CN111009614A - Construction method of high-sensitivity photoelectric detector based on one-dimensional fullerene material/PEDOT (Polytetrafluoroethylene)/PSS (Polytetrafluoroethylene) composite film - Google Patents

Construction method of high-sensitivity photoelectric detector based on one-dimensional fullerene material/PEDOT (Polytetrafluoroethylene)/PSS (Polytetrafluoroethylene) composite film Download PDF

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CN111009614A
CN111009614A CN201911326871.1A CN201911326871A CN111009614A CN 111009614 A CN111009614 A CN 111009614A CN 201911326871 A CN201911326871 A CN 201911326871A CN 111009614 A CN111009614 A CN 111009614A
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CN111009614B (en
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崔大祥
蔡葆昉
卢静
金彩虹
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10Deposition of organic active material
    • H10K71/12Deposition of organic active material using liquid deposition, e.g. spin coating
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10Organic polymers or oligomers
    • H10K85/111Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
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    • H10K85/211Fullerenes, e.g. C60
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Abstract

The invention relates to a construction method of a high-sensitivity photoelectric detector based on a one-dimensional fullerene material/PEDOT (Polytetrafluoroethylene)/PSS (Polytetrafluoroethylene) composite film, which synthesizes and prepares high-quality one-dimensional fullerene (C) by adopting a solution interface molecule self-assembly method60) Nano material, spin coating or dropping the one-dimensional C60The nano material is uniformly distributed on any clean substrate, and a conductive polymer PEDOT, PSS is introduced to prepare the one-dimensional fullerene material/PEDOT, PSS composite film high-sensitivity photoelectric detector. The method is simple and controllable, low in cost, high in repeatability and easy to realize batch production, the constructed one-dimensional fullerene material/PEDOT/PSS composite film device presents excellent photoresponse circulation stability, and the photoelectric response is sensitive under the excitation of monochromatic wavelength laser of 405nmThe degree (photocurrent/dark current) reaches 1800%, and the method has wide application value.

Description

Construction method of high-sensitivity photoelectric detector based on one-dimensional fullerene material/PEDOT (Polytetrafluoroethylene)/PSS (Polytetrafluoroethylene) composite film
Technical Field
The invention belongs to the field of photoelectric detectors, and particularly relates to a construction method of a one-dimensional fullerene material/PEDOT/PSS composite film photoelectric detector sensitive to light pulse response of a purple light wave band.
Background
In recent years, the technology of the present invention has been developedIn recent years, carbon nanomaterials have attracted much attention and developed rapidly in the fields of nanoelectronics and nanophotonics. For example, fullerene (C)60) The unique properties of the semiconductor material are very advantageous to be applied to optoelectronic devices, for example, the shape of the material is controlled to regulate the band gap of the semiconductor material through different preparation methods; the energy band structure of the direct band gap ensures considerable optical gain; stable chemistry extends the lifetime of the device, etc. C60And the derivatives (such as PCBM) thereof can be used as an ideal electron transport layer in a solar cell, and particularly C with a one-dimensional structure60The nanometer material as light absorbing material has wide application foreground in photoelectronic device. In addition thereto, based on a one-dimensional structure C60Nanomaterial photodetectors can be built not only with low cost solution methods but also on flexible substrates, which are difficult with conventional group III-V semiconductors.
At present, based on a one-dimensional structure C60There are many forms of nanomaterial photodetectors. For example, Shrestha et al showed that it is related to pure C60Powder comparison, C60The number of photogenerated carriers in the nanorods is significantly increased, which makes the C-based60The photodetector of the nanorod has higher photoelectric response sensitivity (R.G. Shrestha, L.K. Shrestha, A.H. Khan, G.S. Kumar, S.Acharya and K. Ariga, ACS appl. mater. Interfaces,2014, 6(17), 15597-. There are also researchers who will convert one-dimensional structures C of the N type60The nanometer material is compounded with other semiconductor material to form heterojunction, so that C with excellent photoelectric response is prepared60A base photodetector. For example, Biebersdorf et al prepared a needle C60Nano material, and then compounding it with InP, CdSe or CdTe to sensitize needle-shaped C60(iii) photoresponse (A. Biebersdorf, R. Dietmu1 ler, A.S. Susha, A.L. Rogach, S.K. Poznyak, D.V. Talapin, H. Weller, T.A. Klar and J. Feldmann, Nano Lett., 2006, 6(7), 1559-. In addition, Meshot et al prepared C60The nanorod/Carbon Nanotube (CNT) all-carbon composite film is used as the photoactive layer of a photodetector, at C60Nanorods andideally, the carbon nano tube is cooperated, and the constructed device shows high photoconductive gain and 10 or more5A/W photoresponse (E.R. Meshot, K.D. Patel, S. Tawfick, K.A.Juggernauth, M. Bedewy, E.A. Verploegen, M.F.L.De Volder and A.J. Hart, adv. Funct. Mater., 2012, 22, 577-.
However, based on a single one-dimensional C60The performance of a material for a photodetector device is limited, and how to effectively improve the performance of the material still faces many challenges. 1) Solution method for preparing one-dimensional C through molecular assembly60The process of the nano material is difficult to control, and the prepared one-dimensional C60The nano material has a large number of structural defects or solvent molecules cannot be uniformly distributed, so that the efficient transmission of current carriers is influenced, and the photoelectric response performance is further influenced; 2) the film formation alone is difficult, and the photoelectric conversion loss caused by accumulation in a conductive channel occurs in the process of constructing the photoelectric detector.
Thus, one-dimensional C is increased60The nanometer material is uniformly distributed and has film forming characteristic, and the improvement is based on one-dimensional C60The high-sensitivity photoelectric detector made of the nano material has important scientific and engineering application significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for constructing a high-sensitivity photoelectric detector based on a one-dimensional fullerene material/PEDOT/PSS composite film, which is a method for constructing a high-sensitivity photoelectric detector based on a one-dimensional fullerene material/PEDOT/PSS composite film by compounding a one-dimensional fullerene material with PEDOT/PSS.
The purpose of the invention is realized by the following scheme: a method for constructing a high-sensitivity photoelectric detector based on a one-dimensional fullerene material/PEDOT/PSS composite film adopts a solution interface molecule self-assembly method to prepare one-dimensional fullerene (C)60) Nano material, spin coating or dropping the one-dimensional C60PSS is introduced into a conductive polymer PEDOT to prepare the nano material, and the nano material is uniformly distributed on any clean substrate and is obtained by the following steps:
1) will be commercial C60Dissolving the powder in a certain amount of 1, 3, 5-trimethylbenzene to obtain a solution with a concentration of 0.7~1.1 mg/mLC60Carrying out ultrasonic dispersion treatment on the solution for 5-10 minutes, then respectively placing 2-4 mL of the solution and 3-7 mL of methanol in a small glass bottle, and heating the solution in a water bath at the temperature of 20-35 ℃ for 20-60 minutes; followed by treatment with C60Slowly and uniformly dripping the solution into methanol by using a dropper, and standing for 1-4 minutes after dripping is finished; collecting brown precipitate, centrifuging and washing with isopropanol solution for 2-3 times, dispersing in isopropanol, and storing to obtain one-dimensional C60Suspension of the nano material;
2) one-dimensional C in the step 1)60The nano material turbid liquid is distributed on any clean substrate by adopting a spin coating method or a drop coating method, the rotating speed is properly controlled during the spin coating, and then a sample is placed on a hot plate to be baked for 2-5 minutes at the temperature of 30-50 ℃, so that the one-dimensional C uniformly distributed on the substrate is obtained60A sample;
3) dynamically spin-coating 200-800 mu L of commercial PEDOT (PSS) aqueous solution on the sample obtained in the step 2), and baking the sample on a hot plate at the temperature of 40-60 ℃ for 2-5 minutes; obtaining a one-dimensional fullerene-based material/PEDOT (Poly ethylene glycol Ether-Co-Polymer) PSS composite film;
4) and preparing an electrode on the one-dimensional fullerene material/PEDOT/PSS composite film to prepare the high-sensitivity photoelectric detector based on the one-dimensional fullerene material/PEDOT/PSS composite film.
The invention prepares high-quality one-dimensional fullerene by an optimized solution interface molecule self-assembly method, uniformly distributes the one-dimensional fullerene material prepared by the method on any clean substrate in a spin coating or drop coating mode, and introduces conductive polymers PEDOT: PSS to enhance the photoelectric conversion efficiency of the one-dimensional fullerene material, thereby successfully preparing the high-sensitivity photoelectric detector of the one-dimensional fullerene material/PEDOT: PSS composite film.
Based on the scheme, C in the step 1)60The preferred concentration of the 1, 3, 5-trimethylbenzene solution of the base material powder is 0.9 mg/mL.
Step 1) C configured in the previous step60The optimal dosage of the 1, 3, 5-trimethylbenzene solution is 3mL, and the optimal dosage of the methanol is 5 mL.
The optimal value of the water bath heating in the step 1) is that the water bath heating is carried out for 40 minutes at the temperature of 25 ℃.
The samples in step 2) were baked on a hotplate at 49 ℃ for 3 minutes.
The optimal spin coating amount of the PEDOT/PSS aqueous solution in the step 3) is 400 muL.
Preferably, the sample in step 3) is dried on a hot plate at 45 ℃ for 4 minutes.
And 2) the substrate is any one of a rigid substrate of a silicon wafer and glass, or any one of a flexible substrate of PDMS and PET.
When spin coating is adopted, the rotating speed of a spin coater is set to be 1000-1400 rpm.
The invention provides a construction method of a high-sensitivity photoelectric detector based on a one-dimensional fullerene material/PEDOT-PSS composite film, which adopts an optimized solution interface molecule self-assembly method to synthesize and prepare a high-quality one-dimensional C60The nano-structure (line, flower, derivative, etc.) is uniformly distributed on any substrate in a spin coating or drop coating mode, and a conductive polymer PEDOT: PSS is introduced to form a composite film, so that one-dimensional C is improved60Based on the photoelectric conversion efficiency of the nano material, the high-sensitivity photoelectric detector based on the one-dimensional fullerene-based material/PEDOT/PSS composite film is obtained. The device construction method provided by the invention is simple and controllable, has high repeatability and has important application potential.
The preparation method specifically comprises the steps of uniformly distributing a one-dimensional fullerene material prepared by a solution method on any clean substrate (such as a rigid substrate of a silicon wafer, glass and the like or a flexible substrate of PDMS, PET and the like) by a spin coating or drop coating method, forming a conductive high polymer material PEDOT with excellent film forming performance by spin coating on the basis, wherein the PSS forms a composite film, and the ideal hole transmission characteristic is utilized, so that the problem of low photoelectric conversion efficiency of a photogenerated carrier caused by poor film forming characteristic of the fullerene material and incapability of being effectively lapped with an electrode material is greatly improved. Through the optimization of the proportion of the one-dimensional fullerene material of the photoactive layer of the device to PEDOT (p-phenylene sulfide), the photoelectric response sensitivity (photocurrent/dark current) of the high-sensitivity photoelectric detector of the prepared one-dimensional fullerene material/PEDOT (p-phenylene sulfide)/PSS composite film under the excitation of monochromatic wavelength laser of 405nm reaches 1800%.
The invention has the advantages that: the provided method is simple and controllable, has low cost and high repeatability, and is easy to realize batch production; the constructed one-dimensional fullerene material/PEDOT/PSS composite film device has excellent photoresponse cycle stability, the photoelectric response sensitivity (photocurrent/dark current) reaches 1800% under the excitation of monochromatic wavelength laser of 405nm, and the application value is wide.
Drawings
FIG. 1: c used in example 160Raman spectra of the nanowires;
FIG. 2: the response curve of the device constructed in example 1 to monochromatic laser pulses with a wavelength of 405 nm.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
A high-sensitivity photoelectric detector based on one-dimensional fullerene material/PEDOT (PSS) composite film adopts a solution interface molecule self-assembly method to prepare one-dimensional fullerene (C)60) Nano material, spin coating or dropping the one-dimensional C60The nano material is uniformly distributed on any clean substrate, and conductive polymer PEDOT is introduced, wherein the conductive polymer PEDOT is prepared by PSS and is prepared by the following steps:
1) 18 mg of commercial C60The powder was dissolved in 20 mL of 1, 3, 5-trimethylbenzene to give a concentration of 0.9mg/mLC60Carrying out ultrasonic dispersion treatment on the solution for 8 minutes to obtain the solution; 3mL of the solution A and 5mL of methanol are respectively put into a small glass bottle and heated for 40 minutes in water bath at 25 ℃; then slowly and uniformly dripping the treated 3mL of solution A into 5mL of methanol by using a dropper at the speed of 2 seconds per drop, and standing for 1-4 minutes after the dripping is finished; the above solution was centrifuged with an isopropanol solution and the precipitate was collected (8000 rpm, 3 minutes) and dispersed in 8mL of an isopropanol solution to obtain C60A nanowire suspension;
2) mixing C in step 1)60Nanowire suspension is coated on Si/SiO in a spinning mode2On the substrate, the spin coater rotation speed was set to 1000 rpm, and the sample was then transferredBaking the product on a hot plate at 40 deg.C for 3 min to obtain C uniformly distributed on the substrate60A wire sample;
3) 400 μ L of commercial PEDOT: PSS aqueous solution was dynamically spin-coated (spin coater rotation speed 1200 rpm) on the sample obtained in step 2), baked on a hot plate at 45 ℃ for 4 minutes to obtain C60The nano wire/PEDOT is a PSS composite conductive film;
4) at C60PSS composite film is coated with conductive silver glue as electrode to prepare C-based material60The nanowire/PEDOT is a high-sensitivity photoelectric detection device of a PSS composite conductive film. C used in the device 1 of the present example60The Raman spectrum of the nanowire is shown in the attached figure 1; the response curve of the device constructed in the example 1 to the monochromatic laser pulse of 405nm is shown in fig. 2, and the device shows excellent photoresponse cycle stability.
Example 2
A high-sensitivity photoelectric detector based on a one-dimensional fullerene material/PEDOT: PSS composite film is similar to that of the embodiment 1, and is prepared by the following steps:
1) 15 mg of commercial C60The powder was dissolved in 20 mL of 1, 3, 5-trimethylbenzene to give a concentration of 0.75 mg/mLC60Carrying out ultrasonic dispersion treatment on the solution for 8 minutes to obtain a solution A; 3mL of the solution and 5mL of methanol are respectively put into a small glass bottle and heated in water bath at the temperature of 30 ℃ for 30 minutes; then slowly and uniformly dripping a treated dropper of the solution A with the volume of 3mL into methanol at the speed of 2 seconds per drop, and standing for 1-4 minutes after the dripping is finished; centrifuging at 8000 rpm for 3 min to collect brown precipitate, centrifuging with isopropanol solution for 3 times, dispersing the washed brown precipitate in 8mL isopropanol, and storing to obtain C dispersed in isopropanol60A nanowire suspension;
2) mixing C in step 1)60The nanowire suspension is spin-coated on a clean flexible substrate such as PET, PDMS or PMMA, the rotation speed of a spin coating machine is set to be 1000 r/s, and then a sample is placed on a hot plate at 40 ℃ to be baked for 3 minutes to obtain C uniformly distributed on the substrate60A wire sample;
3) c to be obtained60Dynamic spin coating (spin coater rotation speed) of 200-800 mu L of linear sample1200 rpm) of commercial PEDOT, PSS in water, followed by baking the sample on a hot plate at 45 ℃ for 4 minutes; obtaining a one-dimensional fullerene-based material/PEDOT (Poly ethylene glycol Ether-Co-Polymer) PSS composite film;
4) c on flexible substrate60And (3) coating conductive silver colloid on the nanowire/PEDOT (PSS) sample to be used as an electrode to prepare the high-sensitivity photoelectric detector based on the one-dimensional fullerene material/PEDOT/PSS composite film.
Example 3
A high-sensitivity photoelectric detector based on a one-dimensional fullerene material/PEDOT: PSS composite film is similar to that of the embodiment 1, and is prepared by the following steps:
1) c prepared by solution method60Nanoneedles (also nanosheets or nanoflowers) dispersed in a relevant solution, C60A nano needle suspension;
2) spin-coating the suspension obtained in step 1) on a clean arbitrary substrate (such as a rigid substrate like a silicon wafer or glass, or a flexible substrate like PDMS or PET), placing the obtained sample on a hot plate, and drying at 40 deg.C for 3 min to obtain C uniformly distributed on the substrate60A needle sample;
3) dynamically spin-coating 400 μ L PEDOT: PSS aqueous solution on the sample; then, putting the sample on a hot plate, and drying the sample for 4 minutes at 45 ℃ to form a composite conductive film;
4) and coating conductive silver adhesive on the composite conductive film to serve as an electrode, and finishing construction of the device.
Example 4
A high-sensitivity photoelectric detector based on a one-dimensional fullerene material/PEDOT: PSS composite film is similar to that of the embodiment 1, and is prepared by the following steps:
1) dispersing a one-dimensional fullerene derivative (including but not limited to PCBM) nano material prepared by a solution method in a related solution to obtain a one-dimensional fullerene derivative suspension;
2) spin-coating the suspension obtained in the step 1) on a clean arbitrary substrate (such as a rigid substrate like a silicon wafer and glass, or a flexible substrate like PDMS and PET), placing the obtained sample on a hot plate, and drying at 20-40 ℃ for 3-5 minutes to obtain one-dimensional fullerene derivative samples uniformly distributed on the substrate;
3) dynamically spin-coating 300 muL of PEDOT (Polytetrafluoroethylene)/PSS (Polytetrafluoroethylene) aqueous solution on the sample, and then putting the sample on a hot plate and drying the sample for 4 minutes at 45 ℃ to obtain a one-dimensional fullerene derivative/PEDOT (Polytetrafluoroethylene)/PSS sample which is uniformly distributed on a substrate;
4) and (3) coating conductive silver adhesive on a one-dimensional fullerene derivative/PEDOT (PSS) sample as an electrode, and finishing the construction of the device.
Example 5
A high-sensitivity photoelectric detector based on a one-dimensional fullerene material/PEDOT: PSS composite film is similar to that of the embodiment 1, and is prepared by the following steps:
1) dispersing a one-dimensional fullerene derivative (including but not limited to PCBM) nano material prepared by a solution method in a related solution to obtain a one-dimensional fullerene derivative suspension;
2) spin-coating the suspension on a clean arbitrary substrate (such as a rigid substrate like a silicon wafer and glass, or a flexible substrate like PDMS and PET), setting the rotation speed of a spin coater to be 1000-1400 rpm, and drying the obtained sample on a hot plate at 20-40 ℃ for 3-5 minutes to obtain one-dimensional fullerene derivative samples uniformly distributed on the substrate;
3) dynamically spin-coating 400 mu L of PEDOT: PSS aqueous solution on the obtained sample (the rotation speed of a spin coater is 1000-1200 rpm), and then putting the sample on a hot plate and drying the sample for 4 minutes at 45 ℃ to obtain a one-dimensional fullerene derivative/PEDOT: PSS sample uniformly distributed on a substrate;
4) and photoetching an Au electrode on a one-dimensional fullerene derivative/PEDOT (power off diode) PSS sample on the substrate, and finishing the construction of the device.

Claims (9)

1. A construction method of a high-sensitivity photoelectric detector based on a one-dimensional fullerene material/PEDOT: PSS composite film is characterized by comprising the following steps: preparing one-dimensional fullerene (C) by adopting solution interface molecule self-assembly method60) Nano material, spin coating or dropping the one-dimensional C60PSS is introduced into a conductive polymer PEDOT to prepare the nano material, and the nano material is uniformly distributed on any clean substrate and is obtained by the following steps:
1)will be commercial C60Dissolving the powder in a certain amount of 1, 3, 5-trimethylbenzene to obtain a solution with a concentration of 0.7-1.1 mg/mLC60Carrying out ultrasonic dispersion treatment on the solution for 5-10 minutes, then respectively placing 2-4 mL of the solution and 3-7 mL of methanol in a small glass bottle, and heating the solution in a water bath at the temperature of 20-35 ℃ for 20-60 minutes; followed by treatment with C60Slowly and uniformly dripping the solution into methanol by using a dropper, and standing for 1-4 minutes after dripping is finished; collecting brown precipitate, centrifuging and washing with isopropanol solution for 2-3 times, dispersing in isopropanol, and storing to obtain one-dimensional C60Suspension of the nano material;
2) one-dimensional C in the step 1)60The nano material turbid liquid is distributed on any clean substrate by adopting a spin coating method or a drop coating method, and then a sample is placed on a hot plate and baked for 2-5 minutes at the temperature of 30-50 ℃ to obtain the one-dimensional C uniformly distributed on the substrate60A sample;
3) dynamically spin-coating 200-800 mu L of commercial PEDOT (PSS) aqueous solution on the sample obtained in the step 2), and baking the sample on a hot plate at the temperature of 40-60 ℃ for 2-5 minutes; obtaining a one-dimensional fullerene-based material/PEDOT (Poly ethylene glycol Ether-Co-Polymer) PSS composite film;
4) and preparing an electrode on the one-dimensional fullerene material/PEDOT/PSS composite film to prepare the high-sensitivity photoelectric detector based on the one-dimensional fullerene material/PEDOT/PSS composite film.
2. The method for constructing a high-sensitivity photoelectric detector based on a one-dimensional fullerene material/PEDOT: PSS composite film as claimed in claim 1, wherein C in step 1)60The concentration of the 1, 3, 5-trimethylbenzene solution was 0.9 mg/mL.
3. The method for constructing a high-sensitivity photoelectric detector based on a one-dimensional fullerene material/PEDOT: PSS composite film as claimed in claim 1, wherein C is provided in step 1)60The dosage of the 1, 3, 5-trimethylbenzene solution is 3mL, and the dosage of the methanol is 5 mL.
4. The method for constructing a high-sensitivity photoelectric detector based on the one-dimensional fullerene material/PEDOT: PSS composite film as claimed in claim 1, wherein the step 1) is carried out by heating in water bath at 25 ℃ for 40 minutes.
5. The method for constructing a high-sensitivity photoelectric detector based on the one-dimensional fullerene material/PEDOT: PSS composite film as claimed in claim 1, wherein the sample in the step 2) is baked for 3 minutes at a baking temperature of 49 ℃ on a hot plate.
6. The method for constructing a high-sensitivity photoelectric detector based on the one-dimensional fullerene material/PEDOT: PSS composite film as claimed in claim 1, wherein the spin coating amount of the PEDOT: PSS aqueous solution in the step 3) is 400 μ L.
7. The method for constructing a high-sensitivity photoelectric detector based on the one-dimensional fullerene material/PEDOT: PSS composite film as claimed in claim 1, wherein the sample in the step 3) is dried on a hot plate at 45 ℃ for 4 minutes.
8. The method for constructing a high-sensitivity photoelectric detector based on one-dimensional fullerene material/PEDOT: PSS composite film as claimed in claim 1, wherein the substrate in step 2) is any one of a rigid substrate of silicon chip and glass, or any one of a flexible substrate of PDMS and PET.
9. The method of claim 1, wherein the spin coating is performed at a spin coater speed of 1000 to 1400 rpm.
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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN112635671A (en) * 2020-12-19 2021-04-09 南京理工大学 Femtosecond laser modification-based resistance reduction method for conductive polymer PEDOT (PEDOT-PSS)
CN114133347A (en) * 2021-10-28 2022-03-04 丁皓璇 Fullerene supermolecular framework material and preparation method and application thereof

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