Stretchable broadband light self-adaption-synaptic transistor based on quasi-continuous hybrid photosensitive layer and preparation method of stretchable broadband light self-adaption-synaptic transistor

Abstract

The invention discloses a stretchable broadband light self-adaption-synaptic transistor based on a quasi-continuous hybrid photosensitive layer and a preparation method of the stretchable broadband light self-adaption-synaptic transistor. The full-stretchable quantum dot / elastomer hybrid light-sensitive sensor is constructed by a full-stretchable transistor with a bottom gate top contact structure and a stretchable quantum dot / elastomer hybrid light-sensitive layer. The stretchable quantum dot / elastomer hybrid photosensitive layer is prepared by regulating and controlling the blending proportion of photosensitive quantum dots and elastomer polymers, the pre-aggregation form and the self-assembly quasi-continuous-microsphere morphology. The intrinsic stretchable broadband light adaptive-synaptic transistor prepared by the invention has excellent field effect characteristics, excellent photoelectric response performance and high tensile strain capacity; meanwhile, the quantum dot has an excellent synaptic behavior simulation function, a broadband bionic visual self-adaption function and an imaging effect, the application prospect of the quantum dot in stretchable device construction is widened, and a feasible strategy is provided for the fields of wearable photoelectric devices, electronic skin, brain-like nerve calculation, bionic visual networks and the like in the future.

Description

Technical Field

[0001] The present invention belongs to the technical field of wearable and skin-like optoelectronic devices, and specifically relates to a method for regulating the self-assembly of a photosensitive quantum dot / elastomer hybrid photosensitive film, mainly to the preparation of a hybrid photosensitive layer with a quasi-continuous-microsphere morphology, and a stretchable wide-band light-adaptive-synaptic transistor constructed based on the quasi-continuous hybrid photosensitive layer and a preparation method thereof, ultimately achieving excellent light-adaptive imaging. Background Art

[0002] Stretchable optoelectronic devices are the main research direction for the development of smart wearable electronic devices, showing extraordinary potential in the fields of electronic skin, medical monitoring, human-computer interaction, etc. Stretchable optoelectronic devices have the characteristics of high conformability, flexibility and optoelectronic stability, and can realize accurate perception, conversion and display of optoelectronic signals under highly flexed conditions ((a) YS Bian, K. Liu, Y. Ran, et al. Nat. Commun 2022, 13, 7163. (b) K. Liu, YS Bian, JH Kuang, Adv. Mater. 2022, 34, 2107. (c) Lee, Y., Liu, Y., Seo, DG. et al. Nat. Biomed. Eng., 2023, 7, 511–519.). The development of smart wearable electronic devices urgently requires the development of high-efficiency, low-power and multifunctional systems, especially flexible electronic devices that integrate perception, computing and storage. Stretchable phototransistors can achieve fast response, high bandwidth and low crosstalk, and show obvious advantages in simulating the development of visual neural systems, including synaptic plasticity, bionic visual adaptation, neural network learning, etc. However, phototransistors that realize intrinsic stretchable adaptation and synaptic integration still face many challenges, such as the development of stretchable photosensitive materials and the construction and integration of stretchable phototransistors (CJ Wang, YH Liu, P. Feng, et al. Advanced Materials. 2016, 28, 5878-5885.).

[0003] Stretchable photosensitive materials are the key to the development of stretchable optoelectronic devices. The high-performance photosensitive layers reported so far mainly rely on inorganic materials such as perovskite, molybdenum disulfide, and lead sulfide. Such materials usually have problems such as high brittleness, low stability, rough interfaces, and complex preparation processes, which make it difficult to achieve flexible integration. Organic optoelectronic materials have unique advantages such as intrinsic flexibility, biocompatibility, and adjustable molecular structure, but their limited photoresponse and wavelength range hinder their further development and application ((a) ZH He, HG Shen, DKYe, et al. Nature Electronics. 2021, 4, 522-529. (b) Liao, F., Zhou, Z., Kim, BJ, et al. Nature Electronics. 2022, 5, 84–91. (c) MY Zhang, ZG Chi, GQ Wang, et al. Advanced Materials. 2022, 2205679). Therefore, the development of stretchable photosensitive materials with wide response, high stability, and durability is an important prerequisite for the construction of intrinsic stretchable optoelectronic devices. In addition, the realization of multifunctional integrated stretchable light-adaptive devices still faces many challenges, especially maintaining the interface and performance stability between the functional layers of the device under high deformation. Therefore, designing effective interface regulation methods and functional integration technologies is of great research significance to further expand the application of functional electronic skin in the field of neuromorphic computing and imaging. Summary of the invention

[0004] In view of the above-mentioned deficiencies in the existing research, one object of the present invention is to prepare a quantum dot / elastomer hybrid photosensitive film with a quasi-continuous-microspherical morphology having intrinsic stretchability, high photosensitivity and easy integration properties by regulating the pre-aggregation morphology of photosensitive quantum dots and elastomeric polymers and the self-assembly morphology of hybrid films.

[0005] Another object of the present invention is to provide a stretchable broadband light-adaptive-synaptic transistor based on a morphology-controllable stretchable quasi-continuous quantum dot / elastomer hybrid photosensitive layer and a preparation method thereof. The transistor has a high mobility (>0.2cm 2 V -1 s -1 ), high light-to-dark current ratio (>10 5 ), high tensile strain (>100%), excellent synaptic behavior simulation (double-pulse facilitation PPF>270%, short-range plasticity STM, long-range plasticity LTM), broad-band (ultraviolet light, visible light and near-infrared light) bionic visual adaptive function (light intensity and gate voltage-dependent light-dark adaptation) and imaging effect.

[0006] The stretchable wide-band light-adaptive-synaptic transistor provided by the present invention is a bottom-gate top-contact structure, and its structure includes, from bottom to top, a stretchable substrate, a stretchable gate electrode, a stretchable hybrid dielectric layer, a stretchable hybrid polymer semiconductor layer, a stretchable source electrode and a stretchable drain electrode in the same plane, and a stretchable quantum dot / elastomer hybrid photosensitive layer, wherein the stretchable quantum dot / elastomer hybrid photosensitive layer covers the stretchable source and drain electrodes;

[0007] The light adaptation range of the stretchable wide-band light-adaptive-synaptic transistor includes ultraviolet light, visible light, and near-infrared light.

[0008] The stretchable gate electrode, the stretchable source electrode and the stretchable drain electrode of the stretchable wide-band light-adaptive-synaptic transistor are all made of carbon nanotube material or silver nanowire material;

[0009] The carbon nanotube material is a single-walled carbon nanotube, including any one of the models P2-SWNT, P3-SWNT, P5-SWNT, P8-SWNT and P9-SWNT;

[0010] The silver nanowire material is any one of GS-SNW-20, GS-SNW-25, GS-SNW-30 and GS-SNW-40.

[0011] The stretchable hybrid dielectric layer in the stretchable broadband light-adaptive-synaptic transistor is prepared by blending an elastomer and carbon quantum dots;

[0012] The elastomeric 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);

[0013] The carbon quantum dots have the characteristics of being uncharged, high dielectric and having a narrow particle size, with a size of 1-5 nm;

[0014] The mixing mass ratio of the elastomeric polymer and the carbon quantum dots is 100:0.5 to 100:10, preferably 100:1.5 to 100:5, specifically 100:3.5, 100:5;

[0015] The thickness of the stretchable hybrid dielectric layer may be 1300-2500 nm, preferably 1600-1900 nm.

[0016] The stretchable hybrid polymer semiconductor layer of the stretchable broadband light-adaptive-synaptic transistor is prepared from a stretchable hybrid polymer blend system of an elastomeric polymer and a conjugated polymer;

[0017] The elastomeric polymer is the same as the elastomeric polymer used in the stretchable hybrid dielectric layer;

[0018] The conjugated polymer is any one of poly(2,5-bis(2-octyldodecyl)-3,6-di(thiophene-2-yl)diketopyrrole[3,4-c]pyrrole-1,4-dione-alt-thiophene[3,2-b]thiophene) (DPPT-TT), poly(2,5-bis(3-alkylthiophene-2-yl)thiophene[3,2-b]thiophene) (PBTTT), poly(quaterthiopheneacetic acid diketopyrrole) (PTDPPTFT4), polyisoindigodithiophene (PII2T) and poly(3-hexylthiophene) (P3HT);

[0019] The mass ratio of the conjugated polymer to the elastomeric polymer is 1:9 to 9:1, preferably 3:7 to 5:5;

[0020] The thickness of the stretchable hybrid polymer semiconductor layer is 30-100 nm, preferably 50-70 nm.

[0021] The stretchable quantum dot / elastomer hybrid photosensitive layer of the stretchable wide-band light-adaptive-synaptic transistor is prepared by regulating the blending ratio, pre-aggregation morphology and self-assembled quasi-continuous-microsphere morphology of the photosensitive quantum dots and the elastomer polymer;

[0022] The photosensitive quantum dots are any one of cesium lead chlorine quantum dots (CsPbCl3), cesium lead bromine quantum dots (CsPbBr3), cesium lead iodine quantum dots (CsPbI3), cesium lead iodine quantum dots (CsPbI3), cadmium telluride (CdTe), cadmium sulfide (CdS) and lead sulfide (PbS);

[0023] The photosensitive quantum dots have the characteristics of high quantum yield and a size of 1 to 10 nm;

[0024] The elastomeric polymer is the same as the elastomeric polymer used in the stretchable hybrid dielectric layer and the stretchable hybrid polymer semiconductor layer;

[0025] The mass ratio of the photosensitive quantum dots to the elastomeric polymer is 10:0.5 to 10:3, preferably 10:1;

[0026] The thickness of the stretchable quantum dot / elastomer hybrid photosensitive layer film is 10-50nm;

[0027] The self-assembled quasi-continuous-microsphere morphology is achieved by regulating the surface energy of the substrate;

[0028] The surface energy of the substrate is achieved through vacuum oxygen plasma treatment, and the surface energy control range is 10-65 millijoules per square centimeter.

[0029] In the stretchable broadband light-adaptive-synaptic transistor, the stretchable substrate is prepared by any one of the elastomeric polymers used in the stretchable hybrid dielectric layer;

[0030] The thickness of the stretchable substrate is 100 μm to 2 mm, preferably 0.6-1 mm.

[0031] The method for preparing the above-mentioned stretchable wide-band light-adaptive-synaptic transistor provided by the present invention comprises the following steps:

[0032] (1) preparing the stretchable substrate, the stretchable gate electrode, the stretchable hybrid dielectric layer, the stretchable hybrid polymer semiconductor layer, the stretchable source electrode and the stretchable drain electrode on the substrate with the self-assembled molecular layer respectively;

[0033] (2) preparing the stretchable quantum dot / elastomer hybrid photosensitive layer on a polydimethylsiloxane (PDMS) elastomer film substrate that has been subjected to vacuum oxygen plasma surface energy treatment;

[0034] (3) Using tweezers, the stretchable substrate is transferred from the substrate with the self-assembled molecular layer, and then the stretchable substrate is gently covered on the stretchable gate electrode from one side; the stretchable gate electrode is transferred to the stretchable substrate by a thermal bonding-transfer method; and then the same method and steps are used to sequentially transfer the stretchable hybrid dielectric layer, the stretchable hybrid polymer semiconductor layer, the stretchable source electrode and the stretchable drain electrode located on the same plane, and the stretchable quantum dot / elastomer hybrid photosensitive layer from the self-assembled monolayer substrate or the substrate with an elastomer film to the stretchable gate electrode, thereby obtaining a stretchable wide-band light-adaptive-synaptic transistor based on a morphology-controllable quasi-continuous quantum dot / elastomer hybrid photosensitive layer.

[0035] In the above preparation steps, the substrate is selected from any one of silicon wafer, glass, ceramic and quartz;

[0036] The substrate is cleaned by ultrasonic cleaning with detergent, deionized water, acetone, and ethanol in sequence, blown dry with a nitrogen gun, and then subjected to vacuum oxygen plasma treatment to obtain a clean substrate;

[0037] The ultrasonic cleaning conditions are as follows: ultrasonic power is 10-100 watts, ultrasonic time is 1-30 minutes, and ultrasonic frequency is 10-100 kHz;

[0038] The vacuum oxygen plasma treatment conditions are: the treatment time is 1-30 minutes.

[0039] The substrate with the self-assembled molecular layer is prepared by heating the clean substrate with any one of octadecyltrimethoxysilane, octadecyltrichlorosilane, octadecyltrichlorosilane and phenyltrichlorosilane under vacuum conditions or immersing the substrate in a solution;

[0040] The conditions for the heating treatment under vacuum conditions are: vacuum degree of 0.1 Pascal, heating temperature of 50-150° C., and heating time of 1-5 hours;

[0041] The conditions for the immersion treatment in the solution are: using any one of n-hexane, n-heptane, isohexane and cyclohexane as a 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 to 3 hours.

[0042] In the above preparation steps, the polydimethylsiloxane (PDMS) elastomer film substrate is prepared by cross-linking and diluting a polydimethylsiloxane (PDMS) stock solution, a cross-linking agent and a solvent in a certain proportion and then depositing the resultant solution on the clean substrate;

[0043] The mass ratio of the polydimethylsiloxane (PDMS) stock solution to the cross-linking agent is 10:1 to 20:1, preferably 10:1;

[0044] The mass ratio of the mixed solution of the polydimethylsiloxane (PDMS) stock solution and the cross-linking agent to the solvent is 1:5 to 1:10, preferably 1:5;

[0045] The solvent is any one of cyclohexane, n-hexane, isohexane and toluene, preferably cyclohexane;

[0046] The crosslinking agent is a commercial PDMS matching crosslinking agent purchased, the trade name is SYLGARD TM 184 SiliconeElastomer or SYLGARD TM 186 Silicone Elastomer (including prepolymer solution and cross-linking agent); manufacturer: Dow Chemical Company; model: Sylgard-184 or Sylgard-186.

[0047] The thickness of the polydimethylsiloxane (PDMS) elastomer film substrate is 500-3000 nm, preferably 1000 nm;

[0048] The vacuum oxygen plasma treatment has a vacuum degree of 0.3 to 0.8 Pascal, a power of 10 to 30 watts, and a time of 0.5 to 10 minutes.

[0049] In the above preparation steps, the stretchable substrate, the stretchable hybrid dielectric layer, the stretchable hybrid polymer semiconductor layer, the stretchable quantum dot / elastomer hybrid photosensitive layer and the elastomer film substrate are all prepared by solution deposition;

[0050] The solution deposition method is any one of drop coating, spin coating, scraping, rolling, brushing and drawing;

[0051] The solvent used in the solution deposition method is any one of toluene, xylene, chlorobenzene, dichlorobenzene, methane, chloroform, dichloromethane, n-hexane or cyclohexane;

[0052] The solution concentration of the stretchable substrate is 100-300 mg / mL;

[0053] The solution concentration of the stretchable hybrid dielectric layer is 50-100 mg / mL;

[0054] The solution concentration of the stretchable hybrid polymer semiconductor layer is 5-15 mg / mL.

[0055] In the above preparation steps, the stretchable gate electrode, the stretchable source electrode and the stretchable drain electrode are all prepared by spraying;

[0056] The solvent used is any one of water, ethanol, isopropanol or a mixed solvent thereof;

[0057] The spraying conditions are as follows: the temperature of the substrate is 60-120° C., the distance between the spray gun nozzle and the substrate is 5-12 cm, the spraying rate is 0.3-3 mL / min, and the spraying amount is 1-3 mL.

[0058] In order to ensure high resolution of the stretchable gate electrode, the stretchable source electrode and the stretchable drain electrode, the substrate with the self-assembled molecular layer is placed between a strong magnet and a patterned nickel or iron mask;

[0059] In the above preparation steps, the thermal bonding process is carried out in a vacuum drying oven;

[0060] The conditions for the thermal bonding are: a vacuum degree of 0.1 to 3 Pasla, a temperature of 30 to 80° C. during the heating treatment, and a heating treatment time of 0.1 to 1 hour.

[0061] The beneficial effects of the present invention are as follows: the present invention prepares a quasi-continuous-microsphere morphology of quantum dot / elastomer hybrid photosensitive film with intrinsic stretchability, high photosensitivity and easy integration characteristics by regulating the pre-aggregation morphology of photosensitive quantum dots and elastomeric polymers and modifying the surface energy of the substrate film to achieve regulation of the quasi-continuous morphology of the quantum dot / elastomer hybrid photosensitive layer film, and obtains an intrinsically stretchable wide-band photosensitivity-synaptic transistor based on the quasi-continuous quantum dot / elastomer hybrid photosensitive layer. The intrinsically stretchable wide-band light-adaptive-synaptic transistor prepared by the present invention has excellent field effect characteristics, outstanding photoelectric response performance and high tensile strain capacity; at the same time, it has excellent synaptic behavior simulation functions (double pulse facilitation PPF, short-range plasticity STM, long-range plasticity LTM), wide-band (ultraviolet light, visible light and near-infrared light) bionic visual adaptive functions (light intensity and gate voltage dependent light and dark adaptation) and imaging effects, which broadens the application prospects of quantum dots in the construction of stretchable devices and provides a practical strategy for future wearable optoelectronic devices, electronic skin, brain-like neural computing, bionic visual networks and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0062] Figure 1 It is a schematic structural diagram of the intrinsically stretchable wide-band light-adaptive-synaptic transistor based on the morphology-controllable quasi-continuous quantum dot / elastomer hybrid photosensitive layer of the present invention.

[0063] Figure 2 The atomic force microscope images of the quasi-continuous quantum dot / elastomer hybrid photosensitive layer with controllable morphology prepared by Example 1 and Comparative Example 2 of the present invention through surface energy modification of the elastomer film substrate. Figure 2 a is an atomic force microscope image of Example 1; Figure 2 Figure b is the atomic force microscope image of comparative example 2.

[0064] Figure 3 The characteristic transfer curves of the stretchable wide-band light-adaptive-synaptic transistor prepared in Example 1 and Comparative Example 1 of the present invention under different 365nm light intensities. Figure 3 a is the characteristic transfer curve of Example 1; Figure 3 In b, the left axis is the characteristic transfer curve of comparative example 1; the left axes of a and b are both the relationship between |source-drain current| and gate voltage.

[0065] Figure 4 This is a single light pulse time-current comparison curve of the stretchable wide-band light-adaptive-synaptic transistor prepared in Example 1 of the present invention and Comparative Example 1.

[0066] Figure 5 In the figure a, the visual bionic adaptive characteristics of the stretchable wide-band light-adaptive-synaptic transistor prepared in Example 1 of the present invention. Figure 5 Middle b and Figure 5 c is the relationship between the on-state current and the light-to-dark current ratio of the stretchable wide-band light-adaptive-synaptic transistor prepared in Example 1 of the present invention and the tensile strain; wherein Figure 5 b is the relationship between the on-state current and the light-to-dark current ratio of the stretchable wide-band light-adaptive-synaptic transistor prepared in Example 1 of the present invention and the number of stretching cycles; Figure 5 In the figure c, the relationship between the bionic visual adaptive function of the stretchable wide-band light adaptive-synaptic transistor prepared in Example 1 of the present invention and the tensile strain.

[0067] Figure 6 This is a diagram of the visual bionic adaptive characteristics of the stretchable wide-band light-adaptive-synaptic transistor prepared in Example 1 of the present invention under different gate voltages and different stretching states.

[0068] Figure 7 This is an adaptive imaging diagram of the stretchable wide-band light-adaptive-synaptic transistor prepared in Example 1 of the present invention under 365nm light at different time intervals. DETAILED DESCRIPTION

[0069] The present invention is further described in detail below in conjunction with specific embodiments, and the examples provided are only for illustrating the present invention, rather than for limiting the scope of the present invention. The examples provided below can be used as a guide for further improvements by those of ordinary skill in the art, and do not constitute a limitation of the present invention in any way.

[0070] The experimental methods in the following examples, unless otherwise specified, are all conventional methods, and are performed according to the techniques or conditions described in the literature in the field or according to the product instructions. The materials, reagents, etc. used in the following examples, unless otherwise specified, can all be obtained from commercial channels.

[0071] In the present invention, the optical and electrical properties of the intrinsically stretchable wide-band light-adaptive-synaptic transistor are measured under atmospheric environment and room temperature conditions.

[0072] The carbon quantum dots used in the following examples were purchased from Suzhou Guona Hi-Tech Co., Ltd.

[0073] Cesium lead bromine quantum dots were purchased from Nanjing 2D Nanotechnology Co., Ltd., with the trade name 513nm perovskite quantum dots and model number CsPbBr3.

[0074] The polydimethylsiloxane stock solution and cross-linking agent used are SYLGARD μ184 Silicone Elastomer.

[0075] Example 1

[0076] In this embodiment, the intrinsically stretchable broadband light-adaptive-synaptic transistor based on the quasi-continuous-microsphere morphology quantum dot / elastomer hybrid photosensitive layer is prepared according to the following steps:

[0077] 1) Using a silicon wafer as a substrate, ultrasonically treat with detergent, deionized water, acetone and ethanol at a power of 40 W and a frequency of 30 kHz for 10 min in sequence, blow dry with a nitrogen gun, and then perform vacuum oxygen plasma treatment (power of 60 Hz) for 5 min on the cleaned silicon wafer. Then, the clean silicon wafer and 1 μL of octadecyltrimethoxysilane are placed in the same culture dish, and the culture dish is placed in a vacuum drying oven at a vacuum degree of 0.1 Pascal and 120° C. for 3 h. After the vacuum drying oven is cooled to room temperature, the culture dish is taken out to obtain a silicon wafer with a self-assembled molecular layer.

[0078] 2) Place the silicon wafer with the self-assembled molecular layer on a hot stage, slowly draw 0.5 ml of SEBS toluene solution (concentration of 150 mg / mL) with a 1 mL syringe and evenly drop it on the silicon wafer with the self-assembled molecular layer, then keep it at 40°C for 2 hours and then keep it at 90°C for 1 hour to obtain a stretchable substrate with a thickness of 1 mm.

[0079] 3) Place the silicon wafer with the self-assembled molecular layer prepared in step 1) on a magnet, and then place the patterned nickel mask plate on the silicon wafer, so that the mask plate is tightly attached to the silicon wafer with the self-assembled molecular layer, gently place the magnet, silicon wafer and mask plate on a hot plate at 60°C for 5 minutes, use a 2mL pipette to transfer 1.5mL of carbon nanotube P3-SWNT isopropanol solution (0.2mg / mL) to the volume chamber of the spray gun, and then evenly spray it on the silicon wafer with the self-assembled molecular layer at a rate of 0.15mL / min (wherein the distance between the spray gun nozzle and the silicon wafer is 8cm), and a patterned stretchable gate electrode can be obtained.

[0080] 4) Place the silicon wafer with the self-assembled molecular layer prepared in step 1) at the center of the rotor of the coating machine, extract 200 μL of the mixed solution of SEBS and carbon quantum dots (the solvent is toluene, the mass ratio of SEBS and carbon quantum dots is 100:3.5, and the concentration of the mixed solution is 100 mg / mL) with a 1 mL pipette, and then evenly drop it on the silicon wafer with the self-assembled molecular layer, start the coating machine, and keep it at a speed of 1000 rad / min for 1 min. Finally, remove the silicon wafer and place it on a hot plate at 80°C for annealing for 30 min to obtain a stretchable hybrid dielectric layer with a thickness of 1800 nm.

[0081] 5) Place the silicon wafer with the self-assembled molecular layer prepared in step 1) at the center of the rotor of the coating machine, use a 50μL pipette to extract 30μL of chlorobenzene solution of poly(2,5-bis(2-octyldodecyl)-3,6-di(thiophene-2-yl)dionepyrrolo[3,4-c]pyrrole-1,4-dione-3-thieno[3,2-b]thiophene) / hydrogenated styrene-butadiene block copolymer (wherein the mass ratio of the two polymers is 5:5 and the concentration of the mixture solution is 10mg / mL), then drop it evenly on the silicon wafer, start the coating machine, and keep it at a speed of 3000rad / min for 1min. Finally, remove the silicon wafer and place it on a hot plate at 150°C for 20 minutes to obtain a stretchable hybrid polymer semiconductor layer with a thickness of 50nm.

[0082] 6) Place the silicon wafer with the self-assembled molecular layer prepared in step 1) on a magnet, and then place the patterned nickel mask plate on the silicon wafer, so that the mask plate is tightly attached to the silicon wafer with the self-assembled molecular layer, gently place the magnet, silicon wafer and mask plate on a hot stage at 110°C for 15 minutes, and then use a 2mL pipette to extract 1.5mL of an isopropanol solution of carbon nanotubes P3-SWNT (concentration 0.15mg / mL), and then evenly spray it on the silicon wafer with the self-assembled molecular layer at a rate of 0.1mL / min (wherein the distance between the spray gun nozzle and the silicon wafer is 9cm), and a patterned stretchable source electrode and a stretchable drain electrode (channel length and channel width are 200μm and 4000μm, respectively) are obtained.

[0083] 7) Weigh the polydimethylsiloxane stock solution and the cross-linking agent in a mass ratio of 10:1 to obtain a mixed solution, and then dilute the mixed solution to the cyclohexane solution in a mass ratio of 1:5. Use a silicon wafer as a substrate and place it at the center of the rotor of the coating machine. Use a 50μL pipette to extract 30μL of the obtained mixed elastomer solution, evenly drop it on the silicon wafer, start the coating machine, and keep it at a speed of 6000rad / min for 1min. Finally, remove the silicon wafer and place it on a hot plate at 120℃ for 20 minutes to obtain an elastomer film substrate.

[0084] 8) The elastomer film substrate prepared in step 7) is placed in a vacuum oxygen plasma treatment instrument, the vacuum degree is set to 0.5 Pascal, the power is 50 watts, and the vacuum oxygen plasma treatment is performed for 6 minutes to obtain a surface-activated elastomer film substrate (surface energy is 40.49 millijoules per square centimeter). Then the substrate is placed at the center of the rotor of the glue machine, and 30 μL of cesium lead bromide quantum dots / hydrogenated styrene-butadiene block copolymer n-hexane solution (wherein the mass ratio of quantum dots to copolymers is 10: 1, and the concentration of the mixture solution is 10 mg / mL) is extracted with a 50 μL pipette, and evenly dropped on the substrate, the glue machine is started, and maintained at a speed of 2000 rad / min for 1 minute. Finally, the substrate is removed and placed on a hot stage at 50°C for 5 minutes to obtain a stretchable quantum dot / elastic hybrid photosensitive layer with a quasi-continuous-microsphere morphology.

[0085] 9) Use pointed tweezers to gently peel off the stretchable substrate from the substrate with the self-assembled molecular layer, then gently cover the stretchable substrate from one side on the stretchable gate electrode, and place it in a vacuum drying oven with a vacuum degree of 0.1 Pascal at 60°C for 20 minutes. After the temperature drops to room temperature, use pointed tweezers to gently transfer the stretchable substrate. Through this process, the stretchable gate electrode can be transferred to the stretchable substrate. Then, using the same method and steps, the stretchable hybrid dielectric layer, the stretchable hybrid polymer semiconductor layer, the stretchable source electrode and the stretchable drain electrode located in the same plane, and the stretchable quasi-continuous-microspherical morphology quantum dot / elastomer hybrid photosensitive layer are transferred to the stretchable gate electrode in turn, and an intrinsic stretchable wide-band light-adaptive-synaptic transistor based on the quasi-continuous-microspherical morphology quantum dot / elastomer hybrid photosensitive layer can be obtained, and the structure is as follows Figure 1 shown.

[0086] Comparative Example 1

[0087] According to the same preparation method as Example 1, only the mixed solution of cesium lead bromide (CsPbBr3) quantum dots and SEBS in step 8) (the solvent is n-hexane, the mass ratio of CsPbBr3 quantum dots and SEBS is 10:1, and the concentration of the mixed solution is 10 mg / mL) is changed to cesium lead bromide (CsPbBr3) quantum dot solution (the solvent is n-hexane, and the solution concentration is 10 mg / mL). The thickness of the perovskite quantum dot photosensitive layer prepared in Comparative Example 1 is consistent with the thickness of the intrinsic stretchable quasi-continuous-microsphere quantum dot / elastomer hybrid photosensitive layer prepared in Example 1, which is about 20nm.

[0088] Comparative Example 2

[0089] The same preparation method as in Example 1 was followed, except that in step 8), the elastomer film substrate was placed in a vacuum oxygen plasma treatment apparatus, the vacuum degree was set to 0.5 Pascal, the power was set to 50 W, and the vacuum oxygen plasma treatment was performed for 6 min, while the elastomer film substrate was not subjected to additional treatment.

[0090] Figure 2 The atomic force microscope images are of the quasi-continuous-microsphere morphology regulated by the stretchable quantum dot / elastomer hybrid photosensitive layer film prepared in Example 1 and the original morphology of the stretchable quantum dot / elastomer hybrid photosensitive layer film prepared in Comparative Example 2. Figure 2 It can be seen that by treating the substrate surface with oxygen plasma, the morphology of the stretchable quantum dot / elastomer hybrid film changes from the original needle-like morphology to the quasi-continuous-microsphere morphology, and the surface roughness of the film is reduced, which will promote the contact and carrier transport between the layers of the stretchable device.

[0091] Figure 3 a and b are characteristic transfer curves of the stretchable wideband light-adaptive-synaptic transistor prepared in Example 1 and Comparative Example 1 under different 365nm illumination conditions. Compared with Comparative Example 1, after adding SEBS to the photosensitive layer of the stretchable wideband light-adaptive-synaptic transistor prepared in Example 1, the device light response can still be maintained at an extremely high level, and it exhibits better sensitivity under lower light intensity. And combined with Figure 4 From the time-current comparison curves under single light pulses of Example 1 and Comparative Example 1, it can be seen that the stretchable wide-band light-adaptive-synaptic transistor prepared in Example 1 can present more ideal synaptic characteristics.

[0092] Figure 5 In a, it is the visual bionic adaptive characteristic of Example 1 of the present invention, which shows that the stretchable wide-band light adaptive-synaptic transistor prepared based on the quasi-continuous-microsphere morphology quantum dot / elastomer hybrid photosensitive layer can realize the adaptation to the light intensity (the photocurrent gradually decays under strong light, and the photocurrent gradually increases under weak light), and has the adjustable adaptive performance dependent on the gate voltage (the photocurrent gradually increases under the positive operating voltage, and the photocurrent gradually decays under the negative operating voltage). At the same time, Figure 5 Middle b and Figure 5 It can be seen from c that the stretchable wide-band optically adaptive-synaptic transistor prepared in Example 1 can still maintain relatively stable field effect performance and photoelectric response when subjected to 0-100% biaxial tensile strain and 0-1000 stretching cycles, and can still realize synaptic simulation and bionic visual adaptive functions, and when the tensile strain is released, the performance of the stretchable transistor returns to its initial value. Figure 6 It is proved that the stretchable wide-band optically adaptive-synaptic transistor prepared in Example 1 also has extremely excellent adjustable adaptive performance in the stretched state. Figure 7The imaging images of the stretchable wide-band light-adaptive-synaptic transistor prepared in Example 1 at different time intervals show its outstanding adaptive imaging effect. These experimental results show that the stretchable wide-band light-adaptive-synaptic transistor prepared based on the quasi-continuous-microsphere morphology of quantum dot / elastomer hybrid photosensitive layer can not only achieve high photoelectric response, but also has high resistance to mechanical deformation and excellent synaptic simulation, bionic visual adaptive function and imaging effect, which provides a practical strategy for future wearable optoelectronic devices, electronic skin, brain-like neural computing and bionic visual networks.

[0093] The present invention has been described in detail above. For those skilled in the art, without departing from the purpose and scope of the present invention, and without the need to carry out unnecessary experimental conditions, the present invention can be implemented in a wide range under equivalent parameters, concentrations and conditions. Although the present invention provides specific embodiments, it should be understood that the present invention can be further improved. In a word, according to the principles of the present invention, the application is intended to include any changes, uses or improvements to the present invention, including departure from the disclosed scope in the application, and changes made with conventional techniques known in the art.

Claims

1. A stretchable wide-band light-adaptive-synaptic transistor, which is a bottom-gate top-contact structure, and its structure from bottom to top includes: A stretchable substrate, a stretchable gate electrode, a stretchable hybrid dielectric layer, a stretchable hybrid polymer semiconductor layer, a stretchable source electrode and a stretchable drain electrode in the same plane, and a stretchable quantum dot / elastomer hybrid photosensitive layer; The stretchable quantum dot / elastomer hybrid photosensitive layer is prepared by regulating the blending ratio, pre-aggregation morphology and self-assembled quasi-continuous-microsphere morphology of the photosensitive quantum dots and the elastomer polymer.

2. The stretchable broadband optically adaptive synaptic transistor according to claim 1, characterized in that: The self-assembled quasi-continuous-microsphere morphology is achieved by regulating the surface energy of the substrate; The surface energy of the substrate is achieved through vacuum oxygen plasma treatment, and the surface energy control range is 10-65 millijoules per square centimeter.

3. The stretchable broadband optically adaptive synaptic transistor according to claim 2, characterized in that: The substrate is a polydimethylsiloxane elastomer film substrate.

4. The stretchable broadband optically adaptive synaptic transistor according to any one of claims 1 to 3, characterized in that: The photosensitive quantum dots are any one of cesium lead chlorine quantum dots, cesium lead bromine quantum dots, cesium lead iodine quantum dots, cesium lead iodine quantum dots, cadmium telluride, cadmium sulfide and lead sulfide; The size of the photosensitive quantum dots is 1 to 10 nm; The elastomeric polymer is selected from any one of polydimethylsiloxane, hydrogenated styrene-butadiene block copolymer, polyurethane elastomer, styrene-butadiene rubber and natural rubber; The mass ratio of the photosensitive quantum dots to the elastomeric polymer is 10:0.5 to 10:3; The thickness of the stretchable quantum dot / elastomer hybrid photosensitive layer film is 10-50nm.

5. The stretchable broadband optically adaptive synaptic transistor according to any one of claims 1 to 4, characterized in that: The stretchable substrate is prepared from any one of the following elastomeric polymers: polydimethylsiloxane, hydrogenated styrene-butadiene block copolymer, polyurethane elastomer, styrene-butadiene rubber and natural rubber; The thickness of the stretchable substrate is 100 μm to 2 mm; The stretchable gate electrode, the stretchable source electrode and the stretchable drain electrode are all made of carbon nanotube material or silver nanowire material; The stretchable hybrid dielectric layer is prepared by blending an elastomer 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 size of the carbon quantum dots is 1-5 nm; The mixing mass ratio of the elastomeric polymer and the carbon quantum dots is 100:0.5 to 100:10; The thickness of the stretchable hybrid dielectric layer is 1300-2500 nm.

6. The stretchable broadband optically adaptive synaptic transistor according to any one of claims 1 to 5, characterized in that: The stretchable hybrid polymer semiconductor layer is prepared from a stretchable hybrid polymer blend system of an elastomeric polymer and a conjugated polymer; The elastomeric polymer is selected from any one of polydimethylsiloxane, hydrogenated styrene-butadiene block copolymer, polyurethane elastomer, styrene-butadiene rubber and natural rubber; The conjugated polymer is any one of poly(2,5-bis(2-octyldodecyl)-3,6-di(thiophene-2-yl)diketopyrrole[3,4-c]pyrrole-1,4-dione-alt-thiophene[3,2-b]thiophene) (DPPT-TT), poly(2,5-bis(3-alkylthiophene-2-yl)thiophene[3,2-b]thiophene) (PBTTT), poly(quaterthiopheneacetic acid diketopyrrole) (PTDPPTFT4), polyisoindigodithiophene (PII2T) and poly(3-hexylthiophene) (P3HT); The mass ratio of the conjugated polymer to the elastomeric polymer is 1:9 to 9:1; The thickness of the stretchable hybrid polymer semiconductor layer is 30-100 nm.

7. A method for preparing the stretchable broadband light-adaptive-synaptic transistor according to any one of claims 1 to 6, comprising the following steps: (1) preparing the stretchable substrate, the stretchable gate electrode, the stretchable hybrid dielectric layer, the stretchable hybrid polymer semiconductor layer, the stretchable source electrode and the stretchable drain electrode on the substrate with the self-assembled molecular layer respectively; (2) preparing the stretchable quantum dot / elastomer hybrid photosensitive layer on a substrate having a polydimethylsiloxane (PDMS) elastomer film that has been surface-treated by vacuum oxygen plasma; (3) using tweezers to transfer the stretchable substrate from the substrate with the self-assembled molecular layer, and then covering the stretchable substrate on the stretchable gate electrode from one side; The stretchable gate electrode is transferred to the stretchable substrate by a thermal bonding-transfer method; then the stretchable hybrid dielectric layer, the stretchable hybrid polymer semiconductor layer, the stretchable source electrode and the stretchable drain electrode located on the same plane, and the stretchable quantum dot / elastomer hybrid photosensitive layer are sequentially transferred from a self-assembled monolayer substrate or a substrate with an elastomer film to the stretchable gate electrode by the same method and steps, thereby obtaining a stretchable wide-band light-adaptive-synaptic transistor based on a morphology-controllable quasi-continuous quantum dot / elastomer hybrid photosensitive layer.

8. The method according to claim 7, characterized in that: The substrate is selected from any one of silicon wafer, glass, ceramic and quartz; The substrate with the self-assembled molecular layer is prepared by heating the substrate and any one of octadecyltrimethoxysilane, octadecyltrichlorosilane, octadecyltrichlorosilane and phenyltrichlorosilane under vacuum conditions or immersing the substrate in a solution; The elastic film substrate is obtained by cross-linking and diluting a polydimethylsiloxane (PDMS) stock solution, a cross-linking agent and a solvent in a proportion, depositing the solution on the substrate, and then treating the substrate with vacuum oxygen plasma; Wherein, the mass ratio of the polydimethylsiloxane (PDMS) stock solution to the cross-linking agent is 10:1 to 20:1; The mass ratio of the mixed solution of the polydimethylsiloxane (PDMS) stock solution and the cross-linking agent to the solvent is 1:5 to 1:10; The solvent is any one of cyclohexane, n-hexane, isohexane and toluene; The thickness of the elastic film substrate is 500 to 3000 nm; The vacuum oxygen plasma treatment has a vacuum degree of 0.3 to 0.8 Pascal, a power of 10 to 30 W, and a time of 0.5 to 10 min.

9. The preparation method according to claim 7, characterized in that: The stretchable substrate, the stretchable hybrid dielectric layer, the stretchable hybrid polymer semiconductor layer and the stretchable quasi-continuous quantum dot / elastomer hybrid photosensitive layer film are prepared by solution deposition; The solution deposition method is any one of drop coating, spin coating, scraping, rolling, brushing and drawing; The solvent used in the solution deposition method is toluene, xylene, methane, chloroform, dichloromethane, n-hexane or cyclohexane; The solution concentration of the stretchable substrate is 100 to 300 mg / mL; The solution concentration of the stretchable hybrid dielectric layer is 50 to 100 mg / mL; The solution concentration of the stretchable hybrid polymer semiconductor layer is 5 to 15 mg / mL; The solution concentration of the stretchable quasi-continuous quantum dot / elastomer hybrid photosensitive layer is 5 to 15 mg / mL; The stretchable gate electrode, the stretchable source electrode and the stretchable drain electrode are all made by a spray coating method; The spraying conditions are as follows: the temperature of the substrate is 60-120° C., the distance between the spray gun mouth and the substrate is 5-12 cm, the spraying rate is 0.3-3 mL / min, and the spraying amount is 1-3 mL.

10. The preparation method according to claim 7, characterized in that: The thermal bonding process is carried out in a vacuum drying oven; The conditions for the thermal bonding are: a vacuum degree of 0.1 to 3 Pasla, a temperature of 30 to 80° C. during the heating treatment, and a heating treatment time of 0.1 to 1 hour.

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