CN113410383B - Battery type electrochemical synapse transistor based on polythiophene and preparation method thereof - Google Patents
Battery type electrochemical synapse transistor based on polythiophene and preparation method thereof Download PDFInfo
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- 229920000123 polythiophene Polymers 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000003860 storage Methods 0.000 claims abstract description 53
- 150000001768 cations Chemical class 0.000 claims abstract description 38
- 150000001450 anions Chemical class 0.000 claims abstract description 34
- 239000003792 electrolyte Substances 0.000 claims abstract description 30
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 239000004065 semiconductor Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 14
- 210000004027 cell Anatomy 0.000 claims abstract 3
- -1 polycarbonyl Polymers 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 11
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 10
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- JOTQIXXCBHIDKJ-UHFFFAOYSA-N 1-ethyl-3-methylimidazolidine Chemical compound CCN1CCN(C)C1 JOTQIXXCBHIDKJ-UHFFFAOYSA-N 0.000 claims description 6
- DZUNDTRLGXGTGU-UHFFFAOYSA-N 2-(3-dodecylthiophen-2-yl)-5-[5-(3-dodecylthiophen-2-yl)thiophen-2-yl]thiophene Chemical compound C1=CSC(C=2SC(=CC=2)C=2SC(=CC=2)C2=C(C=CS2)CCCCCCCCCCCC)=C1CCCCCCCCCCCC DZUNDTRLGXGTGU-UHFFFAOYSA-N 0.000 claims description 6
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- LOQUCRDTGKHSBC-UHFFFAOYSA-N 1-ethyl-3-methylimidazolidin-1-ium trifluoromethanesulfonate Chemical compound FC(S(=O)(=O)[O-])(F)F.C(C)[NH+]1CN(CC1)C LOQUCRDTGKHSBC-UHFFFAOYSA-N 0.000 claims description 2
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- PZOFIRMIGXUPJG-UHFFFAOYSA-N CCN1CN(C)CC1.N#CNC#N Chemical compound CCN1CN(C)CC1.N#CNC#N PZOFIRMIGXUPJG-UHFFFAOYSA-N 0.000 claims description 2
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- PAMIQIKDUOTOBW-UHFFFAOYSA-N N-methylcyclohexylamine Natural products CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 2
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- CRUIOQJBPNKOJG-UHFFFAOYSA-N thieno[3,2-e][1]benzothiole Chemical compound C1=C2SC=CC2=C2C=CSC2=C1 CRUIOQJBPNKOJG-UHFFFAOYSA-N 0.000 claims description 2
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- GVZJRBAUSGYWJI-UHFFFAOYSA-N 2,5-bis(3-dodecylthiophen-2-yl)thiophene Chemical compound C1=CSC(C=2SC(=CC=2)C2=C(C=CS2)CCCCCCCCCCCC)=C1CCCCCCCCCCCC GVZJRBAUSGYWJI-UHFFFAOYSA-N 0.000 claims 1
- VBXNPZZQSDEMTB-UHFFFAOYSA-N pentacene-1,2,3,4-tetrone Chemical compound C1=CC=C2C=C(C=C3C(C=C4C(C(C(=O)C(=O)C4=C3)=O)=O)=C3)C3=CC2=C1 VBXNPZZQSDEMTB-UHFFFAOYSA-N 0.000 claims 1
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
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- G06N3/00—Computing arrangements based on biological models
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- G06N3/06—Physical realisation, i.e. hardware implementation of neural networks, neurons or parts of neurons
- G06N3/061—Physical realisation, i.e. hardware implementation of neural networks, neurons or parts of neurons using biological neurons, e.g. biological neurons connected to an integrated circuit
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- 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
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Abstract
The invention relates to a polythiophene-based battery type electrochemical synapse transistor and a preparation method thereof, belonging to the technical field of organic semiconductor materials and devices. The cell type electrochemical transistor is based on an electrochemical transistor and an electric double layer effect thereof, combines a reversible redox mechanism of a double-ion cell, takes a classical Hodgkin-Huxley model in neurobiology as guidance, and introduces an N type polymer semiconductor layer on the basis of a traditional P type electrochemical transistor, thereby greatly stabilizing the doping concentration of anions in a P type polymer and successfully solving a plurality of problems of unstable conducting state and the like caused by carrier recombination. The battery type device realizes the construction of a stable anion/cation storage interface, and simultaneously, the cation storage layer/the electrolyte layer/the anion storage layer respectively realize the deep simulation of three parts of biological synapses, namely presynaptic neurons/synaptic clefts/postsynaptic neurons.
Description
Technical Field
The invention belongs to the technical field of organic semiconductor materials and devices, and particularly relates to a polythiophene-based battery type electrochemical synapse transistor and a preparation method thereof.
Background
In recent years, with the rapid development of information technology, computer networks based on the conventional von neumann architecture have been difficult to satisfy the demand for information processing. The brain-like computing is a novel computing framework, and is expected to realize simulation of the biological neural network from hardware by means of simulation of a neuromorphic device capable of integrating computing into a whole, so that a classical computing strategy is expected to be fundamentally subverted, an information processing platform which is highly parallel, low in power consumption, highly integrated and capable of being prepared in a high-throughput mode is realized, and the requirements of future distributed computing and artificial intelligence deep development are further met.
In a neuromorphic computing system, an ideal artificial synapse device needs to have the characteristics of low power consumption, continuously adjustable electrical conduction state, good stability and durability and the like. Among neuromorphic devices constructed based on numerous mechanisms, organic electrochemical synapse transistors (OECTs) have received considerable attention from researchers because of the unique ion-electron coupled modulation processes that are very similar to the dynamic processes of ions in biological synapses. In the current research, the electric charge state of the electric double layer of the presynaptic gate/electrolyte interface cannot be maintained for a long time due to the diffusion, migration and interface recombination of carriers, which directly results in short state retention time of the presynaptic device and unstable storage of information. Therefore, how to design a synaptic transistor to have excellent electrochemical ion storage performance and synaptic plasticity is a core challenge in the development of the synaptic devices at present.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a polythiophene-based battery type electrochemical synapse transistor, wherein a battery type electrochemical synapse transistor is built by introducing an N-type organic semiconductor capable of storing cations into a grid electrode, and a double-ion battery is built by coupling the cation storage in an electrolyte/grid electrode presynaptic interface with the anion storage in a P-type semiconductor, so that the concentration of hole carriers in a channel is stabilized, and the problems of difficult charge storage, carrier recombination at the grid electrode/electrolyte interface and the like are solved. The device shows excellent ion response behavior and synapse plasticity, and realizes deep simulation of neurons before and after biological synapses, synaptic gaps and interface structures thereof.
Technical scheme
A polythiophene-based battery-type electrochemical synapse transistor is characterized by comprising an anion storage layer, an electrolyte layer, a cation storage layer, a source electrode, a drain electrode and a gate electrode; the anion storage layer is made of a P-type polythiophene semiconductor, namely a conjugated polymer with a main chain containing thiophene units; the material used for the cation storage layer is an organic semiconductor material capable of storing cations, and the material comprises, but is not limited to, a polycarbonyl compound; the electrolyte layer is made of a polymer which can provide enough anions/cations for the normal operation of the device, and is composed of electrolyte salt, solvent and gel polymer, including but not limited to liquid or gel electrolyte.
Preferably: the conjugated polymer having a thiophene unit in the main chain includes, but is not limited to, poly 3,3 ' -dialkyltetrathiophene (PQT-12), poly (3-hexylthiophene-2, 5-diyl) (P3HT), poly [2, 5-bis (3-dodecylthiophene-2-yl) thiophene [3,2-B ] thiophene (PBTTT-C12), poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT: PSS), poly [ (9, 9-dioctylfluorene-2, 7-diyl) -alt- (2,2' -bidithiophene-5, 5' -diyl) ] (F8T2), poly [ (9, 9-dioctylfluorene-2, 7-diyl) -alt- (2,1, 3-benzothiadiazole-4, 7-diyl) ] (F8BT), poly [ (benzodithiophene) -alt- (2, 5-bis (2-octyldodecyl) -3, 6-bis (thienyl) -pyrrolopyrroledione) ] (DPP-DTT), poly [2, 5-bis (2-octyldodecyl) pyrrolo [3,4-c ] pyrrolopyrrole-1, 4(2H,5H) -dione-3, 6-yl) -alt- (2, 2'; 5', 2 ", 5", 2 "' -tetrathiophene-5, 5" ' -yl) ] (PDPP 4T).
Preferably: the polycarbonyl compound includes, but is not limited to, 5,7,12, 14-Pentacenetetrone (pentalene tetrane), perylenetetracarboxylic dianhydride (PTCDA), 3,4,9, 10-tetracarboxydiimide (PTCDI), Poly (phenanthroline-9, 10-dione-2, 7-diyl) (Poly-PA), Poly (anthraquinone-9, 10-diyl) (Poly-AQ), Poly (anthraquinone-1, 5-diyl) (Poly-1,5AQ), Poly [ (cyclo-hexane-2, 5-diene-1, 4-dione-2, 5-diyl) -alt-sulfur ] (Poly-BQ-S), Poly [ (anthraquinone-1, 4-diyl) -alt-sulfur ] (Poly-AQ-S), Poly [ (anthraquinone-1, 5-diyl) -alt-thio ] (Poly-1,5AQ-S), Poly [ (benzimidazolyl) benzophenanthroline ] (BBL).
Preferably: the electrolyte salt includes but is not limited to lithium salt, zinc salt, ammonium salt, organic salt and ionic liquid; ionic liquids include, but are not limited to, 1-ethyl-3-methylimidazoline bis (trifluoromethylsulfonyl) imide ([ EMIM ] [ TFSI ]), 1-butyl-3-methylimidazoline bis (trifluoromethylsulfonyl) imide ([ BMIM ] [ TFSI ]), 1-allyl-3-methylimidazoline bis (trifluoromethylsulfonyl) imide salt ([ ami ] [ TFSI ]) or 1-butyl 1-methylpiperidine bis (trifluoromethylsulfonyl) imide salt ([ PP14] [ TFSI ]), 1-ethyl-3-methylimidazoline triflate ([ EMIM ] [ OTF ]), 1-ethyl-3-methylimidazoline dicyanamide salt ([ EMIM ] [ DCA ]), 1-ethyl-3-methylimidazoline hydrosulfate salt ([ EMIM ] [ SCN ]); solvents include, but are not limited to, ethyl carbonate, water, acetonitrile, Ethylene Carbonate (EC), diethyl carbonate (DEC), acetone; polymers used for the gel include, but are not limited to, polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polyvinylidene fluoride copolymer P (VDF-TrFE), polyvinylidene fluoride-hexafluoropropylene copolymer (P (VDF-HFP)), gelatin, chitosan.
Preferably: the anion storage layer is prepared through a spin coating process, and the thickness of the anion storage layer is 1-500 nm.
Preferably: the cation storage layer is prepared by deposition through a thermal evaporation or spin coating process, and the thickness of the cation storage layer is 10-500 nm.
Preferably: the electrolyte is prepared by a spin coating or blade coating process, and the thickness of the electrolyte is 1-100 mu m.
Preferably: the source electrode, the drain electrode and the gate electrode are made of materials including, but not limited to, gold, aluminum, silver and copper, and the thickness of the source electrode, the drain electrode and the gate electrode is 5-200 nm.
A method for preparing a polythiophene-based battery type electrochemical synapse transistor is characterized by comprising the following steps:
step 1: removing the dustproof film on the surface of the substrate, sequentially performing ultrasonic treatment by using acetone, isopropanol and deionized water, and drying the substrate after ultrasonic treatment;
step 2: preparing a source electrode and a drain electrode on the clean substrate obtained in the step (1) by a vacuum evaporation instrument;
and 3, step 3: spin-coating a polymer capable of storing anions on the substrate with the source and drain electrodes obtained in the step 2 by using a spin coater, and annealing to obtain an anion storage layer;
and 4, step 4: preparing an ion gel electrolyte on the basis of the polymer semiconductor layer obtained in the step 3, and drying the ion gel electrolyte to obtain a proper size to obtain an electrolyte layer;
and 5: carrying out evaporation on a polymer capable of storing cations on the basis of the electrolyte layer obtained in the step 4 to prepare a cation storage layer;
step 6: preparing a gate electrode on the active layer obtained in the step 5 by means of a vacuum evaporation instrument;
and 7: and (4) on the basis of the anion storage layer prepared in the step (3), transferring the gel electrolyte layer evaporated with the cation storage layer and the gate electrode obtained in the step (6) onto the anion storage layer obtained after the step (3), thereby obtaining the battery type electrochemical synapse transistor with a complete structure.
Advantageous effects
The invention is based on an electrochemical transistor and an electric double layer effect thereof, combines a reversible redox mechanism of a double-ion battery, takes a classical Hodgkin-Huxley model in neurobiology as a guide, introduces an N-type polymer semiconductor layer on the basis of a traditional P-type electrochemical transistor, realizes the storage of cations at a presynaptic interface of an electrolyte/grid while constructing a stable channel/electrolyte anion storage interface, and successfully solves the problems of difficult charge storage, carrier recombination at the grid/electrolyte interface and the like. Through the design and the construction of the battery type electrochemical synapse transistor structure similar to a double-ion battery structure, the front and back neurons of biological synapses, the synaptic gap and the interface structure of the synapses are deeply simulated, and excellent ion response behavior and synaptic plasticity are realized in a unit device. The invention not only shows the application potential of the battery type electrochemical synapse transistor in the neuromorphic calculation, but also provides a brand new thought for breaking the neck of Von Neumann and developing a high-performance calculation-integrated calculation architecture.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, wherein like reference numerals are used to designate like parts throughout.
FIG. 1 is a schematic diagram of a polythiophene-based electrochemical synapse transistor in accordance with example 1 of the present disclosure.
FIG. 2 is a graph of the transfer characteristics of the polythiophene-based electrochemical synapse transistor fabricated in example 1 of the present disclosure.
FIG. 3 is a memristive performance test curve for polythiophene-based electrochemical synapse transistors prepared in example 1 of the present disclosure.
FIG. 4 shows the EPSC behavior of polythiophene-based electrochemical synapse transistors of example 1 in various amplitudes and pulse widths.
FIG. 5 is a PPF test of polythiophene-based electrochemical synapse transistors prepared in accordance with example 1 hereof under various strength pulses.
FIG. 6 is a graphical representation of the double-pulse facilitation test and the relationship between PPF index and pulse interval, width, and amplitude for the polythiophene-based electrochemical synapse transistor fabricated in accordance with example 1 herein.
FIG. 7 is a process of synaptic weight enhancement/inhibition for a polythiophene-based electrochemical synapse transistor made in example 1 of the present disclosure.
FIG. 8 is the pulse frequency dependent plasticity of polythiophene-based electrochemical synapse transistors prepared in example 1 of the present invention.
FIG. 9 is a graph of the transfer characteristics of polythiophene-based electrochemical synapse transistors made in example 2 of the present disclosure.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a polythiophene-based battery type electrochemical synapse transistor, which is based on an electrochemical redox mechanism similar to presynaptic and postsynaptic membrane ion motion behaviors, and the overall device structure is characterized in that an N-type semiconductor layer is introduced to store cations on the basis of a traditional P-type organic electrochemical transistor, so that while a stable anion/cation storage interface is constructed, a cation storage layer/an electrolyte layer/an anion storage layer respectively realize deep simulation on three parts of biological synapses, namely presynaptic neurons/synaptic gaps/postsynaptic neurons. The device mechanism is an electrochemical oxidation-reduction reaction mechanism, namely when external bias is applied to the device, anions and cations in the electrolyte layer move and are doped to the anion storage layer and the cation storage layer respectively, and then the whole device realizes the stable storage of the anions and the cations.
The polythiophene-based battery-type electrochemical synapse transistor comprises a polymer semiconductor channel layer (anion storage layer), an electrolyte layer, a cation storage layer, a source electrode, a drain electrode and a gate electrode. The material used for the polymer semiconductor channel layer (anion storage layer) is a P-type polythiophene semiconductor, namely a conjugated polymer with a main chain containing thiophene units. The material used for the cation storage layer is an organic semiconductor material capable of storing cations, and includes but is not limited to a polycarbonyl compound. The electrolyte layer is made of a polymer which can provide enough anions/cations for normal operation of the device and consists of electrolyte salt, solvent and gel polymer.
Example 1
1) Cleaning of the substrate: removing the dustproof film on the surface of the substrate, sequentially carrying out ultrasonic treatment for 10 minutes by using acetone, isopropanol and deionized water, drying the substrate by using nitrogen, and transferring the substrate into a drying oven for drying, thereby obtaining a clean silicon oxide wafer as the substrate;
2) preparing a source electrode and a drain electrode: putting a customized electrochemical transistor source-drain electrode mask (the channel width W is 30 mu m and the channel length L is 2000 mu m) on a sample frame of an evaporation system, putting a substrate on the mask and fixing, and putting the sample frame into an evaporation cavityIn the method, 3-5cm of gold is placed on an evaporation tungsten boat, and then a cavity is closed; starting the cooling system and the compression pump, starting the power supply of the evaporation system and the vacuum gauge switch, then starting the mechanical pump and the electromagnetic valve in sequence, starting the molecular pump when the vacuum gauge reading is lower than 10Pa, and enabling the vacuum degree of the cavity to reach 2 multiplied by 10 -5 Turning on a thermal evaporation power supply when the pressure is lower than Pa, setting a heating current of about 180A to wait for the heating source to heat up, paying attention to the frequency change condition displayed by a quartz crystal oscillator plate on a film thickness instrument during heating, turning on a sample frame baffle after the frequency reduction rate of the crystal oscillator plate is stabilized, recording the frequency of the film thickness instrument as an initial value, turning off the baffle and a current switch of the thermal evaporation power supply when the frequency is reduced by 5000Hz, pressing a 'stop' button of a molecular pump, turning off the thermal evaporation power supply after the heating current of the thermal evaporation power supply and the working frequency of the molecular pump are reduced to 0, and sequentially turning off an electromagnetic valve, a mechanical pump, a power supply switch, a start cooling system and a compression pump; then opening an air inlet valve of a cavity of the evaporation instrument, filling argon until the internal pressure of the vacuum cavity is recovered to normal pressure, and then opening the cavity to finally finish the preparation of the source electrode and the drain electrode;
3) 5mg of poly 3,3 '-dialkyltetrathiophene (PQT-12) is weighed to prepare 5mg/ml of poly 3, 3' -dialkyltetrathiophene (PQT-12)/chlorobenzene solution, a magneton is added into the solution, and then the solution is sealed and placed on a heating plate of a magnetic stirrer, and the parameters of the heating plate are set to be 80 ℃ and 1500 revolutions per minute. After dissolution with stirring for at least 1 hour, filtration was carried out using a 0.22 μm PTFE hydrophobic filter and spin-coating parameters were set at 1000 rpm for 40 seconds. After the poly 3, 3' -dialkyl tetrathiophene (PQT-12) solution is cooled, a pipette is used for sucking the 100 mu m prepared solution to quickly and uniformly coat the whole substrate obtained in the step 2), a spin coating instrument is started at the same time, the spin-coated substrate is placed into an oven with the parameter set at 140 ℃ for annealing within 20 minutes, and finally the annealed substrate is placed into a vacuum drying oven for vacuum storage for later use.
4) Weighing 300mg of polyvinylidene fluoride-hexafluoropropylene copolymer (P (VDF-HFP)) into a sample bottle, sucking an acetone solvent into the sample bottle by using a liquid transfer gun, keeping the mass ratio of the polyvinylidene fluoride-hexafluoropropylene copolymer (P (VDF-HFP)) to the acetone at 1:7, and placing the sample bottle in an ultrasonic cleaner at the water temperature of 50 ℃ for ultrasonic treatment for 30 minutes. The steps of heating at 80 ℃ for 15 minutes and sonicating in a water bath at 50 ℃ for 15 minutes were repeated until the polyvinylidene fluoride-hexafluoropropylene copolymer (P (VDF-HFP)) was completely dissolved in the acetone solvent to clear. Finally, the solution is placed on a heating plate at 80 ℃ and is heated and stirred for 20 minutes, 1-ethyl-3-methylimidazoline bis (trifluoromethylsulfonyl) imide ([ EMIMTFSI ]) ionic liquid is taken by a liquid transfer gun and is added into a completely dissolved polyvinylidene fluoride-hexafluoropropylene copolymer (P (VDF-HFP))/acetone solution, the mass ratio of the polyvinylidene fluoride-hexafluoropropylene copolymer (P (VDF-HFP)) to the 1-ethyl-3-methylimidazoline bis (trifluoromethylsulfonyl) imide ([ EMIMTFSI ]) is kept at 1:4, finally, the obtained ionic gel solution is poured into a culture dish with consistent size and is placed into a vacuum drying box, setting the temperature of a drying oven to be 90 ℃, drying for 24 hours to ensure that the solvent is completely volatilized, and finally attaching the ion gel film which can completely cover the size of the channel on the substrate which is obtained in the step 2) and is evaporated with the source and drain electrodes.
5) Weighing 500mg of perylenetetracarboxylic dianhydride (PTCDA) powder, placing the powder into a clean crucible, placing the crucible into a tungsten wire coil of an evaporation instrument for fixing, and placing the silicon wafer substrate with the attached ionic gel obtained in the step 4) into a sample rack of the evaporation instrument. Opening an evaporation instrument to wait for a system to reach a specified vacuum degree, starting a thermal evaporation power switch, setting heating current to be 35A, opening a sample frame baffle and starting counting after waiting for the frequency of a quartz crystal vibrating piece on a film thickness instrument to uniformly decrease, closing the sample frame baffle after the frequency decreases by 800Hz, and closing a thermal evaporation power supply to finally obtain the substrate with the cation storage layer.
6) And (3) preparing a gate electrode on the substrate obtained in the step 5) by using a special mask in a thermal evaporation mode, wherein the preparation method is the same as the step 2).
7) On the basis of the anion storage layer (poly 3, 3' -dialkyl tetrathiophene (PQT-12)) prepared in the step 3), transferring the gel electrolyte layer steamed with the cation storage layer (perylene tetracarboxylic dianhydride (PTCDA)) and the gate electrode, which is obtained in the step 6), onto the anion storage layer obtained in the step 3), so as to obtain the battery-type electrochemical synapse transistor with a complete structure.
8) And (3) testing the electrical performance, the memristive performance and the synaptic plasticity of the battery-type electrochemical synaptic transistor obtained in the step 7) by using a Keithley 4200A-SCS type semiconductor parameter analyzer and a TTPX low-temperature probe table.
Example 2
Example 2 differs from example 1 only in that the ionic liquid used in step (4) is 1-ethyl-3-methylimidazole trifluoromethanesulfonate ([ EMIM ] [ OTF ]).
When the device is subjected to basic electrical performance tests, the device shows excellent electrochemical properties including but not limited to that the gate voltage-current of the device has typical oxidation/reduction characteristics, the output and transfer characteristic curve of the device has typical hysteresis characteristics of a memristor, and the memristor characteristics of which the electric conduction state is continuously adjustable.
When the device is tested for synaptic function, the device has good synaptic plasticity, including but not limited to excitatory postsynaptic current (EPSC), double pulse facilitation (PPF), enhancement/inhibition of synaptic weights (latency/suppression), pulse frequency dependent plasticity (SRDP).
While the invention has been described with reference to specific embodiments, the invention is not limited thereto, and various equivalent modifications or substitutions can be easily made by those skilled in the art within the technical scope of the present disclosure.
Claims (9)
1. A cell type electrochemical synapse transistor based on polythiophene is characterized by sequentially comprising a source electrode, a drain electrode, an anion storage layer, an electrolyte layer, a cation storage layer and a gate electrode; the anion storage layer is made of a P-type polythiophene semiconductor, namely a conjugated polymer with a main chain containing thiophene units; the material used for the cation storage layer is an organic semiconductor material capable of storing cations and comprises a polycarbonyl compound; the electrolyte layer is made of a polymer which can provide enough anions/cations for the normal operation of the device, and consists of electrolyte salt, solvent and gel polymer, and comprises liquid or gel electrolyte.
2. The polythiophene-based battery-type electrochemical synapse transistor of claim 1, wherein said backbone comprises conjugated polymers of thiophene units, including poly 3,3 ' ' ' -dialkyltetrathiophene (PQT-12), poly (3-hexylthiophene-2, 5-diyl) (P3HT), poly [2, 5-bis (3-dodecylthiophen-2-yl) thiophene [3,2-B ] thiophene (PBTTT-C12), poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT: PSS), poly [ (9, 9-dioctylfluorene-2, 7-diyl) -alt- (2,2' -dithiophene-5, 5' -diyl) ] (F8T2), poly [ (9, 9-dioctylfluorene-2, 7-diyl) -alt- (2,1, 3-benzothiadiazole-4, 7-diyl) ] (F8BT), poly [ (benzodithiophene) -alt- (2, 5-bis (2-octyldodecyl) -3, 6-bis (thienyl) -pyrrolopyrroledione) ] (DPP-DTT), poly [2, 5-bis (2-octyldodecyl) pyrrolo [3,4-c ] pyrrolopyrrole-1, 4(2H,5H) -dione-3, 6-yl) -alt- (2,2 '; 5', 2 '', 5 '', 2 '' '-tetrathiophene-5, 5' '' -yl) ] (PP 4 PD 4T).
3. The polythiophene-based battery-type electrochemical synapse transistor of claim 1, wherein said polycarbonyl compound comprises 5,7,12, 14-Pentacenetetrone (pentacene tetrone), perylenetetracarboxylic dianhydride (PTCDA), 3,4,9, 10-tetracarboxydiimide (PTCDI), Poly (phenanthroline-9, 10-dione-2, 7-diyl) (Poly-PA), Poly (anthraquinone-9, 10-diyl) (Poly-AQ), Poly (anthraquinone-1, 5-diyl) (Poly-1,5AQ), Poly [ (cyclo-2, 5-diene-1, 4-dione-2, 5-diyl) -alt-sulfur ] (Poly-BQ-S), Poly [ (anthraquinone-1, 4-diyl) -alt-sulfur ] (Poly-AQ-S) Poly [ (anthraquinone-1, 5-diyl) -alt-thio ] (Poly-1,5AQ-S), Poly [ (benzimidazolyl) benzophenanthroline ] (BBL).
4. The polythiophene-based battery-type electrochemical synapse transistor of claim 1, wherein said electrolyte salt comprises a lithium salt, a zinc salt, an ammonium salt, an organic salt, an ionic liquid; the ionic liquid comprises 1-ethyl-3-methylimidazoline bis (trifluoromethylsulfonyl) imide ([ EMIM ] [ TFSI ]), 1-butyl-3-methylimidazoline bis (trifluoromethylsulfonyl) imide ([ BMIM ] [ TFSI ]), 1-allyl-3-methylimidazoline bis (trifluoromethylsulfonyl) imide salt ([ AMIM ] [ TFSI ]) or 1-butyl 1-methylpiperidine bis (trifluoromethylsulfonyl) imide salt ([ PP14] [ TFSI ]), 1-ethyl-3-methylimidazoline triflate ([ EMIM ] [ OTF ]), 1-ethyl-3-methylimidazoline dicyanamide salt ([ EMIM ] [ DCA ]), 1-ethyl-3-methylimidazoline hydrosulfate ([ EMIM ] [ SCN ]); the solvent comprises ethyl carbonate, water, acetonitrile, Ethylene Carbonate (EC), diethyl carbonate (DEC), acetone; the polymer for gel comprises polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polyvinylidene fluoride copolymer P (VDF-TrFE), polyvinylidene fluoride-hexafluoropropylene copolymer (P (VDF-HFP)), gelatin, and chitosan.
5. The polythiophene-based battery-type electrochemical synapse transistor of claim 1, wherein said anion storage layer is formed by a spin-coating process, and has a thickness of 1-500 nm.
6. The polythiophene-based battery-type electrochemical synapse transistor of claim 1, wherein said cation storage layer is deposited by thermal evaporation or spin coating process, and has a thickness of 10-500 nm.
7. The polythiophene-based battery-type electrochemical synapse transistor of claim 1, wherein said electrolyte is prepared by spin-coating or doctor-blading process, and has a thickness of 1-100 μm.
8. The polythiophene-based battery-type electrochemical synapse transistor of claim 1, wherein the source, drain, and gate electrodes are made of gold, aluminum, silver, and copper with a thickness of 5-200 nm.
9. A method for preparing a polythiophene-based battery type electrochemical synapse transistor is characterized by comprising the following steps:
step 1: removing the dustproof film on the surface of the substrate, sequentially performing ultrasonic treatment by using acetone, isopropanol and deionized water, and drying the substrate after ultrasonic treatment;
step 2: preparing a source electrode and a drain electrode on the clean substrate obtained in the step (1) by a vacuum evaporation instrument;
and step 3: spin-coating a polymer capable of storing anions on the substrate with the source and drain electrodes obtained in the step 2 by using a spin coater, and annealing to obtain an anion storage layer;
and 4, step 4: preparing an ionic gel electrolyte, drying and then taking the ionic gel electrolyte to obtain an electrolyte layer with a proper size;
and 5: carrying out evaporation on a polymer capable of storing cations on the basis of the electrolyte layer obtained in the step 4 to prepare a cation storage layer;
step 6: preparing a gate electrode on the cation storage layer obtained in the step 5 by means of a vacuum evaporation instrument;
and 7: on the basis of the anion storage layer prepared in the step 3, transferring the gel electrolyte layer evaporated with the cation storage layer and the gate electrode obtained in the step 6 onto the anion storage layer obtained after the step 3, thereby obtaining a battery type electrochemical synapse transistor with a complete structure;
the anion storage layer is made of a P-type polythiophene semiconductor, namely a conjugated polymer with a main chain containing thiophene units; the material used for the cation storage layer is an organic semiconductor material capable of storing cations and comprises a polycarbonyl compound; the material used for the electrolyte layer is a polymer which can provide enough anions/cations for the normal operation of the device, and the electrolyte layer consists of electrolyte salt, solvent and gel polymer and comprises liquid or gel electrolyte.
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