Multifunctional Organic Vertical Diodes Integrating Transient Optical Detection, Energy Conversion, and Neuromorphic Computing Functions and Their Applications

Abstract

The present invention discloses a multifunctional organic vertical diode integrating transient optical detection, energy conversion, and neuromorphic computing functions. The diode includes a glass substrate, an anode material, a hole transport layer, an active layer, an electron transport layer, and a metal cathode that are sequentially connected. The anode material, hole transport layer, active layer, electron transport layer, and metal cathode are sequentially evaporated or spin-coated on the glass substrate to obtain the multifunctional organic vertical diode. The diode of the present invention is a multifunctional organic vertical diode that can realize the functions of optical synapse and energy conversion under forward bias and transient optical detection function under reverse bias under the combined action of the built-in potential and the applied bias voltage, providing a new building unit for self-powered Internet of Things systems.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic optoelectronic sensing and energy storage, and in particular, to a multifunctional organic vertical diode integrating transient light detection, energy conversion, and neuromorphic computing functions and its applications. Background Art

[0002] Organic optoelectronic sensing and energy storage have always been a research hotspot. Effective detection of near-infrared light in the range of 760 - 3000 nanometers is of great significance for optical communication technology, near-infrared image sensors, neuromorphic computing, and biological imaging. Sensing of optical signals in the range of 900 - 950 nanometers is particularly crucial for the above applications because 900 - 950 nanometers has reduced photon scattering and lower sunlight intensity. According to different light response modes, organic optoelectronic sensor devices are divided into organic photodetectors and organic photoreceptors.

[0003] Organic photodetectors can respond quickly to light, while organic photoreceptors respond slowly to light and perform certain processing on light information. However, organic photodetectors that respond to 900 - 950 nanometers generally have problems of low responsivity and low detectivity, and at the same time, there are still few organic photoreceptors that respond to 900 - 950 nanometers.

[0004] The 21st century is the era of information. How to encode and decode information is extremely important. International Morse code is still in use today, and in some special cases, Morse code still plays its key role. Using organic photoreceptors for Morse encoding is of great significance for the development of hardware-based information decoding and encoding. However, the reported Morse encodings are all based on visible light, and in practical applications, it will inevitably interfere with sunlight. Near-infrared light-driven Morse code encoding has become the focus of attention due to its advantages such as good information propagation ability and anti-interference.

[0005] With the rapid development of the Internet of Things and big data, single-functional devices can no longer meet people's needs for miniaturized and multi-functional devices. Integrating optoelectronic sensing and energy storage is of great significance for self-powered Internet of Things systems. There are still few integrated energy conversion, as well as organic photoreceptors and organic photodetectors that respond to 900 - 950 nanometers.

[0006] Through retrieval, no patent disclosure documents related to the present invention patent application have been found. Summary of the Invention

[0007] The purpose of the present invention is to overcome the deficiencies in the prior art and provide a multifunctional organic vertical diode integrating transient light detection, energy conversion, and neuromorphic computing functions and its applications.

[0008] The technical solution adopted by the present invention to solve its technical problems is as follows:

[0009] A multifunctional organic vertical diode integrating transient optical detection, energy conversion, and neuromorphic computing functions. The diode includes a glass substrate, an anode material, a hole transport layer, an active layer, an electron transport layer, and a metal cathode that are sequentially connected. The anode material, hole transport layer, active layer, electron transport layer, and metal cathode are sequentially evaporated or spin-coated on the glass substrate to obtain the multifunctional organic vertical diode.

[0010] Further, the hole transport layer is a hole transport layer material such as copper thiocyanate (CuSCN), 3,4-ethylenedioxythiophene mixed with polystyrene sulfonate (PEDOT:PSS), poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)-benzene (poly-TPD), or nickel oxide (NiO x )

[0011] Further, the active layer is an organic blend heterojunction structure of an organic P-type material and a narrow-bandgap organic n-type material that absorbs in the near-infrared region.

[0012] Further, the active layer is a blend system thin film of the organic P-type material PCE10 and the narrow-bandgap organic n-type material BTPV-4F-eC9 that absorbs in the near-infrared region, with a donor-acceptor mass ratio of 1:1.5, or a blend system thin film of the organic P-type material PTB7-Th and the organic n-type material IEICO-4F, with a donor-acceptor mass ratio of 1:1.2, or a blend system thin film of the organic P-type materials PM7, PM6 and the organic n-type materials BTPV-4F-eC9, BTPV-4Cl-eC9, BTP-4Cl, or BTP-4F, with a donor-acceptor mass ratio of 1:1.2, or a blend system thin film of the organic P-type materials PM7, PM6 and the organic n-type materials BTPV-4F-eC9, BTPV-4Cl-eC9, BTP-4Cl, or BTP-4F, with a donor-acceptor mass ratio of 1:1.2, or a blend system thin film of the organic P-type material PBDB-T and the organic n-type material ITIC, with a donor-acceptor mass ratio of 1:1.2;

[0013] Alternatively, the organic P-type material is an electron donor material of the active layer, and the narrow-bandgap organic n-type material that absorbs in the near-infrared region is an electron acceptor material of the active layer;

[0014] Alternatively, the organic p-type material is: PCE10, or, poly[[4,8-bis[5-(2-ethylhexyl)-4-chloro-2-thienyl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl]-2,5-thiophenediyl[5,7-bis(2-ethylhexyl)-4,8-dioxo-4H,8H-benzo[1,2-c:4,5-c']dithiophene-1,3-diyl]-2,5-thiophenediyl](PM7);

[0015] or, poly([2,6-4,8-bis-((2-ethylhexyl)-thiophen-5-yl)benzo[1,2-B; PBDB-T, poly([2,6'-4,8-bis-((2-ethylhexyl)-thiophen-5-yl)benzoChemicalbook[1,2-B; 3,3-B]dithiophene]-ALT-[1,3-bis-(thiophen-5-yl)-5,7-bis-(2-ethylhexyl)benzo[1,2-C:4,5-C']dithiophene-4,8-dione])(PBDB-T);

[0016] or, poly[2,6′]-4,8-bis(5-ethylhexylthiophene)benzo[1,2-b; 3,3-b]dithiophene{3-fluoro-2[(2-ethylhexyl)carbonyl]thiophene[3,4-b]thiophenediyl})(PTB7-Th)

[0017] or, poly[[4,8-bis[5-(2-ethylhexyl)-4-fluoro-2-thienyl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl]-2,5-thiophenediyl[5,7-bis(2-ethylhexyl)-4,8-dioxo-4H,8H-benzo[1,2-c:4,5-c']dithiophene-1,3-diyl]-2,5-thiophenediyl](PM6);

[0018] Alternatively, the narrow-bandgap organic n-type material that absorbs in the near-infrared region is: IEICO-4F, IECIO-4Cl, 2,2'-[[[6,6,12,12-tetra(4-hexylphenyl)-6,12-dihydrodithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene-2,8-diyl]bis[methylene(3-oxo-1h-indene-2,1(3h)-dimethylene)]]bis[propylamine](ITIC), BTPV-4F-eC9, BTPV-4Cl-eC9, BTP-4Cl, or BTP-4F.

[0019] Furthermore, the electron transport layer is a water-alcohol soluble material such as PFN, PFN-Br, PEIE, PDINN, PDINO, and the electron transport layer material of F3N;

[0020] Alternatively, the electron transport layer is an electron transport layer material of C70 or C60.

[0021] Furthermore, the metal cathode is Al, Ag or Au; alternatively, the anode material is ITO or FTO, and the glass substrate is a transparent substrate or a flexible substrate.

[0022] Furthermore, under zero volts and negative bias voltages, the diode can be used as a transient light detection device, and a high detection rate and responsivity can be obtained; under a forward bias voltage greater than or equal to the built-in potential, the diode can be used as a neuromorphic device; under a forward bias voltage less than or equal to the built-in potential, the diode can be used as an energy conversion device, and a high energy conversion efficiency can be obtained.

[0023] A method for preparing the multifunctional organic vertical diode integrating transient light detection, energy conversion and neuromorphic computing functions is as follows: The diode includes a glass substrate, an anode material, a hole transport layer, an active layer, an electron transport layer and a metal cathode which are connected in sequence. The anode material, the hole transport layer, the active layer, the electron transport layer and the metal cathode are sequentially evaporated or spin-coated on the glass substrate from bottom to top to obtain the multifunctional organic vertical diode.

[0024] (1) Evaporate the anode material on the glass substrate by vacuum evaporation or ion sputtering to obtain a glass substrate with the anode material.

[0025] (2) Ultrasonically clean the glass substrate with the anode material with soapy water, deionized water, acetone and isopropanol for 15 minutes each; after cleaning, dry it with a nitrogen gun, and then perform ultraviolet ozone treatment for more than half an hour for use as the anode of the diode.

[0026] (3) Spin-coat the hole transport layer on the anode.

[0027] (4) Spin-coat the active layer on the hole transport layer.

[0028] (5) Spin-coat the electron transport layer on the active layer; evaporate the metal cathode by vacuum evaporation or ion sputtering. The overlapping part of the metal cathode and the anode is the effective area of the device, and finally form a multifunctional organic optoelectronic diode of Glass / ITO / hole transport layer / active layer / electron transport layer / cathode metal.

[0029] Furthermore, the thickness of the anode material layer is 100 nanometers, the thickness of the active layer film is 100 nanometers, the thickness of the electron transport layer film is 10 nanometers, the thickness of the metal cathode is 100 nanometers, and the thickness of the hole transport layer is 10 nanometers; the effective area of the overlapping part of the metal cathode and the anode in step (5) is 0.04 square centimeters.

[0030] Alternatively, (3) spin-coat the hole transport layer onto the anode at a speed of 2500 revolutions per minute;

[0031] (4) spin-coat the active layer onto the hole transport layer at a speed of 500 - 4000 revolutions per minute;

[0032] (5) spin-coat the electron transport layer onto the active layer at a speed of 2500 revolutions per minute.

[0033] Application of the multifunctional organic vertical diode integrating transient optical detection, energy conversion, and neuromorphic computing functions in contactless heart rate detection and / or data encryption and / or image recognition.

[0034] The advantages and positive effects achieved by the present invention are as follows:

[0035] 1. The diode of the present invention is a multifunctional organic vertical diode that can achieve opto - synaptic and energy conversion functions under forward bias and transient optical detection function under reverse bias under the combined action of built - in potential and applied bias, providing a new building unit for self - powered Internet of Things systems.

[0036] 2. When the diode of the present invention is used as a photodetector at zero volts and reverse bias, it has the characteristics of high responsivity, high detectivity, and self - driving, and can be used to monitor heart rate.

[0037] 3. When the diode of the present invention is used for energy conversion, a short - circuit current of 28.77 mA cm -2 can be obtained, which is one of the highest values of organic solar cells.

[0038] 4. When the diode of the present invention is used as an opto - synapse under a forward bias less than or equal to the built - in potential, it can achieve near - infrared light - driven Morse code encoding and decoding based on synaptic devices and handwritten digit recognition based on convolutional neural networks.

[0039] 5. The manufacturing process of the diode of the present invention is simple and can be prepared by solution method, having important application prospects in indoor Internet of Things and data encryption.

[0040] 6. When the diode of the present invention is used as a self - driving photodetector at 0 V, it exhibits an extremely low dark current density of 0.465 nA cm -2 in the self - driving mode, and the specific detectivity exceeds 10 13 Jones in the wavelength range from 340 nm (ultraviolet) to 1030 nm (near - infrared). The present invention realizes for the first time a synaptic device for near - infrared light - driven Morse code encoding and decoding, and is also the first two - terminal vertical opto - synapse for infrared light - driven Morse code encoding and decoding, providing a new design idea for Internet of Things applications and integrated multifunctional encrypted optical information transmission platforms.

[0041] 7. The diode of the present invention can be used as a transient optical detection device under zero volts and negative bias voltages, having the advantages of high detectivity, high responsivity, and self-driving; under forward bias voltages greater than or equal to the built-in potential, it can be used as a neuromorphic device, capable of performing data encryption of Morse code and recognition of handwritten digits; under forward bias voltages less than or equal to the built-in potential, it is used as an energy conversion device, and a high energy conversion efficiency can be obtained.

[0042] 8. When this device is used as a transient optical detection device under zero volts and negative bias voltages, a responsivity of 0.54 A / W at 900 nm and a detectivity of 4.4E13 can be obtained, and it is used for non-contact heart rate monitoring; under forward bias voltages greater than or equal to the built-in potential, it can be used as an optical synapse to achieve near-infrared light-driven Morse code encoding and decoding; when used as an energy conversion device under forward bias voltages less than or equal to the built-in potential, an energy conversion efficiency of 12.77% and a short-circuit current of 28.87 mA cm -2 can be obtained. Under forward bias voltages greater than or equal to the built-in potential, it can be used as an optical synapse to achieve near-infrared light-driven Morse code encoding and decoding based on synaptic devices and handwritten digit recognition based on convolutional neural networks. Description of the Drawings

[0043] Figure 1 is a schematic structural connection diagram of the multifunctional organic vertical diode in Embodiment 1 of the present invention;

[0044] Figure 2 is a schematic diagram of the transient optical detection function, energy conversion function, and optical synapse function of the multifunctional organic vertical diode in Embodiment 1 of the present invention; among them, a is the current-voltage curve of the device as an energy conversion device under 1 sun, b is the specific detectivity-wavelength curve of the device as a transient optical detection device, and c is the paired pulse stimulation index-time curve of the device as an optical synapse device;

[0045] Figure 3 is a schematic diagram of the negative operation of the multifunctional organic vertical diode in Embodiment 2 of the present invention;

[0046] Figure 4 is a schematic diagram of the transient optical response of the multifunctional organic vertical diode used as a photodetector under negative bias in Embodiment 2 of the present invention; among them, a is the -3dB bandwidth schematic diagram of the device, and b is the transient optical response diagram of the device under 940 nm light illumination of 134 μW cm -2 ;

[0047] Figure 5 is the external quantum efficiency, responsivity-wavelength schematic diagram of the multifunctional organic vertical diode used as a photodetector under negative bias in Embodiment 2 of the present invention;

[0048] Figure 6Schematic diagram of the negative transient optical detection of the multifunctional organic vertical diode for heart rate monitoring in Embodiment 2 of the present invention;

[0049] Figure 7 Schematic diagram of the forward operation of the multifunctional organic vertical diode in Embodiment 3 of the present invention;

[0050] Figure 8 Schematic diagram of the built-in potential of the multifunctional organic vertical diode in Embodiment 3 of the present invention;

[0051] Figure 9 Schematic diagram of the optical synapse of the multifunctional organic vertical diode under a voltage greater than the built-in potential in Embodiment 3 of the present invention;

[0052] Figure 10 Schematic diagram of the forward optical synapse of the multifunctional organic vertical diode for Morse code encoding and decoding in Embodiment 3 of the present invention;

[0053] Figure 11 Schematic diagram of the forward optical synapse of the multifunctional organic vertical diode for ANN network handwritten digit recognition in Embodiment 4 of the present invention.

[0054] Figure 12 Schematic diagram of the recognition rate of digits 0-9 by the forward optical synapse of the multifunctional organic vertical diode for ANN network handwritten digit recognition in Embodiment 4 of the present invention. Detailed implementation manners

[0055] The embodiments of the present invention will be described in detail below. It should be noted that this embodiment is narrative and not restrictive, and the protection scope of the present invention cannot be limited thereby.

[0056] The raw materials used in the present invention are all conventional commercially available products without special instructions; the methods used in the present invention are all conventional methods in the art without special instructions.

[0057] A multifunctional organic vertical diode integrating transient optical detection, energy conversion and neuromorphic computing functions, the diode includes a glass substrate, an anode material, a hole transport layer, an active layer, an electron transport layer and a metal cathode connected in sequence, and the anode material, the hole transport layer, the active layer, the electron transport layer and the metal cathode are sequentially evaporated or spin-coated on the glass substrate to obtain the multifunctional organic vertical diode.

[0058] Preferably, the hole transport layer is a hole transport layer material such as copper thiocyanate (CuSCN), 3,4-ethylenedioxythiophene mixed with polystyrene sulfonate (PEDOT:PSS), poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)-benzene (poly-TPD) or nickel oxide (NiO x ) etc.

[0059] Preferably, the active layer is an organic blend heterojunction structure of an organic P-type material and a narrow-bandgap organic n-type material that absorbs in the near-infrared region.

[0060] Preferably, the active layer is a blend system thin film of an organic P-type material PCE10 and a narrow-bandgap organic n-type material BTPV-4F-eC9 that absorbs in the near-infrared region, with a mass ratio of donor to acceptor of 1:1.5, or a blend system thin film of an organic P-type material PTB7-Th and an organic n-type material IEICO-4F, with a mass ratio of donor to acceptor of 1:1.2, or a blend system thin film of an organic P-type material PM7, PM6 and an organic n-type material BTPV-4F-eC9, BTPV-4Cl-eC9, BTP-4Cl, or BTP-4F, with a mass ratio of donor to acceptor of 1:1.2, or a blend system thin film of an organic P-type material PM7, PM6 and an organic n-type material BTPV-4F-eC9, BTPV-4Cl-eC9, BTP-4Cl, or BTP-4F, with a mass ratio of donor to acceptor of 1:1.2, or a blend system thin film of an organic P-type material PBDB-T and an organic n-type material ITIC, with a mass ratio of donor to acceptor of 1:1.2;

[0061] Alternatively, the organic P-type material is the electron donor material of the active layer, and the narrow-bandgap organic n-type material that absorbs in the near-infrared region is the electron acceptor material of the active layer;

[0062] Alternatively, the organic P-type material is: PCE10, or poly[[4,8-bis[5-(2-ethylhexyl)-4-chloro-2-thienyl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl]-2,5-thiophenediyl[5,7-bis(2-ethylhexyl)-4,8-dioxo-4H,8H-benzo[1,2-c:4,5-c']dithiophene-1,3-diyl]-2,5-thiophenediyl](PM7);

[0063] Or, poly([2,6-4,8-bis-((2-ethylhexyl)-thiophen-5-yl)benzo[1,2-B;PBDB-T, poly([2,6'-4,8-bis-((2-ethylhexyl)-thiophen-5-yl)benzoChemicalbook[1,2-B;3,3-B]dithiophene]-ALT-[1,3-bis-(thiophen-5-yl)-5,7-bis-(2-ethylhexyl)benzo[1,2-C:4,5-C']dithiophene-4,8-dione])(PBDB-T);

[0064] Or, poly[2,6′]-4,8-bis(5-ethylhexylthiophene)benzo[1,2-b;3,3-b]dithiophene]{3-fluoro-2[(2-ethylhexyl)carbonyl]thiophene[3,4-b]thiophenediyl}(PTB7-Th)

[0065] Or, poly[[4,8-bis[5-(2-ethylhexyl)-4-fluoro-2-thienyl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl]-2,5-thiophenediyl[5,7-bis(2-ethylhexyl)-4,8-dioxo-4H,8H-benzo[1,2-c:4,5-c']dithiophene-1,3-diyl]-2,5-thiophenediyl](PM6);

[0066] Alternatively, the narrow-bandgap organic n-type material that absorbs in the near-infrared region is: IEICO-4F, IECIO-4Cl, 2,2'-[[[6,6,12,12-tetrakis(4-hexylphenyl)-6,12-dihydrodithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene-2,8-diyl]bis[methylene(3-oxo-1h-indene-2,1(3h)-dimethylene)]]bis[propylamine](ITIC), BTPV-4F-eC9, BTPV-4Cl-eC9, BTP-4Cl, or BTP-4F.

[0067] Preferably, the electron transport layer is a water-alcohol-soluble material such as PFN, PFN-Br, PEIE, PDINN, PDINO, and F3N;

[0068] Or, the electron transport layer is a material such as C70 or C60.

[0069] Preferably, the metal cathode is Al, Ag, or Au; alternatively, the anode material is ITO or FTO, and the glass substrate is a transparent substrate or a flexible substrate.

[0070] Preferably, at zero volts and negative bias voltages, the diode can be used as a transient photodetector device, and a high detectivity and responsivity can be obtained; at a forward bias voltage greater than or equal to the built-in potential, the diode can be used as a neuromorphic device; at a forward bias voltage less than or equal to the built-in potential, the diode can be used as an energy conversion device, and a high energy conversion efficiency can be obtained.

[0071] The preparation method of the multifunctional organic vertical diode integrating transient optical detection, energy conversion and neuromorphic computing functions is as follows: The diode includes a glass substrate, an anode material, a hole transport layer, an active layer, an electron transport layer and a metal cathode which are connected in sequence. The anode material, the hole transport layer, the active layer, the electron transport layer and the metal cathode are deposited or spin-coated on the glass substrate from bottom to top to obtain the multifunctional organic vertical diode.

[0072] (1) Deposit the anode material on the glass substrate by vacuum evaporation or ion sputtering to obtain a glass substrate with the anode material.

[0073] (2) Ultrasonically clean the glass substrate with the anode material in soapy water, deionized water, acetone and isopropanol for 15 minutes each step; after cleaning, dry it with a nitrogen gun, and then perform ultraviolet ozone treatment for more than half an hour for use as the anode of the diode.

[0074] (3) Spin-coat the hole transport layer on the anode.

[0075] (4) Spin-coat the active layer composed of a bulk heterojunction mixed solution of an organic P-type material and a narrow-bandgap organic n-type material that absorbs in the near-infrared region on the hole transport layer.

[0076] (5) Spin-coat the electron transport layer on the active layer; deposit the metal cathode by vacuum evaporation or ion sputtering. The overlapping part where the metal cathode and the anode cross is the effective area of the device, and finally form a multifunctional organic optoelectronic diode of Glass / ITO / hole transport layer / active layer / electron transport layer / cathode metal.

[0077] Preferably, the thickness of the anode material layer is 100 nm, the thickness of the active layer film is 100 nm, the thickness of the electron transport layer film is 10 nm, the thickness of the metal cathode is 100 nm, and the thickness of the hole transport layer is 10 nm; the effective area of the overlapping part where the metal cathode and the anode cross in step (5) is 0.04 square centimeters.

[0078] Or, (3) Spin-coat the hole transport layer on the anode at a speed of 2500 revolutions per minute.

[0079] (4) Spin-coat the active layer on the hole transport layer at a speed of 500 - 4000 revolutions per minute.

[0080] (5) Spin-coat the electron transport layer on the active layer at a speed of 2500 revolutions per minute.

[0081] The application of the multifunctional organic vertical diode integrating transient optical detection, energy conversion and neuromorphic computing functions in non-contact heart rate detection and / or data encryption and / or image recognition.

[0082] Specifically, the relevant preparation and detection examples are as follows:

[0083] Example 1

[0084] As Figure 1 shown, a multifunctional organic vertical diode, whose device structure sequentially includes a substrate 1, an anode material 2, a hole transport layer 3, an active layer 4, an electron transport layer 5, and a cathode 6.

[0085] The substrate 1 is glass, the anode material 2 is ITO or Au with a thickness of 100 nanometers. The hole transport layer is a hole transport layer material such as cuprous thiocyanate (CuSCN), 3,4-ethylenedioxythiophene blended with poly(styrenesulfonate) (PEDOT:PSS), poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)-benzene (poly-TPD), and nickel oxide (NiOx). A blend system (donor-acceptor ratio of 1:1.5) thin film of the organic P-type material PCE10 and the narrow-bandgap organic n-type material BTPV-4F-eC9 that absorbs in the near-infrared region, or a blend system (donor-acceptor ratio of 1:1.2) thin film of the organic P-type material PTB7-Th and the organic n-type material IEICO-4F, as well as other possible organic blend heterojunction structures, with a film thickness of 100 nanometers. The electron transport layer 5 is 3,3'-(1,3,8,10-tetraanthra[2,1,9-def:6,5,10-d'e'f']diisoquinoline-2,9(1H,3H,8H,10H)-diyl)bis(N,N-dimethylpropane-1-amine oxide) (PDINO), 2,9-bis(3-((3-(dimethylamino)propyl)amino)propyl)-3,3'-(1,3,8,10-tetraanthra[2,1,9-def:6,5,10-d'e'f']diisoquinoline) (PDINN), F3N, C70, C60, etc. The cathode 6 is metal aluminum, silver, etc., with a thickness of 110 nanometers.

[0086] The preparation method of a multifunctional organic vertical diode described in this example is as follows:

[0087] (1) Evaporate the anode material by vacuum evaporation or ion sputtering for 100 nanometers;

[0088] (2) Ultrasonically clean the glass substrate with the anode using soapy water, deionized water, acetone, and isopropanol for 15 minutes each. Subsequently, perform ultraviolet ozone treatment for more than half an hour and use it as the anode of the diode;

[0089] (3) Spin-coat the hole transport layer on the anode at a suitable rotation speed (2500 revolutions per minute);

[0090] (4) The active layer composed of a bulk heterojunction mixed solution of an organic P-type material and a narrow-bandgap organic n-type material that absorbs in the near-infrared region is spin-coated on the hole transport layer at an appropriate rotation speed (500 - 4000 revolutions per minute);

[0091] (5) The electron transport layer is spin-coated on the active layer at an appropriate rotation speed (2500 revolutions per minute); The cathode metal is deposited by vacuum evaporation or ion sputtering to a thickness of 100 nanometers. The overlapping part where the cathode metal and the anode material cross is the effective area of the device, which is 0.04 square centimeters. Finally, a multifunctional organic optoelectronic diode of Glass / anode / hole transport layer / active layer / electron transport layer / cathode metal is formed.

[0092] Appendix Figure 2 shows the different functions of the multifunctional organic vertical diode involved in this embodiment under different applied bias voltages. As Figure 2 shown in a, it is used as an energy conversion device under a forward bias voltage less than or equal to the built-in potential. The open-circuit voltage is 0.67V, and the short-circuit current is 28.87 mA cm -2 , and the energy conversion efficiency is 12.77%. As Figure 2 shown in b, under zero volts and negative bias voltages, the device is used as a transient light detection device. After the light is turned on, the photocurrent immediately rises to the maximum value and remains stable. After the light is turned off, the photocurrent immediately decays to the initial position. The specific detectivity of the device in the wavelength range from 340 nm (ultraviolet) to 1030 nm (near-infrared) exceeds 10 13 Jones in the self-driven mode (0V). The peak specific detectivity at 900 nm is 4.43E13 Jones. Under a forward bias voltage greater than or equal to the built-in potential, the device can be used as a neuromorphic device. After the light is turned on, the photocurrent slowly rises with the increase of the illumination time. After the light is turned off, the photocurrent slowly decays, which is similar to the process of a living organism responding to stimuli.

[0093] Example 2

[0094] Test for monitoring heart rate when the multifunctional organic vertical diode is used as a photodetector under a negative bias voltage:

[0095] As Figure 3 shown, when the multifunctional organic vertical diode operates under a negative bias voltage, the ITO is connected to the negative terminal and the metal cathode is connected to the positive terminal. Appendix Figure 4 a shows the -3dB bandwidth schematic diagram of the multifunctional organic vertical diode used as a photodetector under a negative bias voltage. As can be seen from the figure, the light response bandwidth of the device for 940 nm light is greater than 10 5 Hz, far higher than the requirements of practical applications. Appendix Figure 4b shows the schematic diagram of the normalized transient optical response of the multifunctional organic vertical diode used as a photodetector under reverse bias. As can be seen from the figure, the rise and fall speeds of the device's optical response to 940 nm light are 8 μs and 6 μs, respectively. Attached Figure 5 shows the schematic diagrams of the external quantum efficiency, responsivity and wavelength of the multifunctional organic vertical diode used as a photodetector under reverse bias. The EQE of the device obtained at 430 - 960 nm is greater than 60%, the responsivity at 760 - 950 nm is about 0.5 A / W, and the peak responsivity at 900 nm is 0.54 A / W, comparable to or exceeding that of commercial inorganic silicon detectors. The results obtained when the fabricated multifunctional organic vertical diode is used for transmissive PPG testing under reverse bias are as Figure 6 . The signals of the tester's contraction and relaxation can be clearly observed in the figure, and the normal heart rate is 84 beats per minute.

[0096] Example 3

[0097] When the multifunctional organic vertical diode is used as a neuromorphic device under a forward bias greater than or equal to the built-in potential, it is used for the test of Morse code encoding:

[0098] As Figure 6 shown, when the multifunctional organic vertical diode operates under forward bias, ITO is connected to the positive terminal and the metal cathode is connected to the negative terminal. Attached Figure 7 shows the test chart of the device's built-in potential. As can be seen from the figure, the built-in potential of the device is 0.67 V. Under a forward bias greater than 0.67 V, the device exhibits neuromorphic device behavior. Under a forward bias greater than 0.67 V, the device exhibits neuromorphic device behavior. Under a forward bias from 0 V to 0.67 V, the device is used as an energy conversion device. Under 0 V and reverse bias, the device is used as a transient light detection device. Attached Figure 8 shows the neuromorphic device behavior of the device under different numbers of 915-nm light stimulation conditions. With the increase in the number of stimulations, the post-stimulus current of the device increases significantly, and the time to decay to the dark state is significantly enhanced. Attached Figure 9 shows the test of the multifunctional organic vertical diode for driving Morse code encoding UCAS, OPES by near-infrared (915 nm) light. Different illumination times can be used to replace dots and dashes to complete Morse code encoding. The letters UCAS and OPES can be distinguished by the post-stimulus current under different light stimulations and the current decay at a fixed time.

[0099] Example 4

[0100] When the multifunctional organic vertical diode is used as a neuromorphic device under a forward bias greater than or equal to the built-in potential, it is used for the test of handwritten digit recognition based on the ANN network.

[0101] Figure 10The schematic diagram of the device conductivity versus the number of light stimulations is given. As can be seen from the figure, an approximately linear conductivity update with the number of stimulations is found in the device.

[0102] Figure 11 The schematic diagram of the device for the handwritten digit recognition test based on the ANN network is given. As can be seen from the figure, the sub-linear conductivity update of the device is used as the input.

[0103] Figure 12 The recognition results of the device for handwritten digits from 0 to 9 are given. From Figure 12 which it can be seen that a small gap is found in the device between the number of samples tested and the number of samples correctly recognized, suggesting the potential of the device as a neuromorphic device.

[0104] Although embodiments of the present invention are disclosed for illustrative purposes, those skilled in the art can understand that various substitutions, variations, and modifications are possible without departing from the spirit and scope of the present invention and the appended claims. Therefore, the scope of the present invention is not limited to the content disclosed in the embodiments.

Claims

1. A multifunctional organic vertical diode integrating transient optical detection, energy conversion, and neuromorphic computing functions, characterized in that: The diode includes a glass substrate, an anode material, a hole transport layer, an active layer, an electron transport layer, and a metal cathode that are sequentially connected. The anode material, hole transport layer, active layer, electron transport layer, and metal cathode are sequentially evaporated or spin-coated on the glass substrate to obtain a multifunctional organic vertical diode.

2. The multifunctional organic vertical diode integrating transient optical detection, energy conversion, and neuromorphic computing functions according to claim 1, wherein: The hole transport layer is cuprous thiocyanate, a mixture of 3,4-ethylenedioxythiophene and polystyrene sulfonate, poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)-benzene or nickel oxide.

3. The multifunctional organic vertical diode integrating transient optical detection, energy conversion, and neuromorphic computing functions according to claim 1, characterized in that: The active layer is an organic blend heterojunction structure of an organic P-type material and a narrow-bandgap organic n-type material that absorbs in the near-infrared region.

4. The multifunctional organic vertical diode integrating transient optical detection, energy conversion, and neuromorphic computing functions according to claim 3, characterized in that: The active layer is a blend system thin film of an organic P-type material PCE10 and a narrow-bandgap organic n-type material BTPV-4F-eC9 that absorbs in the near-infrared region, with a mass ratio of donor to acceptor of 1:1.5, or a blend system thin film of an organic P-type material PTB7-Th and an organic n-type material IEICO-4F, with a mass ratio of donor to acceptor of 1:1.2, or a blend system thin film of an organic P-type material PM7, PM6 and an organic n-type material BTPV-4F-eC9, BTPV-4Cl-eC9, BTP-4Cl, or BTP-4F, with a mass ratio of donor to acceptor of 1:1.2, or a blend system thin film of an organic P-type material PM7, PM6 and an organic n-type material BTPV-4F-eC9, BTPV-4Cl-eC9, BTP-4Cl, or BTP-4F, with a mass ratio of donor to acceptor of 1:1.2, or a blend system thin film of an organic P-type material PBDB-T and an organic n-type material ITIC, with a mass ratio of donor to acceptor of 1:1.2; Alternatively, the organic P-type material is an electron donor material for the active layer, and the narrow-bandgap organic n-type material that absorbs in the near-infrared region is an electron acceptor material for the active layer; Alternatively, the organic P-type material is: PCE10, or poly[[4,8-bis[5-(2-ethylhexyl)-4-chloro-2-thienyl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl]-2,5-thiophenediyl[5,7-bis(2-ethylhexyl)-4,8-dioxo-4H,8H-benzo[1,2-c:4,5-c']dithiophene-1,3-diyl]-2,5-thiophenediyl]; Or, poly([2,6-4,8-bis-((2-ethylhexyl)-thiophen-5-yl)benzo[1,2-B; PBDB-T, poly([2,6'-4,8-bis-((2-ethylhexyl)-thiophen-5-yl)benzoChemicalbook[1,2-B; 3,3-B]dithiophene]-ALT-[1,3-bis-(thiophen-5-yl)-5,7-bis-(2-ethylhexyl)benzo[1,2-C:4,5-C']dithiophene-4,8-dione]); Or, poly[2,6′]-4,8-bis(5-ethylhexylthiophene)benzo[1,2-b;3,3-b]dithiophene{3-fluoro-2[(2-ethylhexyl)carbonyl]thiophene[3,4-b]thiophenediyl}) Or, poly[[4,8-bis[5-(2-ethylhexyl)-4-fluoro-2-thienyl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl]-2,5-thiophenediyl[5,7-bis(2-ethylhexyl)-4,8-dioxo-4H,8H-benzo[1,2-c:4,5-c']dithiophene-1,3-diyl]-2,5-thiophenediyl; Alternatively, the narrow-bandgap organic n-type material that absorbs in the near-infrared region is: IEICO-4F, IECIO-4Cl, 2,2'-[[[6,6,12,12-tetrakis(4-hexylphenyl)-6,12-dihydrodithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene-2,8-diyl]bis[methylene(3-oxo-1h-indene-2,1(3h)-dimethylene)]]bis[propylamine] (ITIC), BTPV-4F-eC9, BTPV-4Cl-eC9, BTP-4Cl, or BTP-4F.

5. The multifunctional organic vertical diode integrating transient optical detection, energy conversion and neuromorphic computing functions according to claim 1, characterized in that: The electron transport layer is a water-alcohol-soluble material PFN, PFN-Br, PEIE, PDINN, PDINO, and the electron transport layer material of F3N; Alternatively, the electron transport layer is the electron transport layer material of C70 and C60.

6. The multifunctional organic vertical diode integrating transient optical detection, energy conversion, and neuromorphic computing functions according to claim 1, wherein: The metal cathode is Al, Ag, or Au; alternatively, the anode material is ITO or FTO, and the glass substrate is a transparent substrate or a flexible substrate.

7. The multifunctional organic vertical diode integrating transient optical detection, energy conversion, and neuromorphic computing functions according to any one of claims 1 to 6, characterized in that: Under zero volts and negative bias voltages, the diode can be used as a transient photodetector device; Under a forward bias voltage greater than or equal to the built-in potential, the diode can be used as a neuromorphic device; Under a forward bias voltage less than or equal to the built-in potential, the diode can be used as an energy conversion device.

8. The preparation method of the multifunctional organic vertical diode integrating transient optical detection, energy conversion and neuromorphic computing functions according to any one of claims 1 to 7, characterized in that: The steps are as follows: The diode includes a glass substrate, an anode material, a hole transport layer, an active layer, an electron transport layer, and a metal cathode that are sequentially connected. The anode material, the hole transport layer, the active layer, the electron transport layer, and the metal cathode are sequentially evaporated or spin-coated on the glass substrate from bottom to top to obtain a multifunctional organic vertical diode. (1) Evaporate the anode material on the glass substrate by vacuum evaporation or ion sputtering to obtain a glass substrate with the anode material; (2) Ultrasonically clean the glass substrate with the anode material with soapy water, deionized water, acetone, and isopropyl alcohol for 15 minutes each step; after cleaning, dry it with a nitrogen gun, and then treat it with ultraviolet ozone for more than half an hour for use as the anode of the diode; (3) Spin-coat the hole transport layer on the anode; (4) Spin-coat the active layer on the hole transport layer; (5) Spin-coat the electron transport layer on the active layer; deposit the metal cathode by vacuum evaporation or ion sputtering. The overlapping part of the intersection of the metal cathode and the anode is the effective area of the device, and finally form a multifunctional organic optoelectronic diode of Glass / ITO / hole transport layer / active layer / electron transport layer / cathode metal.

9. The multifunctional organic vertical diode integrating transient optical detection, energy conversion and neuromorphic computing functions according to claim 8, characterized in that: The thickness of the anode material layer is 100 nm, the thickness of the active layer film is 100 nm, the thickness of the electron transport layer film is 10 nm, the thickness of the metal cathode is 100 nm, and the thickness of the hole transport layer is 10 nm; in the step (5), the effective area of the overlapping part of the intersection of the metal cathode and the anode is 0.04 square centimeters; Alternatively, (3) Spin-coat the hole transport layer on the anode at a speed of 2500 revolutions per minute; (4) Spin-coat the active layer on the hole transport layer at a speed of 500 - 4000 revolutions per minute; (5) Spin-coat the electron transport layer on the active layer at a speed of 2500 revolutions per minute.

10. Application of the multifunctional organic vertical diode integrating transient light detection, energy conversion and neuromorphic computing functions in non-contact heart rate detection and / or data encryption and / or image recognition as claimed in any one of claims 1 to 7.

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