Photoelectric synaptic device capable of identifying light with five wavelengths and preparation method of photoelectric synaptic device

Abstract

The invention discloses a photoelectric synaptic device capable of identifying light with five wavelengths and a preparation method of the photoelectric synaptic device. The photoelectric synapse device is composed of a substrate (blank glass), an active layer (a hollow multi-shell structure metal oxide and a photosensitizer) and a metal electrode. In the system, the metal oxide hollow sphere with the hollow multi-shell structure can realize high-efficiency light utilization rate by utilizing the scattering reflection effect among a plurality of shells, the photosensitizer porphyrin is good in photosensitivity, stable in performance and easy to modify, the light response range is expanded, and the perovskite is easy to synthesize, tunable in band gap, high in electron mobility and excellent in photoelectric property. The hollow multi-shell-layer structure material is compounded with a photosensitizer to serve as a photoresponse layer to be applied to the photoelectric synapse device, and compared with other photoelectric synapse devices, the hollow multi-shell-layer structure material has the advantages that light of various colors can be recognized; (2) the sensitivity is high; (3) the signal retention time is long; and (4) the preparation cost is low, the process is simple and environment-friendly.

Description

Technical Field

[0001] This invention relates to the technical field of photoelectric synaptic devices, specifically to a photoelectric synaptic device capable of recognizing five wavelengths of light and its fabrication method. Background Technology

[0002] The brain, with its highly parallel, low-energy, and fault-tolerant neural network system, achieves ultra-low-energy, highly efficient information processing, enabling complex unstructured and probabilistic information processing such as cognitive learning, image recognition, and language understanding. Inspired by the brain's cognitive functions, neuromorphic computing aims to mimic the working mechanisms of neurons and synapses that make up the brain, imitating key functions of the human nervous system to realize artificial intelligence systems such as neuromorphic memory computing, artificial perception, and humanoid robots. Currently, artificial perception systems mainly use light stimulation to simulate vision, vibration stimulation to simulate hearing, pressure stimulation to simulate touch, chemical stimulation to simulate smell, and temperature stimulation to simulate pain. Since over 70% of the information humans acquire comes from vision, research into simulating visual perception functions, i.e., photoelectric synaptic devices, is particularly important. Choosing a suitable material system is crucial for realizing photoelectric synapses. In recent years, with the development of photoelectric synapses, the enormous potential of two-dimensional materials such as perovskite (Adv. Mater. 2023, 35, 2208497), molybdenum disulfide (Adv. Funct. Mater. 2024, 34, 2302288), metal oxides such as titanium oxide (Adv. Sci. 2022, 9, 2104632), organic semiconductors (Nat. Photonics, 2023, 17, 629-637), silicon nanocrystals (Nano Energy. 2018, 52, 422-430), and various composite materials (Adv. Optical Mater. 2022, 10, 2200409) has been discovered. Utilizing these materials to achieve color-selective recognition and image recognition is an important foundation for realizing visual perception. While previous work has yielded significant results, achieving tri-color recognition, highly selective ultraviolet recognition, and green recognition, breakthroughs in multi-color recognition remain challenging.

[0003] Wide bandgap metal oxides exhibit good stability, high electron mobility, and ease of fabrication. Hollow multi-shell structures can achieve high light utilization efficiency by utilizing the scattering and reflection effects between multiple shells. Porphyrin, a photosensitizer, possesses excellent photosensitivity, stable performance, and is easily modified, thus expanding the photoresponse range. Perovskite quantum dots are easy to synthesize, have tunable bandgap, high electron mobility, and excellent photoelectric properties. Using hollow multi-shell structured metal oxide semiconductors combined with photosensitizers (porphyrin / perovskite) as a photoresponse layer can achieve a wide-spectrum response, multi-color recognition, high sensitivity, and good stability. Summary of the Invention

[0004] To address the shortcomings and deficiencies of existing technologies, the primary objective of this invention is to provide a multi-color recognition photoelectric synaptic device with high sensitivity, long signal retention time, and simple and inexpensive fabrication process. The photoelectric synaptic device of this invention uses glass as a substrate and consists of a wide-bandgap metal oxide hollow multi-shell structure, an active layer composed of a photosensitizer, and metal electrodes, capable of recognizing five wavelengths of light.

[0005] The hollow multi-shell structure of the metal oxide is any one of TiO2, SnO2, and ZnO; the hollow multi-shell structure of the metal oxide is any one of single-shell, double-shell, and triple-shell; the photosensitizer is a porphyrin dye or perovskite quantum dots; the metal electrode includes Cu or Au electrodes.

[0006] Under the test conditions of photoelectric synaptic devices, the photocurrent response signal increases with the increase of the number of shells in the hollow multi-shell structure. Furthermore, after being combined with photosensitizer, the synaptic plasticity is enhanced, realizing current signals of different intensities for five wavelengths of light, including 365nm, 420nm, 460nm, 520nm, and 625nm.

[0007] Another objective of this invention is to provide a method for fabricating a photoelectric synaptic device that recognizes five wavelengths of light.

[0008] The objective of this invention is achieved through the following technical solution:

[0009] A method for fabricating a photoelectric synaptic device capable of recognizing five wavelengths of light includes the following fabrication steps:

[0010] (A) Preparation of hollow multi-shell structures in metal oxides

[0011] (1) A 1.5M sucrose aqueous solution was hydrothermally reacted in a high-pressure reactor at 200℃ for 120-140 min. After natural cooling, the mixture was filtered and washed multiple times with water and ethanol. The product was then dried in an oven at 70℃ for 12 h. The particle size of the carbon sphere template obtained was ~3 μm.

[0012] (2) The carbon ball template is uniformly dispersed in the metal salt solution, stirred for 1 to 6 hours, filtered, washed with deionized water 2 to 3 times, dried in a 70°C oven for 12 hours, and the resulting solid powder is placed in a muffle furnace and heated to 500°C at a heating rate of 4°C / min. It is then calcined at a constant temperature for 2 hours and naturally cooled to obtain a hollow multi-shell structure material.

[0013] In the preparation method of the metal oxide hollow multi-shell structure material of the present invention, the metal salt is TiCl4, SnCl4·5H2O or (CH3COO)2Zn·2H2O, the titanium salt concentration is 3M, the tin salt concentration is 0.2-1M, the zinc salt concentration is 0.1-0.5M, and the solvent is deionized water or a mixture of deionized water and ethanol.

[0014] In the preparation method of the metal oxide hollow multi-shell structure material of the present invention, the obtained multi-shell particle size is 0.8 to 1.4 μm.

[0015] (B) Fabrication of photoelectric synaptic devices

[0016] (1) Clean the blank glass sequentially with deionized water, acetone and alcohol using ultrasonic cleaning, and then dry it.

[0017] (2) After mixing the metal oxide hollow multi-shell structure, terpineol and ethyl cellulose obtained in step (A) in a certain proportion, grind them into a viscous white slurry in a mortar. Apply the white slurry to the blank glass in (1) by screen printing. After calcining to remove organic matter, clean the surface dust with ethanol and dry it. Clean it in an ozone cleaner for 15 minutes, then soak it in a photosensitizer solution. After drying, place it in a thermal evaporation device to deposit the electrode.

[0018] In the optoelectronic device preparation method of the present invention, the thin film slurry ratio is: the mass ratio of hollow multi-shell structure material, terpineol, and ethyl cellulose is 1:3:3; the heat treatment conditions for calcination to remove organic matter are: heating at a rate of 10°C to 500°C and holding at that temperature for 1-2 hours; the photosensitizer solution soaking conditions are: soaking in a 0.01 mM porphyrin solution for 2-4 hours; or soaking in a perovskite precursor solution for 2-6 hours.

[0019] The porphyrin solution of the present invention includes C 44 H 30 N4O 12 C 44 H 28 ClFeN4O8, perovskites include MAPbBr2Cl and MAPbIBr2.

[0020] Compared with the prior art, the present invention has the following advantages:

[0021] This invention designs a multi-level hollow structure as both a carrier material and a photoresponse material. Utilizing the large surface area and cavity structure of this multi-level hollow structure, it is possible to fully adsorb and fill light-absorbing materials such as organic dyes and perovskite quantum dots without increasing the thickness of the photoresponse layer. This allows for the construction of a spectrally complementary multi-component composite photosensitive layer material, achieving high-sensitivity recognition of light waves across the entire spectrum. This is beneficial for the development and application of miniaturized, low-power devices. Conventional multi-component composite photoresponse layer materials can only achieve this by increasing film thickness or sacrificing some spectral sensitivity. This invention allows for flexible design of metal oxide semiconductors combined with other photosensitizers as the photoresponse layer. The device employs a two-terminal structure, requiring only one photoresponse layer fabrication and one electrode fabrication to complete the device fabrication process. This is simple, low-cost, and environmentally friendly. Conventional three-terminal device structures typically involve the fabrication of electrodes with multiple chemical components and multi-step film fabrication processes. The photoelectric synapse device of this invention achieves a power density of 1 mW cm⁻¹. -2 Under ultraviolet light irradiation at a wavelength of 365nm, the response current reaches the nA level, exhibiting high sensitivity and promising commercial applications. The multi-color recognizable photoelectric synapse device of this invention retains its electrical signal for over 5 minutes after the light exposure is removed. This long signal retention time aligns with the fundamental synaptic characteristics of short-term and long-term plasticity in biological synapses. Attached Figure Description

[0022] Figure 1 Scanning electron microscope image of a carbon sphere template.

[0023] Figure 2 These are transmission electron microscope (TEM) images of the hollow multi-shell TiO2 structures prepared in Examples 1, 2, and 3.

[0024] Figure 3 These are transmission electron microscope (TEM) images of the SnO2 hollow multi-shell structures prepared in Examples 4, 5, and 6.

[0025] Figure 4 These are transmission electron microscope (TEM) images of the hollow multi-shell ZnO structures prepared in Examples 7, 8, and 9.

[0026] Figure 5 This is a photograph of the photoelectric synapse device prepared in Example 7.

[0027] Figure 6 This is a photograph of the photoelectric synapse device prepared in Example 6.

[0028] Figure 7 This is a comparison of the current-time curves of the photoelectric synaptic device prepared in Example 7 under different wavelengths of excitation, with a test light intensity of 1 mW cm⁻¹. -2 .

[0029] Figure 8These are comparison graphs of the current-time curves of the photoelectric synaptic devices prepared in Examples 7, 8, and 9, with a measured light intensity of 1 mW / cm². -2 . Detailed Implementation

[0030] To better illustrate the present invention and facilitate understanding of its technical solutions, typical but non-limiting embodiments of the present invention are as follows:

[0031] Example 1

[0032] (1) A 1.5M sucrose aqueous solution was subjected to hydrothermal treatment in a high-pressure autoclave at 200℃ for 120 min; after natural cooling, the filtered carbon spheres were washed repeatedly with water and ethanol, and then dried in a 70℃ oven for 12 h. The synthesized carbon spheres had a particle size of ~3μm. Figure 1 As shown.

[0033] (2) The above carbon spheres were uniformly dispersed in 30 mL of 3M titanium tetrachloride solution, stirred for 1.5 h, filtered, washed 2-3 times with deionized water, and dried in a 70℃ oven for 12 h. The resulting solid powder was placed in a muffle furnace and heated to 500℃ at a rate of 4℃ / min, kept at that temperature for 2 h, and then naturally cooled to obtain a single-shell TiO2. Figure 2 As shown in a.

[0034] (3) The single-shell TiO2, terpineol, and ethyl cellulose prepared above were mixed in a mass ratio of 1:3:3 to form a precursor slurry. The white slurry was then coated onto blank glass using a screen printing method. The glass was heat-treated at 500℃ for 1 hour with a heating rate of 10℃ / min. After rinsing the surface with ethanol to remove dust, the glass was dried and then placed in an ozone cleaner for 15 minutes.

[0035] (4) Place the prepared TiO2 film in a 0.01 mM C atmosphere. 44 H 30 N4O 12 After soaking in the solution for 4 hours, the porphyrin molecules physically adsorbed on the surface are cleaned with anhydrous ethanol solution, dried, and then placed in a thermal evaporation apparatus to deposit a Cu metal electrode.

[0036] (5) The photoelectric synaptic devices prepared above exhibit photocurrent responses of different intensities when excited by LED beads with different pulse numbers and pulse frequencies at wavelengths of 365nm, 420nm, 460nm, 520nm and 625nm.

[0037] Example 2

[0038] (1) A 1.5M sucrose aqueous solution was subjected to hydrothermal treatment in a high-pressure autoclave at 200℃ for 131 min; after natural cooling, the filtered carbon spheres were washed repeatedly with water and ethanol, and then dried in a 70℃ oven for 12 h. The synthesized carbon spheres had a particle size of ~3μm. Figure 1 As shown.

[0039] (2) The above carbon spheres were uniformly dispersed in 30 mL of 3M titanium tetrachloride solution, stirred for 6 h, filtered, washed 2-3 times with deionized water, and dried in a 70℃ oven for 12 h. The resulting solid powder was placed in a muffle furnace and heated to 500℃ at a heating rate of 4℃ / min, calcined at that temperature for 2 h, and then naturally cooled to obtain double-shell TiO2. Figure 2 As shown in b.

[0040] (3) The double-shell TiO2, terpineol, and ethyl cellulose prepared above were mixed in a mass ratio of 1:3:3 to form a precursor slurry. The white slurry was then coated onto blank glass using a screen printing method. The glass was heat-treated at 500℃ for 2 hours at a heating rate of 10℃ / min. After rinsing the surface with ethanol to remove dust, the glass was dried and then placed in an ozone cleaner for 15 minutes.

[0041] (4) Place the prepared TiO2 film in a 0.01 mM C atmosphere. 44 H 28 The surface was soaked in ClFeN4O8 solution for 4 hours, and the physically adsorbed porphyrin molecules were cleaned with anhydrous ethanol solution. After drying, the surface was placed in a thermal evaporation apparatus to deposit a Cu metal electrode.

[0042] (5) The photoelectric synaptic devices prepared above exhibit photocurrent responses of different intensities when excited by LED beads with different pulse numbers and pulse frequencies at wavelengths of 365nm, 420nm, 460nm, 520nm and 625nm.

[0043] Example 3

[0044] (1) A 1.5M sucrose aqueous solution was subjected to hydrothermal treatment in a high-pressure autoclave at 200℃ for 140 min; after natural cooling, the filtered carbon spheres were washed repeatedly with water and ethanol, and then dried in a 70℃ oven for 12 h. The synthesized carbon spheres had a particle size of ~3μm. Figure 1 As shown.

[0045] (2) The above carbon spheres were uniformly dispersed in 30 mL of 3M titanium tetrachloride solution, stirred at 45°C for 12 h, filtered, washed 2-3 times with deionized water, and dried in a 70°C oven for 12 h. The resulting solid powder was placed in a muffle furnace and heated to 500°C at a rate of 4°C / min, calcined at this temperature for 2 h, and then naturally cooled to obtain a three-shell TiO2. Figure 2 As shown in c.

[0046] (3) The three-shell TiO2, terpineol, and ethyl cellulose prepared above were mixed in a mass ratio of 1:3:3 to form a precursor slurry. The white slurry was then coated onto blank glass using a screen printing method. The glass was heat-treated at 500℃ for 2 hours at a heating rate of 10℃ / min. After rinsing the surface with ethanol to remove dust, the glass was dried and then placed in an ozone cleaner for 15 minutes.

[0047] (4) The prepared TiO2 film was immersed in the MAPbIBr2 precursor solution for 4 hours, and after annealing, it was placed in a hot evaporation apparatus to deposit the metal electrode Au electrode.

[0048] (5) The photoelectric synaptic devices prepared above exhibit photocurrent responses of different intensities when excited by LED beads with different pulse numbers and pulse frequencies at wavelengths of 365nm, 420nm, 460nm, 520nm and 625nm.

[0049] Example 4

[0050] (1) A 1.5M sucrose aqueous solution was subjected to hydrothermal treatment in a high-pressure autoclave at 200℃ for 120 min; after natural cooling, the filtered carbon spheres were washed repeatedly with water and ethanol, and then dried in a 70℃ oven for 12 h. The synthesized carbon spheres had a particle size of ~3μm. Figure 1 As shown.

[0051] (2) The above carbon spheres were uniformly dispersed in 30 mL of 0.2 M tin tetrachloride solution, stirred for 4 h, filtered, washed 2-3 times with deionized water, and dried in a 70 °C oven for 12 h. The resulting solid powder was placed in a muffle furnace and heated to 500 °C at a heating rate of 4 °C / min, calcined at this temperature for 2 h, and then naturally cooled to obtain a single-shell SnO2. Figure 3 As shown in a.

[0052] (3) The single-shell SnO2, terpineol, and ethyl cellulose prepared above were mixed in a mass ratio of 1:3:3 to form a precursor slurry. The white slurry was then coated onto blank glass using a screen printing method. The glass was heat-treated at 500℃ for 1 hour with a heating rate of 10℃ / min. After rinsing the surface with ethanol to remove dust, the glass was dried and then placed in an ozone cleaner for 15 minutes.

[0053] (4) Place the prepared SnO2 film in a 0.01mM C atmosphere. 44 H 30 N4O 12 After soaking in the solution for 4 hours, the porphyrin molecules physically adsorbed on the surface are cleaned with anhydrous ethanol solution, dried, and then placed in a thermal evaporation apparatus to deposit a Cu metal electrode.

[0054] (5) The photoelectric synaptic devices prepared above exhibit photocurrent responses of different intensities when excited by LED beads with different pulse numbers and pulse frequencies at wavelengths of 365nm, 420nm, 460nm, 520nm and 625nm.

[0055] Example 5

[0056] (1) The above carbon spheres were uniformly dispersed in 30 mL of 0.5 M tin tetrachloride solution, stirred for 4 h, filtered, washed 2-3 times with deionized water, and dried in a 70 °C oven for 12 h. The resulting solid powder was placed in a muffle furnace and heated to 500 °C at a heating rate of 4 °C / min, calcined at this temperature for 2 h, and then naturally cooled to obtain a double-shell SnO2. Figure 2 As shown in a.

[0057] (2) The double-shell SnO2, terpineol, and ethyl cellulose prepared above were mixed in a mass ratio of 1:3:3 to form a precursor slurry. The white slurry was then coated onto blank glass using a screen printing method. The glass was heat-treated at 500℃ for 1 hour with a heating rate of 10℃ / min. After rinsing the surface with ethanol to remove dust, the glass was dried and then placed in an ozone cleaner for 15 minutes.

[0058] (3) Place the prepared SnO2 film in a 0.01mM C atmosphere. 44 H 28 The sample was soaked in ClFeN4O8 solution for 4 hours, and the physically adsorbed porphyrin molecules on the surface were cleaned with anhydrous ethanol solution. After drying, the sample was placed in a thermal evaporation apparatus to deposit a Cu metal electrode. A photograph of the actual sample is shown below. Figure 3 As shown.

[0059] (4) The photoelectric synaptic devices prepared above exhibit photocurrent responses of different intensities when excited by LED beads with different pulse numbers and pulse frequencies at wavelengths of 365nm, 420nm, 460nm, 520nm and 625nm.

[0060] Example 6

[0061] (1) A 1.5M sucrose aqueous solution was subjected to hydrothermal treatment in a high-pressure autoclave at 200℃ for 131 min; after natural cooling, the filtered carbon spheres were washed repeatedly with water and ethanol, and then dried in a 70℃ oven for 12 h. The synthesized carbon spheres had a particle size of ~3μm. Figure 1 As shown.

[0062] (2) The above carbon spheres were uniformly dispersed in 30 mL of 1 M tin tetrachloride solution (water-to-alcohol ratio 1:1), stirred for 6 h, filtered, washed 2-3 times with deionized water, and dried in an 80 °C oven for 12 h. The resulting solid powder was placed in a muffle furnace and heated to 500 °C at a rate of 4 °C / min, and held for 2 h. After natural cooling, a three-shell SnO2 was obtained. Figure 2 As shown in c.

[0063] (3) The three-shell SnO2, terpineol, and ethyl cellulose prepared above were mixed in a mass ratio of 1:3:3 to form a precursor slurry. The white slurry was then screen-printed onto a blank glass substrate and heat-treated at 500℃ for 60 min at a heating rate of 10℃ / min. After rinsing the surface with ethanol to remove dust, the substrate was dried and then placed in an ozone cleaner for 15 min.

[0064] (4) The SnO2 film prepared above was immersed in MAPbIBr2 precursor solution for 2 hours, and after annealing, it was placed in a hot evaporation device to deposit the metal electrode Au electrode.

[0065] (5) The photoelectric synaptic devices prepared above exhibit photocurrent responses of different intensities when excited by LED beads with different pulse numbers and pulse frequencies at wavelengths of 365nm, 420nm, 460nm, 520nm and 625nm.

[0066] Example 7

[0067] (1) A 1.5M sucrose aqueous solution was subjected to hydrothermal treatment in a high-pressure autoclave at 200℃ for 140 min; after natural cooling, the filtered carbon spheres were washed repeatedly with water and ethanol, and then dried in a 70℃ oven for 12 h. The synthesized carbon spheres had a particle size of ~3μm. Figure 1 As shown.

[0068] (2) The above carbon spheres were uniformly dispersed in 30 mL of 0.1 M zinc acetate solution, stirred for 1 h, filtered, washed 2-3 times with deionized water, and dried in a 70 °C oven for 12 h. The resulting solid powder was placed in a muffle furnace and heated to 500 °C at a rate of 4 °C / min, and held for 2 h. After natural cooling, a single-shell ZnO was obtained. Figure 3 As shown in a.

[0069] (3) The single-shell structure ZnO, terpineol, and ethyl cellulose prepared above were mixed in a mass ratio of 1:3:3 to form a precursor slurry. The white slurry was then screen-printed onto blank glass and heat-treated at 500℃ for 60 min at a heating rate of 10℃ / min. After rinsing the surface with ethanol to remove dust, the glass was dried and then placed in an ozone cleaner for 15 min.

[0070] (4) Place the prepared ZnO film in a 0.01 mM C atmosphere. 44 H 30 N4O 12 After soaking in the solution for 2 hours, the porphyrin molecules physically adsorbed on the surface are cleaned with anhydrous ethanol solution, dried, and then placed in a thermal evaporation apparatus to deposit a Cu metal electrode.

[0071] (5) The photoelectric synaptic devices prepared above exhibit photocurrent responses of different intensities when excited by LED beads with different pulse numbers and pulse frequencies at wavelengths of 365nm, 420nm, 460nm, 520nm and 625nm.

[0072] Example 8

[0073] (1) A 1.5M sucrose aqueous solution was subjected to hydrothermal treatment in a high-pressure autoclave at 200℃ for 140 min; after natural cooling, the filtered carbon spheres were washed repeatedly with water and ethanol, and then dried in a 70℃ oven for 12 h. The synthesized carbon spheres had a particle size of ~3μm. Figure 1 As shown.

[0074] (2) The above carbon spheres were uniformly dispersed in 30 mL of 0.2 M zinc acetate solution, stirred for 6 h, filtered, washed 2-3 times with deionized water, and dried in a 70 °C oven for 12 h. The resulting solid powder was placed in a muffle furnace and heated to 500 °C at a rate of 4 °C / min, and held for 2 h. After natural cooling, a double-shell ZnO was obtained. Figure 3 As shown in b.

[0075] (3) The bilayer ZnO, terpineol, and ethyl cellulose prepared above were mixed in a mass ratio of 1:3:3 to form a precursor slurry. The white slurry was then screen-printed onto blank glass and heat-treated at 500℃ for 60 min at a heating rate of 10℃ / min. After rinsing the surface with ethanol to remove dust, the surface was dried and then cleaned in an ozone cleaner for 15 min.

[0076] (4) Place the prepared ZnO film in a 0.01 mM C atmosphere. 44 H 30 N4O 12 After soaking in the solution for 2 hours, the porphyrin molecules physically adsorbed on the surface are cleaned with anhydrous ethanol solution, dried, and then placed in a thermal evaporation apparatus to deposit a Cu metal electrode.

[0077] (5) The photoelectric synaptic devices prepared above exhibit photocurrent responses of different intensities when excited by LED beads with different pulse numbers and pulse frequencies at wavelengths of 365nm, 420nm, 460nm, 520nm and 625nm.

[0078] Example 9

[0079] (1) A 1.5M sucrose aqueous solution was subjected to hydrothermal treatment in a high-pressure autoclave at 200℃ for 140 min; after natural cooling, the filtered carbon spheres were washed repeatedly with water and ethanol, and then dried in a 70℃ oven for 12 h. The synthesized carbon spheres had a particle size of ~3μm. Figure 1 As shown.

[0080] (2) The above carbon spheres were uniformly dispersed in 30 mL of 0.5 M zinc acetate solution (alcohol-to-water ratio 1:5), stirred for 6 h, filtered, washed 2-3 times with deionized water, and dried in a 70 °C oven for 12 h. The resulting solid powder was placed in a muffle furnace and heated to 500 °C at a rate of 4 °C / min, and held for 2 h. After natural cooling, a three-shell ZnO was obtained. Figure 3 As shown in c.

[0081] (3) The three-shell structure ZnO, terpineol, and ethyl cellulose prepared above were mixed in a mass ratio of 1:3:3 to form a precursor slurry. The white slurry was then screen-printed onto blank glass and heat-treated at 500℃ for 60 min at a heating rate of 10℃ / min. After rinsing the surface with ethanol to remove dust, the glass was dried and then placed in an ozone cleaner for 15 min.

[0082] (4) Place the prepared ZnO film in a 0.01 mM C atmosphere. 44 H 30 N4O 12 After soaking in the solution for 2 hours, the porphyrin molecules physically adsorbed on the surface are cleaned with anhydrous ethanol solution, dried, and then placed in a thermal evaporation apparatus to deposit a Cu metal electrode.

[0083] (5) The photoelectric synaptic devices prepared above exhibit photocurrent responses of different intensities when excited by LED beads with different pulse numbers and pulse frequencies at wavelengths of 365nm, 420nm, 460nm, 520nm and 625nm.

[0084] Example 10

[0085] (1) A 1.5M sucrose aqueous solution was subjected to hydrothermal treatment in a high-pressure autoclave at 200℃ for 131 min; after natural cooling, the filtered carbon spheres were washed repeatedly with water and ethanol, and then dried in a 70℃ oven for 12 h. The synthesized carbon spheres had a particle size of ~3μm. Figure 1 As shown.

[0086] (2) The above carbon spheres were uniformly dispersed in 30 mL of 0.2 M zinc acetate solution, stirred for 6 h, filtered, washed 2-3 times with deionized water, and dried in a 70 °C oven for 12 h. The resulting solid powder was placed in a muffle furnace and heated to 500 °C at a rate of 4 °C / min, and held for 2 h. After natural cooling, a double-shell structure ZnO was obtained. Figure 3 As shown in b.

[0087] (3) The double-shelled ZnO hollow spheres, terpineol, and ethyl cellulose prepared above were mixed in a mass ratio of 1:3:3 to form a precursor slurry. The white slurry was then coated onto blank glass using a screen printing method. The glass was heat-treated at 500℃ for 2 hours at a heating rate of 10℃ / min. After rinsing the surface with ethanol to remove dust, the glass was dried and then placed in an ozone cleaner for 15 minutes.

[0088] (4) Place the prepared ZnO film in a 0.01 mM C atmosphere. 44 H 28 The surface was soaked in ClFeN4O8 solution for 2 hours, and the physically adsorbed porphyrin molecules were cleaned with anhydrous ethanol solution. After drying, the surface was placed in a thermal evaporation apparatus to deposit a Cu metal electrode.

[0089] (5) The photoelectric synaptic devices prepared above exhibit photocurrent responses of different intensities when excited by LED beads with different pulse numbers and pulse frequencies at wavelengths of 365nm, 420nm, 460nm, 520nm and 625nm.

[0090] Example 11

[0091] (1) A 1.5M sucrose aqueous solution was subjected to hydrothermal treatment in a high-pressure autoclave at 200℃ for 140 min; after natural cooling, the filtered carbon spheres were washed repeatedly with water and ethanol, and then dried in a 70℃ oven for 12 h. The synthesized carbon spheres had a particle size of ~3μm. Figure 1 As shown.

[0092] (2) The above carbon spheres were uniformly dispersed in 30 mL of 0.5 M zinc acetate solution (alcohol-to-water ratio 1:5), stirred for 6 h, filtered, washed 2-3 times with deionized water, and dried in a 70 °C oven for 12 h. The resulting solid powder was placed in a muffle furnace and heated to 500 °C at a rate of 4 °C / min, and held at that temperature for 2 h. After natural cooling, a three-shell structure ZnO was obtained. Figure 3 As shown in c.

[0093] (3) The three-shell ZnO hollow spheres, terpineol, and ethyl cellulose prepared above were mixed in a mass ratio of 1:3:3 to form a precursor slurry. The white slurry was then screen-printed onto blank glass and heat-treated at 500℃ for 2 hours at a heating rate of 10℃ / min. After rinsing the surface with ethanol to remove dust, the surface was dried and then cleaned in an ozone cleaner for 15 minutes.

[0094] (4) The ZnO film prepared above was immersed in MAPbIBr2 precursor solution for 6 hours, and after annealing, it was placed in a hot evaporation device to deposit the metal electrode Au electrode.

[0095] (5) The photoelectric synaptic devices prepared above exhibit photocurrent responses of different intensities when excited by LED beads with different pulse numbers and pulse frequencies at wavelengths of 365nm, 420nm, 460nm, 520nm and 625nm.

[0096] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A photoelectric synapse device capable of identifying five wavelengths of light, comprising a glass substrate, an active layer of a hollow multi-shell structure of a wide-bandgap metal oxide and a photosensitizer, and a metal electrode.

2. The optoelectronic synaptic device of claim 1, wherein, The hollow multi-shell structure of the metal oxide is any one of TiO2, SnO2, and ZnO.

3. The optoelectronic synaptic device of claim 1, wherein, The hollow multi-shell structure of the metal oxide is any one of single-shell, double-shell, and triple-shell.

4. The optoelectronic synaptic device of claims 1-3, wherein, The photosensitizer is a porphyrin dye or a perovskite.

5. The optoelectronic synaptic device of any one of claims 1-4, wherein, The metal electrode comprises a Cu or Au electrode.

6. The optoelectronic synaptic device of any one of claims 1-5, wherein, Under the test conditions of the photoelectric synapse device, the photocurrent response signal increases with the increase in the number of shells of the hollow multi-shell structure, and after being combined with the photosensitizer, the synaptic plasticity is enhanced, and the current signals of different intensities of five wavelengths of light, including 365 nm, 420 nm, 460 nm, 520 nm, and 625 nm, are achieved. 7.A method for preparing a photoelectric synapse device capable of identifying five wavelengths of light, comprising the following steps: (A) Preparation of a hollow multi-shell structure A 1.5M aqueous solution of sucrose is hydrothermally reacted in an autoclave at 200℃ for 120-140min, and after natural cooling, it is filtered and washed with water and ethanol for several times, and the product is dried in an oven at 70℃ for 12h, and the obtained carbon sphere template has a particle size of about 3μm; the carbon sphere template is uniformly dispersed in a metal salt solution, stirred for 1-6h, filtered, washed with deionized water for 2-3times, and dried in an oven at 70℃ for 12h, and the obtained solid powder is placed in a muffle furnace, heated to 500℃ at a heating rate of 4℃ / min, and kept at a constant temperature for 2h, and after natural cooling, a hollow multi-shell structure is obtained. (B) Preparation of a photoelectric synapse device After the blank glass is ultrasonically cleaned with deionized water, acetone, and alcohol in sequence and dried, the hollow multi-shell structure of the metal oxide obtained in step (A), terpineol, and ethyl cellulose are mixed in a certain proportion, ground into a thick white paste in a mortar, and the white paste is scraped and coated on the blank glass by a screen printing method, and after calcination to remove the organic matter, the surface dust is cleaned with ethanol and dried, and then the glass is cleaned in an ozone cleaning machine for 15min, immersed in a photosensitizer solution, dried, and then electrodeposited in a thermal evaporation instrument.

8. The method of claim 7, wherein the photoelectric synaptic device capable of identifying five wavelengths of light is prepared by the steps of: In step (A), the metal salt is TiCl4, SnCl4·5H2O, or (CH3COO)2Zn·2H2O, the concentration of the titanium salt is 3M, the concentration of the tin salt is 0.2-1M, the concentration of the zinc salt is 0.1-0.5M, and the solvent is deionized water or a mixture of deionized water and ethanol.

9. The method of producing a photoelectrical synaptic device capable of discriminating five wavelengths of light according to any one of claims 7-8, wherein In step (A), the mass ratio of the hollow multi-shell structure of the metal oxide, terpineol, and ethyl cellulose is 1:3:

3.

10. The method of producing a photoelectrical synaptic device capable of discriminating five wavelengths of light according to any one of claims 7 to 9, wherein The heat treatment conditions for calcination to remove the organic matter are as follows: heating to 500℃ at a heating rate of 10℃ / min, and keeping at a constant temperature for 1-2h.

11. The method of producing a photoelectrical synaptic device capable of discriminating five wavelengths of light according to any one of claims 7 to 10, wherein The photosensitizer solution immersion conditions are as follows: immersion in a 0.01mM porphyrin solution for 2-4h or immersion in a perovskite precursor solution for 2-6h.

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