Flexible wide-spectrum organic phototransistor based on polymer micron line array and preparation method thereof

Abstract

The invention relates to the technical field of organic photoelectric devices, in particular to a flexible wide-spectrum organic photoelectric transistor based on a polymer micron line array and a preparation method of the flexible wide-spectrum organic photoelectric transistor. The flexible wide-spectrum organic phototransistor comprises a substrate, a grid electrode arranged on the substrate, a dielectric layer arranged on the grid electrode, a source electrode and a drain electrode which are arranged on the dielectric layer, and an organic polymer micron line array arranged between the source electrode and the drain electrode, the organic polymer micro-wire array is a PTQ10 micro-wire array which is assembled through capillary liquid bridge confinement. According to the flexible wide-spectrum organic phototransistor disclosed by the invention, the PTQ10 micron line array is used as a channel material, efficient carrier transmission is realized by utilizing highly ordered accumulation of PTQ10 molecules, and the mobility and responsivity of a device are improved.

Description

Technical Field

[0001] The invention relates to the technical field of organic photoelectric devices, and in particular to a flexible wide-spectrum organic photoelectric transistor based on a polymer micrometer line array and a preparation method thereof. Background Art

[0002] Wide-spectrum organic phototransistors can simultaneously detect ultraviolet, visible and near-infrared light, and have broad application prospects in biomedical engineering and artificial intelligence. Wide-spectrum organic phototransistors based on polymer organic semiconductor materials have the advantages of flexibility, low power consumption, low cost, and simple preparation process. They are compatible with future artificial intelligence, wearable electronics and implantable electronics, and have been widely studied. For example: The patent document with publication number CN117580380A discloses an organic bulk heterojunction vertical phototransistor based on polymers PDVT-10 and Y6, which combines the advantages of vertical structure and bulk heterojunction, so that the light detection performance of organic phototransistors is improved; the patent document with publication number CN116390607A discloses a Schiff base nitrogen-functionalized PPAB molecule, which has high planarity and therefore has a higher conjugation length, which is conducive to the improvement of carrier mobility, and an organic phototransistor is made based on the polymer.

[0003] Due to the weak interaction between polymer chains, organic polymer semiconductor films prepared by traditional spin coating, blade coating, inkjet printing and other methods are usually disordered, and the carrier transport of the device is limited, resulting in low mobility and responsiveness of the device. Therefore, a simple and efficient method is needed to enhance the orderly stacking of organic polymer semiconductors, thereby improving the key performance indicators of the device such as mobility and responsiveness. Summary of the invention

[0004] The present invention provides a flexible wide-spectrum organic phototransistor based on a polymer micrometer line array and a preparation method thereof, so as to solve the above-mentioned problems existing in the prior art.

[0005] According to a first aspect of the present invention, the present invention provides a flexible wide-spectrum organic phototransistor based on a polymer microwire array, comprising a substrate, a gate arranged on the substrate, a dielectric layer arranged on the gate, a source and a drain arranged on the dielectric layer, and an organic polymer microwire array arranged between the source and the drain; the organic polymer microwire array is a PTQ10 microwire array assembled by capillary liquid bridge confinement.

[0006] It should be noted that the capillary liquid bridge confined assembly utilizes the different capillary suction forces between the substrate and the top and bottom ends of the silicon column template and the asymmetric wettability of the silicon column template to control the precursor solution filled in the template and the substrate to form a capillary liquid bridge at the top of the silicon column microcolumn, inducing the liquid bridge to be anchored by the gas-liquid-solid three-phase line and move in a directional manner, and realizing the directional nucleation and growth of the polymer through the directional dewetting process of the liquid bridge.

[0007] The molecular structure of PTQ10 is: .

[0008] Experiments have found that the present invention uses PTQ10 micrometer line array as the channel material in the flexible wide-spectrum organic phototransistor, and utilizes the highly ordered stacking of PTQ10 molecules to achieve efficient carrier transport and improve the mobility and responsiveness of the device. The present invention uses PTQ10 as an organic polymer semiconductor material. Compared with materials such as single crystal silicon and polycrystalline silicon, this material has the advantages of low price, easy solution processing, and mechanical flexibility. Compared with other organic polymer semiconductor materials, this material has a wide absorption range from ultraviolet to visible light.

[0009] In order to achieve more efficient carrier transport and improve the mobility and responsiveness of the device, further, the number average molecular weight of the organic polymer in the organic polymer microwire array is 5-500 kDa (preferably 20-50 kDa); and / or, in the organic polymer microwire array, the width of the microwire is 1-3 μm, the thickness is 100-1500 nm, and the spacing between adjacent microwires is 3-7 μm.

[0010] In order to improve the bendability and photoelectric performance of organic phototransistors, the present invention makes the following special restrictions on the materials and thicknesses of the substrate, gate, dielectric layer, source and drain, so that the device itself is flexible and has excellent photoelectric performance, and is compatible with future artificial intelligence, wearable electronics and implantable electronics.

[0011] Furthermore, the substrate is PET with a thickness of 50-1000 μm.

[0012] Furthermore, the gate is a 20-400 nm thick gold, silver, aluminum or copper film.

[0013] Furthermore, the dielectric layer is a PVP film with a thickness of 100-500 nm.

[0014] Furthermore, the source electrode and the drain electrode are each independently a 20-100 nm thick gold, silver, aluminum or copper film.

[0015] According to a second aspect of the present invention, the present invention also provides a method for preparing the above-mentioned flexible wide-spectrum organic phototransistor, comprising the following steps: Step (1): providing a substrate; Step (2): preparing a gate on a substrate; Step (3): preparing a dielectric layer on the gate; Step (4): preparing a source electrode and a drain electrode on the dielectric layer; Step (5): Install a template above the source and drain electrodes, drip a PTQ10 solution onto the surface of the template so that the PTQ10 solution fills the gap between the source and drain electrodes and covers the source and drain electrodes at the same time, and dry the template to evaporate the solvent, thereby obtaining the flexible wide-spectrum organic phototransistor.

[0016] The preparation method of the flexible wide-spectrum organic phototransistor of the present invention adopts a template-induced polymer solution dewetting method to prepare a uniform morphology and orderly stacked polymer one-dimensional micrometer wire array on a flexible substrate. The array has a wide spectrum absorption capacity in the ultraviolet-visible band, so that the flexible organic field-effect transistor with a polymer one-dimensional micro-nanowire array has a wide spectrum detection capability, and has high mobility and response performance. The overall preparation process of the device is simple, and the experimental conditions are low, which provides a new idea for the preparation and integration of flexible wide-spectrum organic phototransistors.

[0017] Furthermore, in step (5), the concentration of PTQ10 in the PTQ10 solution is 5-30 mg / ml (preferably 10-30 mg / ml), and the solvent is chlorobenzene, toluene or chloroform (preferably chlorobenzene). By limiting the concentration of PTQ10 and the type of solvent in the PTQ10 solution, the mobility and responsiveness of the device can be improved.

[0018] Furthermore, in step (5), the drying temperature is 60-120°C and the drying time is 5-20 hours. By limiting the drying temperature and time, the solvent in the PTQ10 solution can be effectively removed to form an ordered PTQ10 micrometer wire array and improve the device performance.

[0019] Furthermore, the template is a silicon column template; preferably, the silicon column template is a silicon column template with asymmetric wettability.

[0020] In a specific application process, the template is a silicon column template of a micro-column structure, and its manufacturing process is: using photolithography to prepare a silicon column array structure. The size and distribution of the silicon columns in the silicon column array structure directly affect the distribution of the polymer micrometer line array on the phototransistor obtained later. In order to obtain micrometer line arrays of different specifications, silicon column arrays of different specifications can be prepared.

[0021] In the specific application process, the silicon column template needs to be treated with asymmetric infiltration. The specific operation is as follows: (1) The surface of the silicon pillar is treated with oxygen plasma to make it hydrophilic.

[0022] (2) Spin-coat the photoresist RZJ-304-50 on the silicon dioxide substrate, and cover the photoresist-spin-coated surface of the silicon dioxide substrate on the silicon column template, so that the photoresist adheres to the top of the silicon column on the silicon column template.

[0023] (3) The silicon column template and octadecyltrichlorosilane are placed together in a vacuum desiccator for high-temperature reaction. The octadecyltrichlorosilane molecules will adhere to the side walls of the silicon columns in the silicon column template, making them hydrophobic.

[0024] (4) Use acetone to wash away the photoresist on the top of the silicon column to obtain a silicon column template with asymmetric wettability.

[0025] Furthermore, the step (1) is specifically as follows: using deionized water, methanol, ethanol, or isopropanol to clean the substrate and blow dry it, and then treating the cleaned substrate with UVO for 5-30 min. Through the above pretreatment, the effect of cleaning the substrate can be achieved, the surface properties of the substrate can be improved, and its interface compatibility with other materials can be improved.

[0026] Furthermore, the step (2) is specifically as follows: placing the substrate into a vacuum coating device, wherein the vacuum degree in the vacuum coating device reaches 5×10 -4 When the evaporation source is turned on, the evaporation rate of the metal is controlled, and a metal deposition layer is evaporated to serve as a gate; preferably, the evaporation rate is 1-5 Å / s and the thickness is 20-100 nm. Deposition by evaporation is conducive to achieving high-purity, high-crystallinity films, improving the mobility and stability of the device, and thus improving the overall device performance.

[0027] Furthermore, the step (3) is specifically as follows: preparing a certain concentration of PVP aqueous solution, taking a certain amount of PVP aqueous solution and evenly spin-coating it on the gate, and then performing annealing treatment to form a dielectric layer on the gate; preferably, the concentration of the PVP aqueous solution is 1-5 wt%, the amount is 10-500 μl, the spin-coating speed is 500-3000 rpm, the spin-coating time is 15-120 s, the annealing temperature is 80-160 ° C, and the annealing time is 1-15 h. Spin coating is conducive to forming a dielectric layer with good film uniformity, thereby improving the overall device performance.

[0028] Furthermore, the step (4) is specifically as follows: placing the sample of the spin-coated dielectric layer into a vacuum coating device, wherein the vacuum degree in the vacuum coating device reaches 5×10 -4When the evaporation source is turned on, the evaporation rate of the metal is controlled, and a metal deposition layer is evaporated to serve as the source and drain; preferably, the evaporation rate is 1-5 Å / s and the thickness is 20-100 nm. Deposition by evaporation is conducive to achieving high-purity, high-crystallinity films, improving the mobility and stability of the device, and thus improving the overall device performance.

[0029] Beneficial effects of the present invention: The flexible wide-spectrum organic phototransistor based on polymer micrometer wire array provided by the present invention uses PTQ10 as an organic polymer semiconductor material. Compared with materials such as single crystal silicon and polycrystalline silicon, this material has the advantages of low price, easy solution processing, and mechanical flexibility; compared with other organic polymer semiconductor materials, this material has a wide absorption range from ultraviolet to visible light. The PTQ10 molecules in the PTQ10 micrometer wire array assembled by capillary liquid bridge confinement are highly orderly stacked, which can realize efficient carrier transmission of the transistor and improve the mobility and responsiveness of the device.

[0030] The present invention provides a flexible wide-spectrum organic phototransistor based on a polymer micrometer wire array, which has a bendable substrate, a gate, a dielectric layer, a source and drain, and a semiconductor layer, so that the device itself is flexible and compatible with future artificial intelligence, wearable electronics, and implantable electronics. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the technical solutions in the present invention or the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0032] Figure 1 This is a schematic structural diagram of a flexible wide-spectrum organic phototransistor according to Example 1 of the present invention.

[0033] Figure 2 This is a scanning electron microscope image of the silicon pillar template used in the embodiment of the present invention.

[0034] Figure 3 This is an optical microscope photograph of the organic polymer PTQ 10 micron line array used in Example 1 of the present invention.

[0035] Figure 4 This is the absorption spectrum of the organic polymer PTQ 10 micron line array used in Example 1 of the present invention.

[0036] Figure 5 The flexible wide-spectrum organic phototransistor of Example 1 of the present invention in the dark state and under different illumination conditions (different wavelengths, the power is 8 mW cm-2 ) transfer curve.

[0037] Figure 6 The wide-spectrum organic phototransistor of Comparative Example 1 of the present invention in the dark state and under different illumination conditions (different wavelengths, the power is 8 mW cm -2 ) transfer curve.

[0038] Figure 7 The mobility performance comparison of the flexible wide-spectrum organic phototransistor of Example 1 of the present invention after being bent 100, 200, and 500 times.

[0039] Figure 8 The flexible wide-spectrum organic phototransistor of Example 2 in the dark state and under different illumination conditions (different wavelengths, the power is 8 mW cm -2 ) transfer curve.

[0040] Fig. 9 The flexible wide-spectrum organic phototransistor of Example 3 in the dark state and under different illumination conditions (different wavelengths, the power is 8 mW cm -2 ) transfer curve.

[0041] Fig.10 The flexible wide-spectrum organic phototransistor of Example 4 in the dark state and under different illumination conditions (different wavelengths, the power is 8 mW cm -2 ) transfer curve.

[0042] Fig.11 The flexible wide-spectrum organic phototransistor of Example 5 in the dark state and under different illumination conditions (different wavelengths, the power is 8 mW cm -2 ) transfer curve.

[0043] Fig.12 The flexible wide-spectrum organic phototransistor of Example 6 in the dark state and under different illumination conditions (different wavelengths, the power is 8 mW cm -2 ) transfer curve.

[0044] Fig.13 The wide-spectrum organic phototransistor of comparative example 2 in the dark state and under different illumination conditions (different wavelengths, the power is 8 mW cm -2 ) transfer curve.

[0045] Fig.14 The wide-spectrum organic phototransistor of comparative example 3 in the dark state and under different illumination conditions (different wavelengths, the power is 8 mW cm -2 ) transfer curve.

[0046] Reference numerals: 1: substrate; 2: gate; 3: dielectric layer; 4: source; 4': drain; 5: organic polymer micrometer line array. DETAILED DESCRIPTION

[0047] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be clearly and completely described below in conjunction with the drawings of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0048] The silicon column templates used in the following examples are all asymmetric wettability silicon column templates. The specific operations are as follows: (1) The surface of the silicon pillar is treated with oxygen plasma to make it hydrophilic.

[0049] (2) Spin-coat the photoresist RZJ-304-50 on the silicon dioxide substrate, and cover the photoresist-spin-coated surface of the silicon dioxide substrate on the silicon column template, so that the photoresist adheres to the top of the silicon column on the silicon column template.

[0050] (3) The silicon column template and octadecyltrichlorosilane are placed together in a vacuum desiccator for high-temperature reaction. The octadecyltrichlorosilane molecules will adhere to the side walls of the silicon columns in the silicon column template, making them hydrophobic.

[0051] (4) Use acetone to wash away the photoresist on the top of the silicon column to obtain a silicon column template with asymmetric wettability.

[0052] Example 1 This embodiment provides a flexible wide-spectrum organic phototransistor based on a polymer microwire array, such as Figure 1 As shown, it includes a substrate 1, a gate 2 arranged on the substrate, a dielectric layer 3 arranged on the gate, a source 4 and a drain 4' arranged on the dielectric layer, and an organic polymer micrometer wire array 5 arranged between the source and the drain.

[0053] The substrate 1 is PET with a thickness of 475 μm. The gate 2 is a 200 nm thick silver film. The dielectric layer 3 is a PVP film with a thickness of 200 nm. The source 4 and the drain 4' are 50 nm thick gold films. The organic polymer micrometer wire array 5 is a PTQ10 micrometer wire array assembled by capillary liquid bridge confinement, with a micrometer wire width of 2 μm, a thickness of 1 μm, and a spacing of 5 μm between adjacent micrometer wires. The number average molecular weight Mn of PTQ10 is 20-50 kDa.

[0054] The preparation method thereof comprises the following steps: (1) The PET substrate was cleaned and dried with deionized water, methanol, ethanol, and isopropanol, and then treated with UVO for 20 min.

[0055] (2) Place the cleaned PET substrate into the vacuum coating equipment, and the vacuum degree in the vacuum coating equipment reaches 5×10 -4 Pa, the evaporation source was turned on, and a 200 nm thick silver deposition layer was evaporated at a deposition rate of 1 Å / s to serve as the gate.

[0056] (3) Prepare a 3.4 wt% aqueous solution of PVP, take 30 μl of the solution and spin it at 1500 rpm for 30 s, then spin-coat it onto the PET substrate with the evaporated gate, and anneal it at 160 °C in a nitrogen environment for 5 h.

[0057] (4) Place the sample with spin-coated PVP dielectric layer into the vacuum coating equipment, and the vacuum degree in the vacuum coating equipment reaches 5×10 -4 Pa, turn on the evaporation source, and evaporate a 50 nm thick gold deposition layer at a deposition rate of 1 Å / s to serve as the source and drain.

[0058] (5) The column width of the silicon column template is 2 μm and the spacing is 5 μm. The scanning electron microscope image is shown in the attached figure. Figure 2 As shown. The silicon pillar template was placed on the source and drain, and 15 μl of 10 mg / ml PTQ10 chlorobenzene solution was dripped on the surface of the silicon pillar template to fill the gap between the silicon pillar template and the source and drain, so that the PTQ10 solution filled the gap between the source and drain and covered the source and drain at the same time to form a sandwich-like structure. The solvent was evaporated by drying at 90 ° C for 12 h to obtain a flexible wide-spectrum organic phototransistor with a polymer PTQ10 micron line array. The optical microscope photo of the organic polymer PTQ10 micron line array is shown in Figure 3 shown.

[0059] from Figure 4 It can be seen that the organic polymer PTQ10 polymer microarray used has good light absorption in the ultraviolet to visible light region and is an advantageous material for preparing wide-spectrum phototransistors.

[0060] Comparative Example 1 This comparative example provides a device based on a PTQ10 thin film semiconductor layer, and its preparation method is different from that of Example 1 in that: in step (5), a device based on a PTQ10 thin film semiconductor layer is prepared by spin coating, the precursor solution is also a 10 mg / ml chlorobenzene solution of PTQ10, the spin coating speed is 3500 rpm, the spin coating time is 30 s, the annealing temperature is 100°C, and the annealing time is 5 min. The remaining steps are the same as in Example 1.

[0061] Depend on Figure 5-6 It can be seen that the mobility of the PTQ10 micrometer line array and PTQ10 thin film device is 2.5 cm 2 V - 1 s -1 , 0.21 cm 2 V -1 s -1 , it is calculated that the flexible wide spectrum phototransistor of Example 1 based on PTQ10 micrometer line array and the flexible wide spectrum phototransistor of Comparative Example 1 based on PTQ10 film have responsivities of 416533 AW under 365 nm illumination respectively. -1 ,89862 AW -1 ; The responsivity under 405 nm light is: 16951 AW -1 , 4987 AW -1 ; Under 530nm light, the responsivity is: 57898 AW -1 , 13557 AW -1 ; Under 595 nm light, the responsivity is: 76442A W -1 , 10415 AW -1 ; The responsivity under 660 nm light is: 11078 AW -1 , 1995 AW -1 . Devices based on PTQ10-micron line arrays have higher mobility and responsivity. Figure 7 It can be seen that the performance of the flexible wide-spectrum organic phototransistor based on the polymer PTQ10-micron line array has no obvious attenuation after being bent 180° 500 times.

[0062] Example 2 This embodiment provides a flexible wide-spectrum organic phototransistor based on a polymer micrometer line array, which is different from the embodiment in that the thickness of the PTQ10 micrometer line array is 200 nm.

[0063] The preparation method thereof comprises the following steps: (1) The PET substrate was cleaned and dried with deionized water, methanol, ethanol, and isopropanol, and then treated with UVO for 20 min.

[0064] (2) Place the cleaned PET substrate into the vacuum coating equipment, and the vacuum degree in the vacuum coating equipment reaches 5×10 -4 Pa, the evaporation source was turned on, and a 200 nm thick silver deposition layer was evaporated at a deposition rate of 1 Å / s to serve as the gate.

[0065] (3) Prepare a 3.4 wt% aqueous solution of PVP, take 30 μl of the solution and spin it at 1500 rpm for 30 s, then spin-coat it onto the PET substrate with the evaporated gate, and anneal it at 160 °C in a nitrogen environment for 5 h.

[0066] (4) Place the sample with spin-coated PVP dielectric layer into the vacuum coating equipment, and the vacuum degree in the vacuum coating equipment reaches 5×10 -4 Pa, turn on the evaporation source, and evaporate a 50 nm thick gold deposition layer at a deposition rate of 1 Å / s to serve as the source and drain.

[0067] (5) The column width of the silicon column template is 2 μm, and the spacing is 5 μm. 15 μl of 5 mg / ml PTQ10 chlorobenzene solution was dripped onto the surface of the silicon column template to fill the gap between the silicon column template and the source and drain electrodes, so that the PTQ10 solution filled the gap between the source and drain electrodes and covered the source and drain electrodes at the same time, forming a sandwich-like structure. The structure was dried at 90 °C for 12 h to evaporate the solvent, and a flexible wide-spectrum organic phototransistor with a polymer PTQ10 micrometer line array was obtained. Figure 8 It can be seen that its mobility is 1.2 cm 2 V -1 s -1 , the maximum responsivity under 365 nm light is: 107855 AW -1 ; Maximum responsivity at 405 nm: 8450 AW -1 ; Maximum responsivity under 530 nm light: 38118 AW -1 ; Maximum responsivity under 595 nm light: 75700 AW -1 ; Maximum responsivity under 660 nm light: 7694 AW -1 .

[0068] Example 3 This embodiment provides a flexible wide-spectrum organic phototransistor based on a polymer micrometer line array, which is different from the embodiment in that the thickness of the PTQ10 micrometer line array is 1.2 μm.

[0069] The preparation method thereof comprises the following steps: (1) The PET substrate was cleaned and dried with deionized water, methanol, ethanol, and isopropanol, and then treated with UVO for 20 min.

[0070] (2) Place the cleaned PET substrate into the vacuum coating equipment, and the vacuum degree in the vacuum coating equipment reaches 5×10 -4Pa, the evaporation source was turned on, and a 200 nm thick silver deposition layer was evaporated at a deposition rate of 1 Å / s to serve as the gate.

[0071] (3) Prepare a 3.4 wt% aqueous solution of PVP, take 30 μl of the solution and spin it at 1500 rpm for 30 s, then spin-coat it onto the PET substrate with the evaporated gate, and anneal it at 160 °C in a nitrogen environment for 5 h.

[0072] (4) Place the sample with spin-coated PVP dielectric layer into the vacuum coating equipment, and the vacuum degree in the vacuum coating equipment reaches 5×10 -4 Pa, turn on the evaporation source, and evaporate a 50 nm thick gold deposition layer at a deposition rate of 1 Å / s to serve as the source and drain.

[0073] (5) The column width of the silicon column template is 2 μm, and the spacing is 5 μm. 15 μl of 20 mg / ml PTQ10 chlorobenzene solution was dripped onto the surface of the silicon column template to fill the gap between the silicon column template and the source and drain electrodes, so that the PTQ10 solution fills the gap between the source and drain electrodes and covers the source and drain electrodes at the same time, forming a sandwich-like structure. The structure was dried at 90 °C for 12 h to evaporate the solvent, and a flexible wide-spectrum organic phototransistor with a polymer PTQ10 micrometer line array was obtained. Fig. 9 It can be seen that its mobility is 2.4 cm 2 V -1 s -1 , the maximum responsivity under 365 nm light is: 407465 AW -1 ; Maximum responsivity under 405nm light: 11818 AW -1 ; Maximum responsivity under 530 nm light: 55833 AW -1 ; Maximum response under 595nm light: 78556 AW -1 ; Maximum responsivity under 660 nm light: 12016 AW -1 .

[0074] Example 4 This embodiment provides a flexible wide-spectrum organic phototransistor based on a polymer micrometer line array, which is different from the embodiment in that the thickness of the PTQ10 micrometer line array is 240 nm.

[0075] The preparation method thereof comprises the following steps: (1) The PET substrate was cleaned and dried with deionized water, methanol, ethanol, and isopropanol, and then treated with UVO for 20 min.

[0076] (2) Place the cleaned PET substrate into the vacuum coating equipment, and the vacuum degree in the vacuum coating equipment reaches 5×10 -4 Pa, the evaporation source was turned on, and a 200 nm thick silver deposition layer was evaporated at a deposition rate of 1 Å / s to serve as the gate.

[0077] (3) Prepare a 3.4 wt% aqueous solution of PVP, take 30 μl of the solution and spin it at 1500 rpm for 30 s, then spin-coat it onto the PET substrate with the evaporated gate, and anneal it at 160 °C in a nitrogen environment for 5 h.

[0078] (4) Place the sample with spin-coated PVP dielectric layer into the vacuum coating equipment, and the vacuum degree in the vacuum coating equipment reaches 5×10 -4 Pa, turn on the evaporation source, and evaporate a 50 nm thick gold deposition layer at a deposition rate of 1 Å / s to serve as the source and drain.

[0079] (5) The column width of the silicon column template is 2 μm, and the spacing is 5 μm. 15 μl of chloroform solution of PTQ10 with a concentration of 5 mg / ml was added to the surface of the silicon column template, and the solution was filled in the gap formed by the silicon column template and the source and drain electrodes, so that the PTQ10 solution filled the gap between the source and drain electrodes and covered the source and drain electrodes at the same time, forming a sandwich-like structure. The structure was dried at 90 °C for 12 h to evaporate the solvent, and a flexible wide-spectrum organic phototransistor with a polymer PTQ10 micrometer line array was obtained. Fig.10 It can be seen that its mobility is 1.2 cm 2 V -1 s -1 , the maximum responsivity under 365 nm light is: 110012 AW -1 ; Maximum responsivity at 405 nm: 9480 AW -1 ; Maximum responsivity under 530 nm light: 33099 AW -1 ; Maximum responsivity under 595 nm light: 37214 AW -1 ; Maximum responsivity under 660 nm light: 7728 AW -1 .

[0080] Example 5 This embodiment provides a flexible wide-spectrum organic phototransistor based on a polymer micrometer line array, which is different from the embodiment in that the thickness of the PTQ10 micrometer line array is 1.5 μm.

[0081] The preparation method thereof comprises the following steps: (1) The PET substrate was cleaned and dried with deionized water, methanol, ethanol, and isopropanol, and then treated with UVO for 20 min.

[0082] (2) Place the cleaned PET substrate into the vacuum coating equipment, and the vacuum degree in the vacuum coating equipment reaches 5×10 -4 Pa, the evaporation source was turned on, and a 200 nm thick silver deposition layer was evaporated at a deposition rate of 1 Å / s to serve as the gate.

[0083] (3) Prepare a 3.4 wt% aqueous solution of PVP, take 30 μl of the solution and spin it at 1500 rpm for 30 s, then spin-coat it onto the PET substrate with the evaporated gate, and anneal it at 160 °C in a nitrogen environment for 5 h.

[0084] (4) Place the sample with spin-coated PVP dielectric layer into the vacuum coating equipment, and the vacuum degree in the vacuum coating equipment reaches 5×10 -4 Pa, turn on the evaporation source, and evaporate a 50 nm thick gold deposition layer at a deposition rate of 1 Å / s to serve as the source and drain.

[0085] (5) The column width of the silicon column template is 2 μm, and the spacing is 5 μm. 15 μl of 30 mg / ml PTQ10 chlorobenzene solution was dripped onto the surface of the silicon column template to fill the gap between the silicon column template and the source and drain electrodes, so that the PTQ10 solution fills the gap between the source and drain electrodes and covers the source and drain electrodes at the same time, forming a sandwich-like structure. The structure was dried at 90 °C for 12 h to evaporate the solvent, and a flexible wide-spectrum organic phototransistor with a polymer PTQ10 micrometer line array was obtained. Fig.11 It can be seen that its mobility is 2.0 cm 2 V -1 s -1 , the maximum responsivity under 365 nm light is: 397412 AW -1 ; Maximum response under 405nm light: 19794 AW -1 ; Maximum responsivity under 530 nm light: 53755 AW -1 ; Maximum response under 595nm light: 74415 AW -1 ; Maximum responsivity under 660 nm light: 11059 AW -1 .

[0086] Example 6 This embodiment provides a flexible wide-spectrum organic phototransistor based on a polymer micrometer line array, which is different from the embodiment in that the thickness of the PTQ10 micrometer line array is 300 nm.

[0087] The preparation method thereof comprises the following steps: (1) The PET substrate was cleaned and dried with deionized water, methanol, ethanol, and isopropanol, and then treated with UVO for 20 min.

[0088] (2) Place the cleaned PET substrate into the vacuum coating equipment, and the vacuum degree in the vacuum coating equipment reaches 5×10 -4 Pa, the evaporation source was turned on, and a 200 nm thick silver deposition layer was evaporated at a deposition rate of 1 Å / s to serve as the gate.

[0089] (3) Prepare a 3.4 wt% aqueous solution of PVP, take 30 μl of the solution and spin it at 1500 rpm for 30 s, then spin-coat it onto the PET substrate with the evaporated gate, and anneal it at 160 °C in a nitrogen environment for 5 h.

[0090] (4) Place the sample with spin-coated PVP dielectric layer into the vacuum coating equipment, and the vacuum degree in the vacuum coating equipment reaches 5×10 -4 Pa, turn on the evaporation source, and evaporate a 50 nm thick gold deposition layer at a deposition rate of 1 Å / s to serve as the source and drain.

[0091] (5) The column width of the silicon column template is 2 μm, and the spacing is 5 μm. 15 μl of a 5 mg / ml PTQ10 toluene solution was dripped onto the surface of the silicon column template to fill the gap between the silicon column template and the source and drain electrodes, so that the PTQ10 solution filled the gap between the source and drain electrodes and covered the source and drain electrodes at the same time, forming a sandwich-like structure. The structure was dried at 90 °C for 12 h to evaporate the solvent, and a flexible wide-spectrum organic phototransistor with a polymer PTQ10 micrometer line array was obtained. Fig.12 It can be seen that its mobility is 0.8 cm 2 V -1 s -1 , the maximum responsivity under 365 nm light is: 104982 AW -1 ; Maximum responsivity at 405 nm: 8521 AW -1 ; Maximum responsivity under 530 nm light: 31325 AW -1 ; Maximum responsivity under 595 nm light: 33745 AW -1 ; Maximum responsivity at 660 nm: 6469 AW -1 .

[0092] Comparative Example 2 This comparative example provides a wide-spectrum organic phototransistor, which is different from Example 1 in that PTQ-C5C7 is used to replace the polymer PTQ10, and the molecular structure of PTQ-C5C7 is as follows: , where Mn is between 20-50 kDa.

[0093] The preparation method thereof comprises the following steps: (1) The PET substrate was cleaned and dried with deionized water, methanol, ethanol, and isopropanol, and then treated with UVO for 20 min.

[0094] (2) Place the cleaned PET substrate into the vacuum coating equipment, and the vacuum degree in the vacuum coating equipment reaches 5×10 -4 Pa, the evaporation source was turned on, and a 200 nm thick silver deposition layer was evaporated at a deposition rate of 1 Å / s to serve as the gate.

[0095] (3) Prepare a 3.4 wt% aqueous solution of PVP, take 30 μl of the solution and spin it at 1500 rpm for 30 s, then spin-coat it onto the PET substrate with the evaporated gate, and anneal it at 160 °C in a nitrogen environment for 5 h.

[0096] (4) Place the sample with spin-coated PVP dielectric layer into the vacuum coating equipment, and the vacuum degree in the vacuum coating equipment reaches 5×10 -4 Pa, turn on the evaporation source, and evaporate a 50 nm thick gold deposition layer at a deposition rate of 1 Å / s to serve as the source and drain.

[0097] (5) The column width of the silicon column template is 2 μm, and the spacing is 5 μm. 15 μl of 10 mg / ml PTQ-C5C7 chlorobenzene solution was dripped onto the surface of the silicon column template to fill the gap between the silicon column template and the source and drain electrodes, so that the PTQ-C5C7 solution filled the gap between the source and drain electrodes and covered the source and drain electrodes at the same time to form a sandwich-like structure. The structure was dried at 90 °C for 12 h to evaporate the solvent, and a flexible wide-spectrum organic phototransistor with a polymer PTQ-C5C7 micrometer line array was obtained. Fig.13 It can be seen that its mobility is 0.19 cm 2 V -1 s -1 , the maximum responsivity under 365 nm light is: 245117 AW -1 ; Maximum responsivity at 405 nm: 7797 AW -1 ; Maximum responsivity under 530 nm light: 7219 AW -1; Maximum responsivity under 595 nm light: 9280A W -1 ; Maximum responsivity under 660 nm light: 5634 AW -1 .

[0098] Comparative Example 3 This comparative example provides a wide-spectrum organic phototransistor, which is different from Example 1 in that PTQ-C7C9 is used to replace the polymer PTQ10, and the molecular structure of PTQ-C7C9 is as follows: , where Mn is between 20-50 kDa.

[0099] The preparation method thereof comprises the following steps: (1) The PET substrate was cleaned and dried with deionized water, methanol, ethanol, and isopropanol, and then treated with UVO for 20 min.

[0100] (2) Place the cleaned PET substrate into the vacuum coating equipment, and the vacuum degree in the vacuum coating equipment reaches 5×10 -4 Pa, the evaporation source was turned on, and a 200 nm thick silver deposition layer was evaporated at a deposition rate of 1 Å / s to serve as the gate.

[0101] (3) Prepare a 3.4 wt% aqueous solution of PVP, take 30 μl of the solution and spin it at 1500 rpm for 30 s, then spin-coat it onto the PET substrate with the evaporated gate, and anneal it at 160 °C in a nitrogen environment for 5 h.

[0102] (4) Place the sample with spin-coated PVP dielectric layer into the vacuum coating equipment, and the vacuum degree in the vacuum coating equipment reaches 5×10 -4 Pa, turn on the evaporation source, and evaporate a 50 nm thick gold deposition layer at a deposition rate of 1 Å / s to serve as the source and drain.

[0103] (5) The column width of the silicon column template is 2 μm, and the spacing is 5 μm. 15 μl of 10 mg / ml PTQ-C7C9 chlorobenzene solution was dripped onto the surface of the silicon column template to fill the gap between the silicon column template and the source and drain electrodes, so that the PTQ-C7C9 solution filled the gap between the source and drain electrodes and covered the source and drain electrodes at the same time to form a sandwich-like structure. The structure was dried at 90 °C for 12 h to evaporate the solvent, and a flexible wide-spectrum organic phototransistor with a 10-micron line array of polymer PTQ was obtained. Fig.14 It can be seen that its mobility is 0.3 cm 2 V -1 s -1, the maximum responsivity under 365 nm light is: 109048 AW -1 ; Maximum responsivity at 405 nm: 6619 AW -1 ; Maximum responsivity under 530 nm light: 13896 AW -1 ; Maximum responsivity under 595 nm light: 15442 AW -1 ; Maximum responsivity under 660 nm light: 3457 AW -1 .

[0104] In summary, the present invention uses a method of inducing the dewetting of a polymer solution by using a silicon pillar template with asymmetric wettability to prepare a uniform morphology and orderly stacked polymer one-dimensional micrometer wire array on a flexible substrate. The array has a wide spectrum absorption capacity in the ultraviolet-visible band, so that the flexible organic field-effect transistor with a polymer one-dimensional micro-nanowire array has a wide spectrum detection capability, and has high mobility and response performance. The overall preparation process of the device is simple and has low requirements for experimental conditions, which provides a new idea for the preparation and integration of flexible wide-spectrum organic phototransistors.

[0105] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A flexible wide-spectrum organic phototransistor based on a polymer microwire array, characterized in that: It includes a substrate, a gate arranged on the substrate, a dielectric layer arranged on the gate, a source and a drain arranged on the dielectric layer, and an organic polymer micrometer wire array arranged between the source and the drain; the organic polymer micrometer wire array is a PTQ10 micrometer wire array assembled by capillary liquid bridge confinement.

2. The flexible wide-spectrum organic phototransistor according to claim 1, characterized in that: The number average molecular weight of the organic polymer in the organic polymer microwire array is 5-500 kDa; And / or, in the organic polymer microwire array, the width of the microwire is 1-3 μm, the thickness is 100-1500 nm, and the spacing between adjacent microwires is 3-7 μm.

3. The flexible wide-spectrum organic phototransistor according to claim 1 or 2, characterized in that: The substrate is PET with a thickness of 50-1000 μm; And / or, the gate is a 20-400 nm thick gold, silver, aluminum or copper film; And / or, the dielectric layer is a PVP film with a thickness of 100-500 nm; And / or, the source electrode and the drain electrode are each independently a 20-100 nm thick gold, silver, aluminum or copper film.

4. The method for preparing a flexible wide-spectrum organic phototransistor according to any one of claims 1 to 3, characterized in that: The steps include: Step (1): providing a substrate; Step (2): preparing a gate on a substrate; Step (3): preparing a dielectric layer on the gate; Step (4): preparing a source electrode and a drain electrode on the dielectric layer; Step (5): Install a template above the source and drain electrodes, drip a PTQ10 solution onto the surface of the template so that the PTQ10 solution fills the gap between the source and drain electrodes and covers the source and drain electrodes at the same time, and dry the template to evaporate the solvent, thereby obtaining the flexible wide-spectrum organic phototransistor.

5. The preparation method according to claim 4, characterized in that: In the step (5), the concentration of PTQ10 in the PTQ10 solution is 5-30 mg / ml, and the solvent is chlorobenzene, toluene or chloroform.

6. The preparation method according to claim 4 or 5, characterized in that: In the step (5), the drying temperature is 60-120°C and the drying time is 5-20 h; And / or, the template is a silicon column template; preferably, the silicon column template is a silicon column template with asymmetric wettability.

7. The preparation method according to claim 4, characterized in that: The step (1) specifically comprises: using deionized water, methanol, ethanol, or isopropanol to clean and dry the substrate, and then treating the cleaned substrate with UVO for 5-30 minutes.

8. The preparation method according to claim 4, characterized in that: The step (2) is specifically as follows: placing the substrate into a vacuum coating device, wherein the vacuum degree in the vacuum coating device reaches 5×10 -4 Pa, turn on the evaporation source, control the evaporation rate of the metal, and evaporate the metal deposition layer as the gate; preferably, the evaporation rate is 1-5 Å / s and the thickness is 20-100 nm.

9. The preparation method according to claim 4, characterized in that: The step (3) specifically comprises: preparing a PVP aqueous solution of a certain concentration, taking a certain amount of the PVP aqueous solution and evenly spin-coating it on the gate, and then performing annealing treatment to form a dielectric layer on the gate; preferably, the concentration of the PVP aqueous solution is 1-5 wt%, the amount is 10-500 μl, the spin-coating speed is 500-3000 rpm, the spin-coating time is 15-120 s, the annealing temperature is 80-160 ° C, and the annealing time is 1-15 h.

10. The preparation method according to claim 4, characterized in that: The step (4) is specifically as follows: placing the sample of the spin-coated dielectric layer into a vacuum coating device, wherein the vacuum degree in the vacuum coating device reaches 5×10 -4 Pa, turn on the evaporation source, control the metal evaporation rate, and evaporate the metal deposition layer to serve as the source and drain; preferably, the evaporation rate is 1-5 Å / s and the thickness is 20-100 nm.

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