic transfer curve of Example 3; Figure 4 In the figure, d is the characteristic transfer curve of Comparative Example 1; the left axis of both a and b is the relationship between the source-drain current and the gate voltage.

[0023] Figure 5 The curves show the time-current comparison of single-pulse light under 808 nm illumination for the all-organic stretchable broadband optical adaptive-synaptic transistors prepared in Examples 1, 2, 3 and Comparative Example 1 of this invention.

[0024] Figure 6 The diagram shows the visual biomimetic adaptive characteristics of the all-organic stretchable broadband optical adaptive-synaptic transistor prepared in Example 1 of this invention under different light intensities and different gate voltages.

[0025] Figure 7 The diagram shows the visual biomimetic adaptive characteristics of the all-organic stretchable broadband optical adaptive-synaptic transistor prepared in Example 1 of the present invention under different stretching states.

[0026] Figure 8 The diagram shows the biomimetic synaptic characteristics of the all-organic stretchable broadband optical adaptive-synaptic transistor prepared in Example 1 of this invention under 10 pulses of light with 0.5s illumination and 0.5 intervals.

[0027] Figure 9 The adaptive hotspot diagrams of the all-organic stretchable broadband optical adaptive-synaptic transistor array prepared in Example 1 of the present invention at different time intervals under 808 nm illumination. Detailed Implementation

[0028] The present invention will now be described in further detail with reference to specific embodiments. The given embodiments are merely illustrative of the invention and not intended to limit its scope. The embodiments provided below can serve as a guide for further improvements by those skilled in the art and do not constitute a limitation on the invention in any way.

[0029] Unless otherwise specified, the experimental methods used in the following examples are conventional methods, performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Unless otherwise specified, the materials and reagents used in the following examples are commercially available.

[0030] Example 1 This embodiment fabricates an all-organic stretchable broadband photoadaptive-synaptic transistor based on a donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer according to the following steps: 1) Using silicon wafers as substrates, patterned silicon wafers of different sizes were sequentially ultrasonicated with detergent, deionized water, acetone and ethanol at a power of 40 W and a frequency of 30 kHz for 10 min. After drying with a nitrogen gun, the cleaned silicon wafers were subjected to vacuum oxygen plasma treatment (power of 60 Hz) for 5 min. Then, the cleaned silicon wafers were placed in the same petri dish with 1 µL of octadecyltrimethoxysilane. The petri dish was placed in a vacuum drying oven at a vacuum degree of 0.1 Pa and a temperature of 120 °C for 3 h. After the vacuum drying oven cooled to room temperature, the petri dish was removed to obtain silicon wafers with self-assembled molecular layers.

[0031] 2) Place the silicon wafer with the self-assembled molecular layer on a hot plate, and slowly draw 0.5 ml of SEBS toluene solution (concentration of 150 mg / mL) with a 1 mL syringe and uniformly drop it onto the silicon wafer with the self-assembled molecular layer. Then keep it at 40 °C for 2 hours and then at 90 °C for 1 hour to obtain a stretchable substrate with a thickness of 1 mm.

[0032] 3) Place the patterned silicon wafer with the self-assembled molecular layer prepared in step 1) at the center of the spin coater rotor. Use a 100 µL pipette to draw 100 µL of poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid and then uniformly drop it onto the silicon wafer. Start the spin coater and maintain a speed of 5000 rad / min for 1 min. Finally, remove the silicon wafer and place it on a hot stage at 150 °C for 30 minutes to obtain the poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid layer of the composite gate electrode with a thickness of 100 nm.

[0033] 4) Place the patterned silicon wafer with the poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid layer prepared in step 3) on a magnet, and then place the patterned nickel mask on the silicon wafer, so that the mask is tightly attached to the silicon wafer with the self-assembled molecular layer. Gently place the magnet, silicon wafer and mask on a hot stage at 60 °C for 5 minutes. Use a 2 mL pipette to transfer 1.5 mL of carbon nanotube P3-SWNT isopropanol solution (0.2 mg / mL) into the volume chamber of the spray gun, and then uniformly spray it on the patterned silicon wafer with the poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid layer at a rate of 0.15 mL / min (wherein, the distance between the spray gun nozzle and the silicon wafer is 8 cm), and a patterned stretchable composite gate electrode can be obtained, wherein the carbon nanotube layer thickness is 100 nm.

[0034] 5) Place the silicon wafer with the self-assembled molecular layer prepared in step 1) at the center of the spin coater rotor. Use a 1 mL pipette to draw 200 µL of a mixed solution of SEBS and carbon quantum dots (solvent is toluene, mass ratio of SEBS to carbon quantum dots is 100:3.5, concentration of mixed solution is 100 mg / mL), and then uniformly drop it onto the silicon wafer with the self-assembled molecular layer. Start the spin coater and maintain a speed of 1000 rad / min for 1 min. Finally, remove the silicon wafer and anneal it on a hot plate at 80 °C for 30 min to obtain a stretchable hybrid dielectric layer with a thickness of 1800 nm.

[0035] 6) Place the silicon wafer with the self-assembled molecular layer prepared in step 1) at the center of the spin coater rotor. Use a 50 µL pipette to draw 30 µL of a chlorobenzene solution of poly(2,5-bis(2-octyldodecyl)-3,6-di(thiophene-2-yl)dionepyrrolo[3,4-c]pyrrolo-1,4-dione-3-thiopheno[3,2-b]thiophene) / poly(2,7-bis(2-octyldodecyl)benzo[LMN][3,8]o-diazaphenanthroline-1,3,6,8(2H,7H)-tetraone-4,9-diyl)([2,2']dithiophene-5,5'-diyl) / polyurethane elastomer (wherein, the mass ratio of donor to acceptor conjugated polymer is 1:1, the mass ratio of donor to acceptor conjugated polymer to elastomer polymer is 3:7, and the concentration of the ternary blend solution is 10 (mg / mL), then uniformly drop it onto the silicon wafer, start the spin coater, and maintain a speed of 3000 rad / min for 1 min. Finally, remove the silicon wafer and place it on a hot stage at 150 °C for 30 minutes to obtain a 50 nm thick photosensitive active layer based on a donor-acceptor-elastomer ternary hybrid network self-assembly.

[0036] 7) Place the silicon wafer with the self-assembled molecular layer prepared in step 1) on a magnet, and then place the patterned nickel mask on the silicon wafer to tightly attach the mask to the silicon wafer with the self-assembled molecular layer. Gently place the magnet, silicon wafer and mask on a hot stage at 110 °C for 15 minutes. Then, use a 2 mL pipette to draw 1.5 mL of isopropanol solution of carbon nanotube P3-SWNT (concentration of 0.15 mg / mL) and spray it uniformly onto the silicon wafer with the self-assembled molecular layer at a rate of 0.1 mL / min (wherein the distance between the nozzle of the spray gun and the silicon wafer is 9 cm). This will give you the patterned stretchable source electrode and stretchable drain electrode (channel length and channel width are 200 µm and 4000 µm, respectively).

[0037] 8) Gently peel the stretchable substrate off the substrate with the self-assembled molecular layer using pointed tweezers. Then, gently cover the stretchable composite gate electrode from one side with the stretchable substrate and place it in a vacuum drying oven with a vacuum degree of 0.1 Pascals at 60 °C for 20 min. After the temperature drops to room temperature, gently transfer the stretchable substrate off with pointed tweezers. Through this process, the stretchable composite gate electrode can be transferred onto the stretchable substrate. Then, using the same method and steps, sequentially transfer the stretchable hybrid dielectric layer, the donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer, and the stretchable source electrode and the stretchable drain electrode located on the same plane onto the stretchable composite gate electrode. This yields an all-organic stretchable broadband photoadaptive-synaptic transistor based on a donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer, with the structure as shown below. Figure 1 As shown.

[0038] Example 2 The preparation method was exactly the same as in Example 1, except that the donor-acceptor-elastomer ternary hybrid semiconductor solution (solvent: chlorobenzene, donor-acceptor conjugated polymer mass ratio: 1:1, donor-acceptor conjugated polymer and elastomer polymer mass ratio: 3:7, ternary blend solution concentration: 10 mg / mL) in step 6) was changed to a donor-acceptor-elastomer ternary hybrid semiconductor solution (solvent: chlorobenzene, donor and acceptor conjugated polymer mass ratio: 1:1, donor, acceptor conjugated polymer and elastomer polymer mass ratio: 7:3, ternary blend solution concentration: 10 mg / mL). The thickness of the ternary hybrid polymer semiconductor prepared in Example 2 was the same as that of the donor-acceptor-elastomer ternary hybrid photosensitive active layer prepared in Example 1, which was approximately 50 nm.

[0039] Example 3 The preparation method was exactly the same as in Example 1, except that the donor-acceptor-elastomer ternary hybrid semiconductor solution (solvent: chlorobenzene, donor-acceptor conjugated polymer mass ratio: 1:1, donor-acceptor conjugated polymer and elastomer polymer mass ratio: 3:7, ternary blend solution concentration: 10 mg / mL) in step 6) was changed to a donor-acceptor-elastomer ternary hybrid semiconductor solution (solvent: toluene, donor and acceptor conjugated polymer mass ratio: 1:1, donor, acceptor conjugated polymer and elastomer polymer mass ratio: 3:7, ternary blend solution concentration: 10 mg / mL). The thickness of the ternary hybrid polymer semiconductor prepared in Example 3 was the same as that of the donor-acceptor-elastomer ternary hybrid photosensitive active layer prepared in Example 1, which was approximately 50 nm.

[0040] Comparative Example 1 The preparation method was exactly the same as in Example 1, except that the donor-acceptor-elastomer ternary hybrid semiconductor solution (solvent: chlorobenzene, donor-acceptor conjugated polymer mass ratio: 1:1, donor-acceptor conjugated polymer and elastomer polymer mass ratio: 3:7, ternary blend solution concentration: 10 mg / mL) in step 6) was replaced with a donor-acceptor binary hybrid semiconductor solution (solvent: chlorobenzene, donor-acceptor conjugated polymer mass ratio: 1:1, no elastomer polymer added, binary blend solution concentration: 10 mg / mL). The thickness of the binary hybrid polymer semiconductor prepared in Comparative Example 1 was the same as that of the donor-acceptor-elastomer ternary hybrid photosensitive active layer prepared in Example 1, which was approximately 50 nm.

[0041] Figure 1 This is a schematic diagram of the structure of the all-organic stretchable broadband photoadaptive-synaptic transistor based on a donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer of the present invention. Figure 1 Compared with traditional optical adaptive-synaptic transistors, the structure shown integrates a semiconductor layer, a photosensitive layer, and a defect introduction layer into one unit, simplifying the device structure.

[0042] Figure 2 The images shown are atomic force microscope (AFM) images of the donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer prepared in Example 1 of this invention, and AFM images of Examples 2, 3, and Comparative Example 1 prepared with varying hybridization ratios, pre-aggregated morphologies, and no elastomer modulation, respectively. Figure 2 It can be seen that by controlling the hybridization conditions of the donor-acceptor-elastomer ternary hybrid semiconductor solution, the morphology of the hybrid photosensitive active layer film changes from the original smooth morphology (Comparative Example 1) to a network morphology (Example 1) after the addition of polar elastomer polyurethane. The addition of elastomer also helps the contact and carrier transport between the layers of the stretchable device. Secondly, by controlling the hybridization ratio and pre-aggregation morphology, the surface roughness of the film in Example 1 is increased within the allowable range compared with Examples 2 and 3, and the network morphology tends to be more obvious. Without affecting the carrier transport and photoelectric performance, defects are introduced, laying the foundation for the subsequent construction of neural-like functions of the device.

[0043] Figure 3 The images show the UV-Vis absorption spectra of the donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer film prepared in Example 1 of this invention and the donor-acceptor binary hybrid photosensitive active layer film in Comparative Example 1. The main absorption peaks of both films are located at 405 nm and 810 nm, and their absorption ranges are almost identical. This indicates that the introduction of the polyurethane elastomer does not disrupt the light absorption of the donor and acceptor, ensuring a wide-band response for subsequent devices.

[0044] Figure 4The graphs show the characteristic transfer curves of the all-organic stretchable broadband optically adaptive synaptic transistors prepared in Examples 1, 2, and 3 of this invention and Comparative Example 1 under dark conditions and 808 nm strong light. Figure 4 In the figure, 'a' represents the characteristic transfer curve of Example 1; Figure 4 In Figure b, the characteristic transfer curve of Example 2 is shown. Figure 4 c represents the characteristic transfer curve of Example 3; Figure 4 In the figure, d represents the characteristic transfer curve of Comparative Example 1. (From...) Figure 4 It can be seen that Example 1 has the best photoresponse capability. Specifically, compared with Example 2, the increase in the mass ratio of donor-acceptor conjugated polymer and elastomer polymer increased the off-state current of the device; compared with Example 3, the relatively low polarity of toluene solvent affected the pre-aggregation morphology of the ternary blend solution, which was reflected in the weakening of the device's photoresponse capability; compared with Comparative Example 1, the introduction of elastomer effectively reduced the off-state current of the device, thereby improving the photoresponse capability.

[0045] Figure 5 The figures show the single-pulse time-current comparison curves of the all-organic stretchable broadband photoadaptive-synaptic transistors prepared in Examples 1, 2, and 3 of this invention and Comparative Example 1 under 808 nm illumination. Compared to Comparative Example 1, the all-organic stretchable broadband photoadaptive-synaptic transistors prepared in Examples 1, 2, and 3 exhibit significant adaptive behavior under illumination after the addition of polyurethane to the photosensitive layer, based on the ternary hybrid network self-assembled morphology. Furthermore, by comparing the adaptive behavior of Example 1 with Examples 2 and 3, it can be demonstrated that different adaptive effects can be obtained by controlling the hybridization ratio and pre-aggregation morphology of the donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer film.

[0046] Figure 6 This diagram illustrates the visual biomimetic adaptive characteristics of the all-organic stretchable broadband photoadaptive-synaptic transistor prepared in Example 1 of this invention under different light intensities and gate voltages. It demonstrates that the all-organic stretchable broadband photoadaptive-synaptic transistor based on a donor-acceptor-elastomer ternary hybrid mesh self-assembled photosensitive active layer can achieve different adaptive capabilities to different light intensities (the stronger the light, the greater the photocurrent attenuation ratio and the faster the photocurrent attenuation rate), and possesses gate voltage-dependent tunable adaptive performance (the photocurrent attenuation ratio has a large tunable range under a positive operating voltage, and the photocurrent attenuation rate is fast under a negative operating voltage).

[0047] Figure 7 This image shows the visual biomimetic adaptive characteristics of the all-organic stretchable broadband optical adaptive-synaptic transistor fabricated in Example 1 of this invention under different stretching states. The device exhibits stable adaptive characteristics under different stretching states, demonstrating its excellent stretching capability and great potential in wearable applications.

[0048] Figure 8 This image shows the biomimetic synaptic characteristics of the all-organic stretchable broadband optically adaptive synaptic transistor prepared in Example 1 of this invention under 10 pulses of light with a 0.5s illumination and a 0.5s interval. The synaptic characteristics that decay under repeated stimulation hold promise for playing a role in neural network learning.

[0049] Figure 9 This is an adaptive hotspot diagram of the all-organic stretchable broadband optical adaptive-synaptic transistor array prepared in Example 1 of the present invention under 808 nm illumination at different time intervals. Under extremely strong illumination, the array can attenuate the photocurrent to a current value similar to that under normal illumination conditions in a very short time, exhibiting excellent adaptive performance.

[0050] These experimental results demonstrate that the all-organic stretchable broadband photoadaptive-synaptic transistors fabricated based on the donor-acceptor-elastomer ternary hybrid photosensitive active film with a mesh morphology can achieve excellent neuromorphic optoelectronic functions, including photodetection, photoadaptation, and photosynapsis. Specifically, it not only achieves high photoresponse but also exhibits high resistance to mechanical deformation and excellent synaptic simulation, biomimetic visual adaptive functions, and imaging effects. This self-assembly control method and device fabrication strategy introduces controllable defects into the photosensitive heterojunction active layer, simplifying the complex structure of current neuromorphic devices, filling the gap in the construction of stretchable adaptive transistor devices in all-organic systems, broadening the application prospects of all-organic stretchable neuromorphic devices, and providing a feasible strategy for future wearable optoelectronic devices, prosthetic eyes and limbs, brain-like neural computing, and biomimetic visual networks.

[0051] The present invention has been described in detail above. Those skilled in the art will recognize that the invention can be practiced in a wide range of ways with equivalent parameters, concentrations, and conditions without departing from its spirit and scope, and without requiring unnecessary experiments. While specific embodiments have been provided, it should be understood that further modifications can be made to the invention. In summary, according to the principles of the invention, this application is intended to include any changes, uses, or improvements to the invention, including changes made using conventional techniques known in the art that depart from the scope disclosed herein.

Claims

1. An all-organic stretchable broadband optical adaptive-synaptic transistor, having a bottom-gate top-contact structure, comprising, from bottom to top: The device comprises a stretchable substrate, a stretchable composite gate electrode, a stretchable hybrid dielectric layer, a stretchable polymer donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer, and a stretchable source electrode and a stretchable drain electrode on the same plane, wherein the stretchable source / drain electrode covers the stretchable polymer donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer.

2. The all-organic stretchable broadband optical adaptive-synaptic transistor according to claim 1, characterized in that, The optical adaptive range of the all-organic stretchable broadband optical adaptive-synaptic transistor includes visible light and near-infrared light.

3. The all-organic stretchable broadband optical adaptive-synaptic transistor according to claim 1 or 2, characterized in that, In the all-organic stretchable broadband optical adaptive-synaptic transistor, the stretchable composite gate electrode is composed of a poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid layer (PEDOT:PSS) and a carbon nanotube or silver nanowire material layer, wherein the thickness of the poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid layer (PEDOT:PSS) is 50-100 nm; and the thickness of the carbon nanotube or silver nanowire material layer is 50-100 nm.

4. The all-organic stretchable broadband optical adaptive-synaptic transistor according to claim 1 or 2, characterized in that, In the all-organic stretchable broadband optical adaptive-synaptic transistor, the stretchable hybrid dielectric layer is made of a blend of elastomeric polymer and carbon quantum dots; The elastomeric polymer is selected from any one of polydimethylsiloxane, hydrogenated styrene-butadiene block copolymer, polyurethane elastomer, styrene-butadiene rubber, and natural rubber. The carbon quantum dots are characterized by being uncharged, having high dielectric properties, and having a narrow particle size of 1-5 nm. The mass ratio of the elastomer polymer to carbon quantum dots is 100:0.5 to 100:10; The thickness of the stretchable hybrid dielectric layer is 1300-2500 nm.

5. The all-organic stretchable broadband optical adaptive-synaptic transistor according to claim 1 or 2, characterized in that, In the all-organic stretchable broadband optical adaptive-synaptic transistor, the stretchable polymer donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer is prepared based on a ternary hybrid system of elastomer polymer and conjugated polymer donor and acceptor materials, and the blending ratio, pre-aggregation morphology and network self-assembly morphology of the three polymers of donor, acceptor and elastomer are controlled.

6. The all-organic stretchable broadband optical adaptive-synaptic transistor according to claim 5, characterized in that, The elastomer polymer is a polyurethane elastomer; The donor conjugated polymer is any one of poly(2,5-bis(2-octyldodecyl)-3,6-bis(thiophen-2-yl)dionepyrrole[3,4-c]pyrrole-1,4-dione-alt-thiophene[3,2-b]thiophene), poly(2,5-bis(3-alkylthiophen-2-yl)thiophene[3,2-b]thiophene, poly(tetrathiophene acetate dionepyrrole), polyisoindigo dithiophene, and poly(3-hexylthiophene); The acceptor conjugated polymers are poly(2,7-bis(2-octyldodecyl)benzo[LMN][3,8]o-diazaphenanthroline-1,3,6,8(2H,7H)-tetraone-4,9-diyl)([2,2']dithienyl-5,5'-diyl), poly[(2,2'-((2Z,2'Z)-((12,13-bis(2-octyldodecyl)-3,9-decyl-12,13-dihydro[1,2,5]thiadiazo[3,4e]thien[2”, [3”:4',5']thieno[2,3':4,5]thieno[3,2-b]-indole-2,10-diyl)bis(methylethylidene))bis(3-oxo-2,3-dihydro-1H-indene-2,1-diyl))dimalonitrile-alt-2,5-thiophene)] and peryleneimide-bithiophene; The mass ratio of the donor conjugated polymer to the acceptor conjugated polymer is 0.8:1.2 to 1.2:0.8; The mass ratio of the donor-acceptor conjugated polymer to the elastomer polymer is 1:9 to 9:1; The thickness of the stretchable polymer donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer is 30-100 nm.

7. The all-organic stretchable broadband optical adaptive-synaptic transistor according to claim 1 or 2, characterized in that, In the all-organic stretchable broadband optical adaptive-synaptic transistor, the stretchable substrate is made of any of the elastomeric polymers used in the stretchable hybrid dielectric layer; The thickness of the stretchable substrate is 100 µm to 2 mm.

8. A method for fabricating the all-organic stretchable broadband optical adaptive-synaptic transistor according to any one of claims 1-7, comprising the following steps: (1) The stretchable substrate, the stretchable composite gate electrode, the stretchable hybrid dielectric layer, the stretchable polymer donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer, the stretchable source electrode and the stretchable drain electrode are respectively fabricated on a substrate with a self-assembled molecular layer. (2) Use tweezers to transfer the stretchable substrate from the substrate with the self-assembled molecular layer, and then cover the stretchable composite gate electrode from one side; transfer the stretchable composite gate electrode to the stretchable substrate by thermal bonding-transfer method; then use the same method and steps to sequentially transfer the stretchable hybrid dielectric layer, the stretchable polymer donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer, and the stretchable source electrode and the stretchable drain electrode located on the same plane from the self-assembled monolayer substrate or the substrate with the elastomer film to the stretchable composite gate electrode, so as to obtain the all-organic stretchable broadband photoadaptive-synaptic transistor based on the stretchable polymer ternary hybrid network self-assembled photosensitive active layer.

9. The method according to claim 8, characterized in that, In step 2), the stretchable substrate, the stretchable hybrid dielectric layer, and the stretchable polymer donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer are all prepared by solution deposition. The solution deposition method is any one of drop coating, spin coating, blade coating, roller coating, brush coating, and stretch coating; The solution concentration of the stretchable substrate is 100-300 mg / mL; The solution concentration of the stretchable hybrid dielectric layer is 50-100 mg / mL; The solution concentration of the stretchable polymer donor-acceptor-elastomer ternary hybrid network self-assembled photosensitive active layer is 5-20 mg / mL.

10. The application of the all-organic stretchable broadband optical adaptive-synaptic transistor according to any one of claims 1-7 in the fabrication of neural-like devices, including the application of the all-organic stretchable broadband optical adaptive-synaptic transistor in future wearable optoelectronic devices, prosthetic eyes and limbs, brain-like neural computing and bionic visual networks.

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