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CN109638166A - A kind of all solid state organic electrochemistry optotransistor and preparation method thereof - Google Patents

A kind of all solid state organic electrochemistry optotransistor and preparation method thereof Download PDF

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Publication number
CN109638166A
CN109638166A CN201811558217.9A CN201811558217A CN109638166A CN 109638166 A CN109638166 A CN 109638166A CN 201811558217 A CN201811558217 A CN 201811558217A CN 109638166 A CN109638166 A CN 109638166A
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solid
phototransistor
state organic
organic electrochemical
layer
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陈惠鹏
严育杰
郭太良
巫晓敏
陈奇珍
刘亚倩
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Fuzhou University
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Fuzhou University
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/60—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation in which radiation controls flow of current through the devices, e.g. photoresistors
    • H10K30/65—Light-sensitive field-effect devices, e.g. phototransistors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Thin Film Transistor (AREA)

Abstract

本发明涉及了一种全固态有机电化学光晶体管及其制备方法。该有机电化学光晶体管采用底栅平面结构，器件从下往上依次是基底、固态电解质层、有源层、源漏电极和吸光层；其中固态电解质层采用聚合物离子凝胶电解质，并利用旋涂或刮涂工艺在基底上形成固态电解质层，从而实现全固态有机电化学光晶体管。本发明提供的全固态有机电化学光晶体管在低电压操作下实现了出色的光响应R和探测率D，同时全固态光晶体管的特性可有望进一步集成至先进电子及电路系统中，扩宽高性能电化学晶体管应用领域。该全固态有机电化学晶体管有望广泛用于光传感器、人工突触及大规模集成电路等领域。

The invention relates to an all-solid-state organic electrochemical phototransistor and a preparation method thereof. The organic electrochemical phototransistor adopts a bottom gate plane structure, and the device is composed of a substrate, a solid electrolyte layer, an active layer, a source-drain electrode and a light absorption layer in order from bottom to top; wherein the solid electrolyte layer adopts a polymer ion gel electrolyte, and uses The spin-coating or blade-coating process forms a solid-state electrolyte layer on the substrate, thereby realizing an all-solid-state organic electrochemical phototransistor. The all-solid-state organic electrochemical phototransistor provided by the present invention achieves excellent photoresponse R and detection rate D under low voltage operation, and the characteristics of the all-solid-state phototransistor can be expected to be further integrated into advanced electronic and circuit systems. Performance Electrochemical Transistor Applications. The all-solid-state organic electrochemical transistor is expected to be widely used in optical sensors, artificial synapses, and large-scale integrated circuits.

Description

A kind of all solid state organic electrochemistry optotransistor and preparation method thereof
Technical field
The invention belongs to electronic material and device arts, be related to a kind of all solid state organic electrochemistry optotransistor and its Preparation method.
Background technique
Extensive concern has been obtained in organic effect optotransistor, however the improvement of its photoelectric characteristic is concentrated mainly on The optimization of active layer material, comprising: n/p type semiconductor material is blended, n/p type semiconductor material layer hetero-junctions etc..In fact, having The raising of airport effect optotransistor performance is limited to the mobility of organic semiconducting materials, it is often more important that field effect transistor The essence of low mutual conductance.Meanwhile the operating voltage of most of organic effect optotransistors is higher than 10V, generates biggish power consumption simultaneously And be also unfavorable for being integrated into wearable device, it limits its scope of application.
The electrochemical transistor for also belonging to one of thin film transistor (TFT), since the coupling effect of its charge and ion occurs In entire active layer channel, to produce biggish body capacitance and the following high transconductance characteristic.Meanwhile lower Operation voltage (usually less than 1V) achieves that biggish density of volume charges regulation.But electrochemical transistors all at present uses Liquid electrolyte, technical process is complex, and the characteristic that liquid electrolyte is volatile, not only causes the shakiness of device performance It is fixed, and be difficult to be integrated into existing solid electronic device, these have seriously affected the application range of electrochemical transistor.Mesh Before, it there is no report about the research for combining the electrochemical transistor of high transconductance to prepare all solid state organic electrochemistry optotransistor.
Summary of the invention
The purpose of the present invention is to provide a kind of all solid state organic electrochemistry optotransistors and preparation method thereof, to improve light The photoelectric properties of detector and the application range of solid-state electrochemistry transistor.
To achieve the above object, the technical scheme is that
A kind of all solid state organic electrochemistry optotransistor, the organic electrochemistry optotransistor is bottom gate planar structure, from lower past On be followed successively by substrate, solid-state electrolyte layer, active layer, source-drain electrode and light-absorption layer, the substrate is highly doped silicon wafer, the silicon wafer Not only it had been substrate but also had been grid, the solid-state electrolyte layer is polymeric ionic gels electrolyte, and the active layer is led for polymer Body material, the light-absorption layer are organic photosensitive semiconductor material.
Further, the polymeric ionic gels electrolyte is to be total to polyacrylonitrile and bis trifluoromethyl sulfimide lithium Mixed object is dissolved in made from the mixed solvent of ethylene carbonate and propene carbonate, wherein polyacrylonitrile: bis trifluoromethyl sulphonyl is sub- Amine lithium: ethylene carbonate: propene carbonate mass ratio be 14.1:3.9:41:41, the solid-state electrolyte layer with a thickness of 2-3 μ m。
Further, the polymer conductor material is PEDOT:PSS or P3HT, and the active layer is to pass through spin coating proceeding Deposition is made, with a thickness of 100-600nm.
Further, the source-drain electrode layer material therefor is gold, aluminium or silver, with a thickness of 50-100nm.
Further, the light-absorption layer with a thickness of 50-120nm, the organic photosensitive semiconductor material includes J71: ITIC、DTS:PCBM。
The preparation method of above-mentioned all solid state organic electrochemistry optotransistor, specifically includes the following steps:
(1) using highly doped silicon wafer to pass through spin coating or doctor blade process deposited polymer ionic gel electrolyte in substrate and move back Fire obtains solid-state electrolyte layer；
(2) active layer is made by spin coating proceeding spin on polymers conductor material on the electrolyte layer that step (1) obtains；
(3) pass through thermal evaporation process on the active layer that step (2) obtains and source-drain electrode is deposited using mask plate and source and drain is made Electrode；
(4) light-absorption layer is made by spin coating proceeding spin coating organic photosensitive semiconductor material on the active layer that step (3) obtains, Obtain all solid state organic electrochemistry optotransistor.
Compared to the prior art, the invention has the following advantages: the present invention is to prepare solid-state electricity by ionic gel Matter layer is solved, to realize all solid state organic electrochemistry transistor, while obtaining electrochemical transistor high transconductance and body transmission Characteristic makes the optical detector based on organic electrochemistry transistor show splendid photoresponse R and detectivity D.Institute in the present invention Solid-state organic electrochemistry optotransistor prepared by the ionic gel preparation method and blade coating of use, spin coating proceeding method, operation Simply, organic electrochemistry luminescent crystal at low cost, being conducive to promote the use, have significant economic and social benefit, and obtain Pipe has outstanding photoelectric properties in visible-light detector.
Detailed description of the invention
Fig. 1 is all solid state organic electrochemistry optotransistor structural schematic diagram of the invention；
Fig. 2 is the three-dimensional structure of all solid state organic electrochemistry optotransistor of the invention and the schematic diagram for adding light source equipment；
Fig. 3 is transfer characteristic curve of the organic electrochemistry optotransistor of the preparation of embodiment 1 in Compound eye；
Fig. 4 is the metal oxide optotransistor of the preparation of embodiment 1 in Compound eye (VDS=-0.5V, P=10 μW/cm2) In the case of photoresponse (R) obtained and detectivity (D)；
In figure: 100- substrate, 110- solid-state electrolyte layer, 120- active layer, 130- source-drain electrode, 140- light-absorption layer, 150- light Source.
Specific embodiment
All solid state organic electrochemistry optotransistor structure of the invention as shown in Figure 1, be followed successively by from the bottom up substrate 100, Solid-state electrolyte layer 110, active layer 120, source-drain electrode 130 and light-absorption layer 140, the substrate 100 are highly doped silicon wafer, the silicon Piece had not only been substrate but also had been grid, and the solid-state electrolyte layer 110 is polymeric ionic gels electrolyte, and the active layer 120 is Polymer conductor material, the light-absorption layer 140 are organic photosensitive semiconductor material.
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited only to these embodiments.
Embodiment 1
1) 1 .5cm × 1.5cm size, heavily doped P-type silicon wafer, through acetone, isopropanol, chloroform, distilled water will have been cut (three times) it cleans, then does substrate with clean silicon wafer is obtained after being dried with nitrogen.
2) ionic gel electrolyte is prepared: by polyacrylonitrile, bis trifluoromethyl sulfimide lithium, ethylene carbonate and carbonic acid Acrylic ester be in mass ratio 14.1:3.9:41:41 mixing and using 90 DEG C of heating water baths and stir to clarify, transparent glue it is solidifying Colloidal state；
3) electrolyte gel prepared by step 2 is paved with silicon wafer using syringe, then uses low speed 500rpm(5s), high speed Spin coating revolution 3500rpm(45s) makes solution form uniform film in silicon wafer, then silicon wafer is moved into 120 DEG C of vacuum oven and is moved back Fiery 10h forms 2 μm of electrolyte layer.
4) by the dispersion liquid of PEDOT:PSS use 1000rpm(60s) revolution spin coating prepare active layer, after in 120 DEG C of items Anneal 1h under part, and film thickness is about 200nm.
5) 30 μm of ditch road length are deposited out on the resulting silicon wafer of step 4) using special mask version by the way of thermal evaporation Wide 1000 μm of 50nm thick source drain electrode.
6) J71:ITIC(1:1) 18mg/ml is dissolved in chloroform on the basis of step 5), uses 1500rpm The spin coating revolution of (60s) prepares light absorbing layer, after anneal under the conditions of 150 DEG C 10min.
Embodiment 2
1) 1 .5cm × 1.5cm size, heavily doped P-type silicon wafer, through acetone, isopropanol, chloroform, distilled water will have been cut (three times) it cleans, then does substrate with clean silicon wafer is obtained after being dried with nitrogen.
2) ionic gel electrolyte is prepared: by polyacrylonitrile, bis trifluoromethyl sulfimide lithium, ethylene carbonate and carbonic acid Acrylic ester be in mass ratio 14.1:3.9:41:41 mixing and using 90 DEG C of heating water baths and stir to clarify, transparent glue it is solidifying Colloidal state；
3) electrolyte prepared by step 2 is layered at scraper and silicon wafer interface edge using syringe, scraper and silicon substrate distance It is 200 μm, blade coating speed is 20mm/s, moves into 120 DEG C of annealing 10h of vacuum oven after forming uniform film.
4) dispersion liquid of PEDOT:PSS is layered at scraper and silicon wafer interface edge on the basis of step 3), scraper and silicon Substrate distance is 100 μm, and blade coating speed is 20mm/s, after anneal under the conditions of 120 DEG C 1h, film thickness is about 300-400nm.
5) 30 μm of ditch road length are deposited out on the resulting silicon wafer of step 4) using special mask version by the way of thermal evaporation Wide 1000 μm of 50nm thick source drain electrode.
6) J71:ITIC(1:1) 18mg/ml is dissolved in chloroform on the basis of step 5), uses 1500rpm The spin coating revolution of (60s) prepares light absorbing layer, after anneal under the conditions of 150 DEG C 10min.
A kind of all solid state organic electrochemistry optotransistor transfer characteristic under the conditions of Compound eye prepared by embodiment 1 Curve is as shown in figure 3, photoresponse R and detectivity D are as shown in Figure 4.From the figure 3, it may be seen that planar structure organic electrochemistry optotransistor Photocurrent variations it is obvious.As shown in Figure 4 the maximum photoresponse (R) of planar structure organic electrochemistry optotransistor more than 6.7 × 105 AW−1With maximum probe rate (D) more than 9.7 × 1014Jones。
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention, It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (6)

1.一种全固态有机电化学光晶体管，其特征在于：所述有机电化学光晶体管为底栅平面结构，从下往上依次为基底、固态电解质层、有源层、源漏电极和吸光层，所述基底为高掺杂硅片，所述固态电解质层为聚合物离子凝胶电解质，所述有源层为聚合物导体材料，所述吸光层为有机光敏半导体材料。1. an all-solid-state organic electrochemical phototransistor, it is characterized in that: described organic electrochemical phototransistor is a bottom grid plane structure, and sequentially from bottom to top is substrate, solid electrolyte layer, active layer, source-drain electrode and light-absorbing The substrate is a highly doped silicon wafer, the solid electrolyte layer is a polymer ion gel electrolyte, the active layer is a polymer conductor material, and the light absorbing layer is an organic photosensitive semiconductor material. 2.根据权利要求1所述的一种全固态有机电化学光晶体管，其特征在于：所述聚合物离子凝胶电解质是将聚丙烯腈和双三氟甲基磺酰亚胺锂共混物溶于碳酸乙烯酯和碳酸丙烯酯的混合溶剂制得的，所述固态电解质层的厚度为2-3μm。2. An all-solid-state organic electrochemical phototransistor according to claim 1, wherein the polymer ion gel electrolyte is a blend of polyacrylonitrile and lithium bis-trifluoromethanesulfonimide It is prepared by dissolving in a mixed solvent of ethylene carbonate and propylene carbonate, and the thickness of the solid electrolyte layer is 2-3 μm. 3.根据权利要求1所述的一种全固态有机电化学光晶体管，其特征在于：所述聚合物导体材料为PEDOT:PSS或P3HT，所述有源层是通过旋涂工艺沉积制成，其厚度为100-600nm。3. a kind of all-solid-state organic electrochemical phototransistor according to claim 1, is characterized in that: described polymer conductor material is PEDOT:PSS or P3HT, and described active layer is deposited by spin coating process and is made, Its thickness is 100-600 nm. 4.根据权利要求1所述的一种全固态有机电化学光晶体管，其特征在于：所述源漏电极层所用材料为金、铝或银，其厚度为50-100nm。4 . The all-solid-state organic electrochemical phototransistor according to claim 1 , wherein the material used for the source and drain electrode layers is gold, aluminum or silver, and the thickness thereof is 50-100 nm. 5 . 5.根据权利要求1所述的一种全固态有机电化学光晶体管，其特征在于：所述吸光层的厚度为50-120nm。5 . The all-solid-state organic electrochemical phototransistor according to claim 1 , wherein the thickness of the light absorbing layer is 50-120 nm. 6 . 6.一种如权利要求1-5任一项所述的全固态有机电化学光晶体管的制备方法，其特征在于：所述方法具体包括以下步骤：6. A method for preparing an all-solid-state organic electrochemical phototransistor according to any one of claims 1-5, wherein the method specifically comprises the following steps: （1）在以高掺杂硅片为基底上通过旋涂或刮涂工艺沉积聚合物离子凝胶电解质并退火，得到固态电解质层；(1) A polymer ion gel electrolyte is deposited on a highly doped silicon wafer by spin coating or blade coating process and annealed to obtain a solid electrolyte layer; （2）在步骤（1）得到的电解质层上通过旋涂工艺旋涂聚合物导体材料，制得有源层；(2) spin-coating a polymer conductor material on the electrolyte layer obtained in step (1) by a spin-coating process to obtain an active layer; （3）在步骤（2）得到的有源层上通过热蒸发工艺制得源漏电极；(3) preparing source-drain electrodes by thermal evaporation process on the active layer obtained in step (2); （4）在步骤（3）得到的有源层上通过旋涂工艺旋涂有机光敏半导体材料，制得吸光层，即得到全固态有机电化学光晶体管。(4) Spin-coating an organic photosensitive semiconductor material on the active layer obtained in step (3) through a spin-coating process to prepare a light-absorbing layer, that is, to obtain an all-solid-state organic electrochemical phototransistor.
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Cited By (5)

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CN110123279A (en) * 2019-05-21 2019-08-16 深圳大学 A kind of stretchable photoelectric sensor and preparation method thereof
CN111048664A (en) * 2019-12-07 2020-04-21 福州大学 Organic electrochemical transistor with vertical structure and preparation method thereof
CN113410383A (en) * 2021-06-19 2021-09-17 西北工业大学 Battery type electrochemical synapse transistor based on polythiophene and preparation method thereof
CN117238929A (en) * 2023-11-10 2023-12-15 太原理工大学 Low-power consumption full-band optical communication chip and preparation method thereof
WO2024187047A1 (en) * 2023-03-09 2024-09-12 Purdue Research Foundation A photonic-organic electrochemical transistor

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110123279A (en) * 2019-05-21 2019-08-16 深圳大学 A kind of stretchable photoelectric sensor and preparation method thereof
CN111048664A (en) * 2019-12-07 2020-04-21 福州大学 Organic electrochemical transistor with vertical structure and preparation method thereof
CN113410383A (en) * 2021-06-19 2021-09-17 西北工业大学 Battery type electrochemical synapse transistor based on polythiophene and preparation method thereof
CN113410383B (en) * 2021-06-19 2022-09-16 西北工业大学 Battery type electrochemical synapse transistor based on polythiophene and preparation method thereof
WO2024187047A1 (en) * 2023-03-09 2024-09-12 Purdue Research Foundation A photonic-organic electrochemical transistor
CN117238929A (en) * 2023-11-10 2023-12-15 太原理工大学 Low-power consumption full-band optical communication chip and preparation method thereof
CN117238929B (en) * 2023-11-10 2024-01-23 太原理工大学 Low-power-consumption full-band optical communication chip and preparation method thereof

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Application publication date: 20190416