CN116600614A - Method for improving operation stability of poly (benzodifurandione) conductive high polymer material solution - Google Patents
Method for improving operation stability of poly (benzodifurandione) conductive high polymer material solution Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 75
- 239000002861 polymer material Substances 0.000 title claims abstract description 42
- 239000000758 substrate Substances 0.000 claims abstract description 121
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 76
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 61
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 33
- 239000001301 oxygen Substances 0.000 claims abstract description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000009832 plasma treatment Methods 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 12
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims abstract description 5
- 229910052736 halogen Chemical group 0.000 claims abstract description 5
- 150000002367 halogens Chemical group 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000004593 Epoxy Substances 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- -1 mercapto, amino, vinyl Chemical group 0.000 claims description 46
- 238000004528 spin coating Methods 0.000 claims description 35
- 239000011521 glass Substances 0.000 claims description 17
- 239000004973 liquid crystal related substance Substances 0.000 claims description 10
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 230000005693 optoelectronics Effects 0.000 claims description 2
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 abstract description 11
- 230000003993 interaction Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 32
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 32
- 239000000463 material Substances 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000004140 cleaning Methods 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 239000003344 environmental pollutant Substances 0.000 description 16
- 238000003760 magnetic stirring Methods 0.000 description 16
- 231100000719 pollutant Toxicity 0.000 description 16
- 238000001291 vacuum drying Methods 0.000 description 16
- 238000010586 diagram Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 229920000144 PEDOT:PSS Polymers 0.000 description 7
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 6
- 238000012876 topography Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 125000000468 ketone group Chemical group 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical group OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 210000001175 cerebrospinal fluid Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011243 crosslinked material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 210000003722 extracellular fluid Anatomy 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- NHBRUUFBSBSTHM-UHFFFAOYSA-N n'-[2-(3-trimethoxysilylpropylamino)ethyl]ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCNCCN NHBRUUFBSBSTHM-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- MQVCTPXBBSKLFS-UHFFFAOYSA-N tri(propan-2-yloxy)-propylsilane Chemical compound CCC[Si](OC(C)C)(OC(C)C)OC(C)C MQVCTPXBBSKLFS-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
-
- 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
- H10K71/60—Forming conductive regions or layers, e.g. electrodes
-
- 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
Abstract
The invention discloses a method for improving the operation stability of a poly (benzodifurandione) conductive high polymer material solution, which comprises the following steps: s1, stirring and mixing a poly (benzodifurandione) solution and a silane coupling agent to obtain a conductive polymer solution; s2, washing and drying the substrate, then performing oxygen plasma treatment, and thenThe conductive polymer solution is spin-coated on the surface of the substrate, and a device is obtained after drying; the structural formula of the silane coupling agent is Y-R-SiX 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein, X is selected from alkoxy, acetoxy or halogen; y is epoxy, sulfhydryl or amino; the R is selected from a hydrogen atom, an alkyl group, an alkyl derivative, an alkylene group or an alkylene derivative. The invention utilizes the chemical bonding action between the coupling agent and the conductive polymer material as well as between the coupling agent and the substrate to improve the interaction force between the conductive polymer material and the substrate, thereby solving the problem of poor operation stability of the corresponding organic electronic device in solution.
Description
Technical Field
The invention relates to the field of semiconductor materials, in particular to a method for improving the operation stability of a poly (benzodifurandione) conductive polymer material solution.
Background
Organic conductive polymer materials have received extensive attention from researchers in recent years, mainly due to the fact that they can be obtained by solution processing at normal temperature, simplifying the processing procedure and facilitating the preparation of flexible organic electronic devices. Thanks to the flexible nature of the organic electronic device, it can be used as a biosensing device for monitoring the electrophysiological activity signal of an organism. Physiological activity of tissue in a living body is produced by ion exchange of body tissue with body fluids (e.g., blood, interstitial fluid, cerebrospinal fluid, etc.). Therefore, the solution operation stability of the organic electronic device is important in order to obtain a stable electrophysiological signal for a long period.
An important factor in determining the operational stability of an organic electronic device is the organic active material, which can undergo ion exchange in an ambient solution environment. Because of the poor adhesion between the organic material and the substrate (such as silicon, quartz, etc.), the organic material is very easy to fall off from the surface of the substrate when the device is operated in a solution, and long-term stable operation is difficult to realize.
Organic conductive polymer materials can be classified into p-type and n-type based on the difference of carriers. The development of p-type and n-type materials with high performance and high operational stability is extremely important in order to construct complex complementary circuits. Currently, for commercial p-type organic conductive materials, poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate (PEDOT: PSS), researchers have mainly employed methods of adding cross-linking agents to the solution to improve the solution stability of the material. However, the introduction of the crosslinking agent is disadvantageous for the removal of the excessive insulating polymer PSS, resulting in a decrease in the conductivity of the material, affecting the conductive properties of the material. For example, the literature Effect of (3-glycylglycidyl) Trimethoxysilane (GOPS) on the Electrical Properties of PEDOT:PSS Films, journal of Polymer Science, part B:Polymer Physics 2017,55,814-820 adopts a method of introducing different amounts of crosslinking agents GOPS into an organic conductive Polymer solution PEDOT:PSS, and the influence of the small molecules on the conductivity of the PEDOT:PSS and the stability of the solution is studied. The research shows that the silane coupling agent can effectively improve the adhesion of PEDOT PSS on the surface of the substrate, thereby improving the solution operation stability of the material; however, since the epoxy groups in the GOPS react with the benzenesulfonic acid groups in the PSS molecules, removal of the excess non-conductive PSS molecules is not favored, resulting in a significant decrease in the conductive properties of the material with increasing levels of GOPS.
The development of n-type organic semiconductor materials has been relatively retarded, mainly due to the poor stability of n-type materials in air and water-oxygen environments. Recently, development of highly conductive, solution processable n-type organic conductive polymer materials has prompted development of n-type organic electronic devices. However, when the material works under the condition of solution, the material is very easy to be stripped from the surface of the substrate under the action of external voltage, which is unfavorable for the preparation and stable operation of the multilayer deposition device.
Therefore, there is a need to improve the operation stability of the organic conductive material, which is not only beneficial to the processing of the multilayer complex structure device, but also helps to construct a complex circuit and widens the application range of the organic electronic device.
Disclosure of Invention
Based on the above, in order to solve the defects existing in the prior art, the invention provides a method for improving the operation stability of a poly (benzodifurandione) (PBFDO) conductive polymer material solution. According to the invention, the small molecular coupling agent is introduced into the conductive polymer solution, and the interaction force between the conductive polymer material and the substrate is improved by utilizing the chemical bonding action between the coupling agent and the substrate, so that the problem of poor operation stability of the corresponding organic electronic device in the solution is solved. The method is suitable for preparing n-type organic semiconductor materials/devices.
The invention adopts the following technical scheme:
an object of the present invention is to provide a method for improving the operation stability of a solution of a poly (benzodifurandione) conductive polymer material, comprising the steps of:
s1, dissolving a poly (benzodifurandione) solution (the poly (benzodifurandione) is dissolved in DMSO (dimethyl sulfoxide)) and a silane coupling agent, and stirring and mixing to obtain a conductive polymer solution;
s2, washing and drying a substrate, performing oxygen plasma treatment, spin-coating the conductive polymer solution on the surface of the substrate, and drying to obtain a device;
the structural formula of the silane coupling agent is Y-R-SiX 3 ；
Wherein, the liquid crystal display device comprises a liquid crystal display device,
the X is selected from alkoxy, acetoxy or halogen;
the Y is selected from epoxy, mercapto, amino, vinyl or methacryloxy;
the R is selected from a hydrogen atom, an alkyl group, an alkyl derivative, an alkylene group or an alkylene derivative;
one or more carbons of the alkyl or alkylene derivative are substituted with one or more of oxygen, amino, sulfone, carbonyl, aryl, alkylene, alkynyl, ester, cyano, nitro;
and/or
One or more hydrogens on the alkyl or alkylene derivative are substituted with one or more of halogen, hydroxy, amino, carboxy, cyano, nitro, aryl, alkenyl, alkynyl.
In the present invention, the silane coupling agent molecule Y-R-SiX 3 Wherein the X groups can generate hydrolysis reaction to generate silicon hydroxyl groups (Si-OH), so that the silicon hydroxyl groups can interact with oxygen-containing functional groups on the surface of a substrate (such as glass, silicon, metals such as aluminum, iron, zinc and the like) and are bonded on the surface of the substrate; the Y group, which is preferably an epoxy group, a mercapto group or an amino group in the silane coupling agent, can be dissolved in an organic solvent and subjected to hydrolysis reaction in water to interact with furan or ketone groups in the PBFDO. By introducing a silane coupling agent between the conductive polymer material and the substrate as a bridge, couplingThe agent is chemically combined with the conductive polymer material and the substrate, so that the interaction force between the material and the substrate is improved.
Further, examples of the alkyl group include a linear alkyl group or a branched alkyl group, and the linear alkyl group includes, but is not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl; branched alkyl groups include, but are not limited to, isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 2-ethylbutyl, 2-ethylhexyl, 2-ethyloctyl, 2-butylhexyl, 2-hexyloctyl, 4-hexyldecyl, 3-hexylundecyl, 2-octyldecyl, 2-octyldodecyl, 3-octyltridecyl, 2-decyldodecyl, 2-decyltetradecyl, 3-decyltentadecyl, 2-dodecylhexadecyl, 4-octyltetradecyl, 4-decyltetradecyl, 4-hexyldecyl, 4-octyldodecyl, 4-decyltetradecyl, 4-dodecylhexadecyl, and the like.
Further, examples of the alkoxy group include, but are not limited to, methoxy, ethoxy, propoxy, n-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecoxy, n-dodecoxy, 2-ethylhexoxy, 2-ethyloctoxy, 2-butylhexoxy, 2-hexyloctoxy, 4-hexyldecoxy, 3-hexylundecoxy, 2-octyldecoxy, 2-octyldodecoxy, 3-octyltridecyloxy, 2-decyldodecoxy, 2-decyltetradecyloxy, 3-decylpentadecyloxy, 2-dodecylhexadecyloxy, 4-octyltetradecyloxy, 4-decylhexadecyloxy, 4-hexyldecyloxy, 4-octyldodecoxy, 4-decyltetradecyloxy, 4-dodecylhexadecyloxy and the like.
Further preferably, the Y is selected from-SH or-NH 2 。
Further preferably, X is selected from an alkoxy group having 1 to 6 carbon atoms or an acetoxy group.
Further preferably, the silane coupling agent is selected from the group consisting of 3- (2, 3-glycidoxy) propyltrimethoxysilane, 3- (2, 3-glycidoxy) propyltriethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-aminopropyl triethoxysilane, diethylenetriaminopropyl trimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane, gamma-methacryloyloxy propyltriisopropoxysilane.
Further, the poly (benzodifurandione) solution has a concentration of 5-15mg/ml.
Further, in the step S1, the volume ratio of the silane coupling agent to the poly (benzodifurandione) solution is 0.5-5%.
Further, the substrate is selected from one of glass and ITO, PET, PI.
Further, in step S1, the stirring time is 1-2h.
Further, in step S2, the oxygen plasma treatment time is 1-5min.
Further, the method for improving the operation stability of the poly (benzodifurandione) conductive high polymer material solution comprises the following steps:
s1, mixing a PBFDO solution and a silane coupling agent through magnetic stirring for 1-2 hours to obtain a conductive polymer solution;
s2, cleaning the substrate in deionized water, acetone and isopropanol for 10min by an ultrasonic method in sequence, removing pollutants on the surface of the substrate, and placing the substrate in an oven for drying at 60 ℃ overnight; and (3) processing the dried substrate in oxygen plasma for 1-5min, spin-coating the conductive polymer solution on the surface of the substrate at 800-3000r/min by a solution spin-coating method, and finally drying to obtain the device.
Further, the substrate material is treated with an oxygen plasma to generate oxygen-containing functional groups on the substrate surface and to increase the substrate surface roughness so as to enhance the interaction force with the material.
Further, by adopting different spin coating speeds of 800-3000 rpm, the PBFDO/coupling agent solution is dripped on the surface of the substrate, and the conductive films with different thicknesses are obtained.
Further, in step S2, the sample is placed in a vacuum drying oven and dried in vacuum at 40-50 ℃ for 5-12 hours, so as to remove the excessive dimethyl sulfoxide solvent in the sample.
Another object of the present invention is to provide an application of the method for improving the operation stability of the poly (benzodifurandione) conductive polymer material solution in an optoelectronic device.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts a method of adding the coupling agent, on the basis of not reducing the conductive performance of the PBFDO material, the interaction of the epoxy group, the mercapto group, the amino group and other groups on the surface of the specific coupling agent and the conductive polymer material group and the interaction of the silane group on the surface of the specific coupling agent and the oxygen-containing group on the surface of the substrate after plasma treatment are utilized, and the specific coupling agent can be used as a bridge for connecting the conductive polymer material and the substrate, so that the adhesive force between the material and the substrate is improved, and the solution operation stability of the poly (benzodifurandione) -based organic electronic device is improved. Meanwhile, compared with other n-type semiconductor materials, the semiconductor material has better conductivity and stability, and is beneficial to the construction of high-performance organic complex circuits.
Drawings
FIG. 1 is a schematic diagram of the reaction of a silane coupling agent GOPS with PBFDO and a substrate;
wherein, the liquid crystal display device comprises a liquid crystal display device,
fig. 1 (a) shows chemical structural formulas of a conductive polymer PBFDO and a silane coupling agent GOPS;
fig. 1 (b) is a schematic view of oxygen plasma treatment of a glass substrate;
fig. 1 (c) is a schematic diagram of bonding between a silane coupling agent molecule GOPS and an organic conductive polymer;
fig. 1 (d) is a schematic diagram of bonding of silane coupling agent molecules GOPS to a plasma-treated glass substrate.
FIG. 2 is a diagram showing the working morphology of an organic conductive polymer film under the action of an externally applied potential;
wherein, the liquid crystal display device comprises a liquid crystal display device,
fig. 2 (a) is a topography diagram of a blank after 1min of operation in a solution under the action of an applied potential;
fig. 2 (b) is a topography of the device 1 after 3 hours of operation in solution under the action of an applied potential;
fig. 2 (c) is a topography of the device 1 after 3h of immersion in solution;
fig. 2 (d) is a morphology diagram of the organic conductive polymer thick film after soaking in the solution for 3 hours;
within the box of the figure are samples immersed in the solution.
Fig. 3 is an ultraviolet-visible spectrum of the organic conductive polymer film of the device 1 after working for 0h and 3h under the action of an external potential in a solution.
Fig. 4 is a cyclic voltammogram of the organic conductive polymer film of device 1 after 3 hours of operation in solution under the action of an applied potential.
Detailed Description
In order to more clearly illustrate the technical scheme of the invention, the following preparation examples and examples are listed. The starting materials, reactions and workup procedures used in the preparation examples and examples are those commonly practiced in the market and known to those skilled in the art unless otherwise indicated.
Example 1
A method for improving the operation stability of a poly (benzodifurandione) conductive high polymer material solution comprises the following steps:
s1, mixing a PBFDO solution (the concentration is 15 mg/ml) and a silane coupling agent M1 (0.5% of the volume of the PBFDO solution) for 1h by magnetic stirring to obtain a conductive polymer solution;
the structural formula of the silane coupling agent M1 is
S2, cleaning the glass substrate in deionized water, acetone and isopropanol for 10min sequentially by an ultrasonic method, removing pollutants on the surface of the substrate, and placing the substrate in an oven for drying at 60 ℃ overnight; and (3) carrying out oxygen plasma treatment on the dried substrate for 5min, spin-coating the conductive polymer solution on the surface of the substrate at 3000r/min by a solution spin-coating method, and carrying out vacuum drying at 45 ℃ for 5h to obtain the device 1.
Fig. 1 is a schematic diagram showing the principle of the reaction of the silane coupling agent M1 of the present embodiment with PBFDO and a substrate; wherein (a) in fig. 1 is a chemical structural formula of a conductive polymer PBFDO and a silane coupling agent M1; fig. 1 (b) is a schematic diagram of oxygen plasma treatment of a glass substrate; in fig. 1, (c) is a schematic diagram of bonding between a silane coupling agent molecule M1 and an organic conductive polymer, and an epoxy group in the M1 molecule may react with furan or ketone groups of a PBFDO molecule to form esters, so that the main chain structure of the PBFDO molecule is not affected, and the conductivity of the material is not significantly changed; in fig. 1, (d) is a schematic diagram of molecular bonding between a silane coupling agent molecule M1 and a glass substrate subjected to plasma treatment, wherein the surface of the glass substrate is rich in oxygen-containing groups such as hydroxyl groups or carboxyl groups after being subjected to oxygen plasma treatment, and silane groups in the molecule M1 can bond with the oxygen-containing groups to form silica groups, so that the adhesive force between the substrate and a PBFDO material is increased, and the operation stability of a PBFDO-based device in a solution is improved.
Example 2
A method for improving the operation stability of a poly (benzodifurandione) conductive high polymer material solution comprises the following steps:
s1, mixing a PBFDO solution (the concentration is 15 mg/ml) and a silane coupling agent M2 (5% of the volume of the PBFDO solution) for 2 hours by magnetic stirring to obtain a conductive polymer solution;
the structural formula of the silane coupling agent M2 is
S2, cleaning the ITO substrate in deionized water, acetone and isopropanol for 10min sequentially by an ultrasonic method, removing pollutants on the surface of the substrate, and placing the substrate in an oven for drying at 60 ℃ overnight; and (3) carrying out oxygen plasma treatment on the dried substrate for 1min, spin-coating the conductive polymer solution on the surface of the substrate by a solution spin-coating method, and carrying out vacuum drying at 45 ℃ for 5h to obtain the device 2.
Example 3
A method for improving the operation stability of a poly (benzodifurandione) conductive high polymer material solution comprises the following steps:
s1, mixing a PBFDO solution (the concentration is 15 mg/ml) and a silane coupling agent M3 (1% of the volume of the PBFDO solution) for 1.5 hours by magnetic stirring to obtain a conductive polymer solution;
the structural formula of the silane coupling agent M3 is
S2, cleaning the glass substrate in deionized water, acetone and isopropanol for 10min sequentially by an ultrasonic method, removing pollutants on the surface of the substrate, and placing the substrate in an oven for drying at 60 ℃ overnight; and (3) carrying out oxygen plasma treatment on the dried substrate for 3min, spin-coating the conductive polymer solution on the surface of the substrate by a solution spin-coating method, and carrying out vacuum drying at 45 ℃ for 5h to obtain the device 3.
Example 4
A method for improving the operation stability of a poly (benzodifurandione) conductive high polymer material solution comprises the following steps:
s1, mixing a PBFDO solution (the concentration is 15 mg/ml) and a silane coupling agent M4 (0.5% of the volume of the PBFDO solution) for 1.8 hours by magnetic stirring to obtain a conductive polymer solution;
the structural formula of the silane coupling agent M4 is
S2, cleaning the PET substrate in deionized water, acetone and isopropanol for 10min sequentially by an ultrasonic method, removing pollutants on the surface of the substrate, and placing the substrate in an oven for drying at 60 ℃ overnight; and (3) carrying out oxygen plasma treatment on the dried substrate for 2min, spin-coating the conductive polymer solution on the surface of the substrate by a solution spin-coating method, and carrying out vacuum drying at 45 ℃ for 5h to obtain the device 4.
Example 5
A method for improving the operation stability of a poly (benzodifurandione) conductive high polymer material solution comprises the following steps:
s1, mixing a PBFDO solution (the concentration is 15 mg/ml) and a silane coupling agent M1 (0.5% of the volume of the PBFDO solution) for 1h by magnetic stirring to obtain a conductive polymer solution;
the structural formula of the silane coupling agent M1 is
S2, cleaning the glass substrate in deionized water, acetone and isopropanol for 10min sequentially by an ultrasonic method, removing pollutants on the surface of the substrate, and placing the substrate in an oven for drying at 60 ℃ overnight; and (3) carrying out oxygen plasma treatment on the dried substrate for 5min, spin-coating the conductive polymer solution on the surface of the substrate at 3000r/min by a solution spin-coating method, and vacuum drying at 45 ℃ for 12h to obtain the device 5.
Example 6
A method for improving the operation stability of a poly (benzodifurandione) conductive high polymer material solution comprises the following steps:
s1, mixing a PBFDO solution (the concentration is 15 mg/ml) and a silane coupling agent M1 (0.5% of the volume of the PBFDO solution) for 1h by magnetic stirring to obtain a conductive polymer solution;
the structural formula of the silane coupling agent M1 is
S2, cleaning the glass substrate in deionized water, acetone and isopropanol for 10min sequentially by an ultrasonic method, removing pollutants on the surface of the substrate, and placing the substrate in an oven for drying at 60 ℃ overnight; and (3) carrying out oxygen plasma treatment on the dried substrate for 5min, spin-coating the conductive polymer solution on the surface of the substrate by a solution spin-coating method, and carrying out vacuum drying at 40 ℃ for 5h to obtain the device 6.
Example 7
A method for improving the operation stability of a poly (benzodifurandione) conductive high polymer material solution comprises the following steps:
s1, mixing a PBFDO solution (the concentration is 15 mg/ml) and a silane coupling agent M1 (0.5% of the volume of the PBFDO solution) for 1h by magnetic stirring to obtain a conductive polymer solution;
the structural formula of the silane coupling agent M1 is
S2, cleaning the glass substrate in deionized water, acetone and isopropanol for 10min sequentially by an ultrasonic method, removing pollutants on the surface of the substrate, and placing the substrate in an oven for drying at 60 ℃ overnight; and (3) carrying out oxygen plasma treatment on the dried substrate for 5min, spin-coating the conductive polymer solution on the surface of the substrate by a solution spin-coating method, and carrying out vacuum drying at 50 ℃ for 5h to obtain the device 7.
Example 8
A method for improving the operation stability of a poly (benzodifurandione) conductive high polymer material solution comprises the following steps:
s1, mixing a PBFDO solution (the concentration is 5 mg/ml) and a silane coupling agent M1 (0.5% of the volume of the PBFDO solution) for 1h by magnetic stirring to obtain a conductive polymer solution;
the structural formula of the silane coupling agent M1 is
S2, cleaning the glass substrate in deionized water, acetone and isopropanol for 10min sequentially by an ultrasonic method, removing pollutants on the surface of the substrate, and placing the substrate in an oven for drying at 60 ℃ overnight; and (3) carrying out oxygen plasma treatment on the dried substrate for 5min, spin-coating the conductive polymer solution on the surface of the substrate at 800r/min by a solution spin-coating method, and carrying out vacuum drying at 45 ℃ for 5h to obtain the device 8.
Example 9
A method for improving the operation stability of a poly (benzodifurandione) conductive high polymer material solution comprises the following steps:
s1, mixing a PBFDO solution (the concentration is 10 mg/ml) and a silane coupling agent M1 (0.5% of the volume of the PBFDO solution) for 1h by magnetic stirring to obtain a conductive polymer solution;
the structural formula of the silane coupling agent M1 is
S2, cleaning the glass substrate in deionized water, acetone and isopropanol for 10min sequentially by an ultrasonic method, removing pollutants on the surface of the substrate, and placing the substrate in an oven for drying at 60 ℃ overnight; and (3) carrying out oxygen plasma treatment on the dried substrate for 5min, spin-coating the conductive polymer solution on the surface of the substrate at 3000r/min by a solution spin-coating method, and carrying out vacuum drying at 45 ℃ for 5h to obtain the device 9.
Example 10
A method for improving the operation stability of a poly (benzodifurandione) conductive high polymer material solution comprises the following steps:
s1, mixing a PBFDO solution (the concentration is 15 mg/ml) and a silane coupling agent M5 (3.5% of the volume of the PBFDO solution) for 1.2 hours by magnetic stirring to obtain a conductive polymer solution;
the structural formula of the silane coupling agent M5 is
S2, cleaning the ITO substrate in deionized water, acetone and isopropanol for 10min sequentially by an ultrasonic method, removing pollutants on the surface of the substrate, and placing the substrate in an oven for drying at 60 ℃ overnight; and (3) carrying out oxygen plasma treatment on the dried substrate for 3min, spin-coating the conductive polymer solution on the surface of the substrate by a solution spin-coating method, and carrying out vacuum drying at 45 ℃ for 5h to obtain the device 10.
Example 11
A method for improving the operation stability of a poly (benzodifurandione) conductive high polymer material solution comprises the following steps:
s1, mixing a PBFDO solution (the concentration is 15 mg/ml) and a silane coupling agent M6 (3% of the volume of the PBFDO solution) for 2 hours by magnetic stirring to obtain a conductive polymer solution;
the structural formula of the silane coupling agent M6 is
S2, cleaning the glass substrate in deionized water, acetone and isopropanol for 10min sequentially by an ultrasonic method, removing pollutants on the surface of the substrate, and placing the substrate in an oven for drying at 60 ℃ overnight; and (3) carrying out oxygen plasma treatment on the dried substrate for 1.5min, spin-coating the conductive polymer solution on the surface of the substrate by a solution spin-coating method, and carrying out vacuum drying at 50 ℃ for 5h to obtain the device 11.
Example 12
A method for improving the operation stability of a poly (benzodifurandione) conductive high polymer material solution comprises the following steps:
s1, mixing a PBFDO solution (the concentration is 15 mg/ml) and a silane coupling agent M7 (2% of the volume of the PBFDO solution) for 1.6 hours by magnetic stirring to obtain a conductive polymer solution;
the structural formula of the silane coupling agent M7 is
S2, cleaning the PET substrate in deionized water, acetone and isopropanol for 10min sequentially by an ultrasonic method, removing pollutants on the surface of the substrate, and placing the substrate in an oven for drying at 60 ℃ overnight; and (3) carrying out oxygen plasma treatment on the dried substrate for 2min, spin-coating the conductive polymer solution on the surface of the substrate by a solution spin-coating method, and carrying out vacuum drying at 40 ℃ for 12h to obtain the device 12.
Example 13
A method for improving the operation stability of a poly (benzodifurandione) conductive high polymer material solution comprises the following steps:
s1, mixing a PBFDO solution (the concentration is 10 mg/ml) and a silane coupling agent M8 (2.5% of the volume of the PBFDO solution) for 1.7 hours by magnetic stirring to obtain a conductive polymer solution;
the structural formula of the silane coupling agent M8 is
S2, cleaning the PET substrate in deionized water, acetone and isopropanol for 10min sequentially by an ultrasonic method, removing pollutants on the surface of the substrate, and placing the substrate in an oven for drying at 60 ℃ overnight; and (3) carrying out oxygen plasma treatment on the dried substrate for 2.5min, spin-coating the conductive polymer solution on the surface of the substrate by a solution spin-coating method, and carrying out vacuum drying at 50 ℃ for 5h to obtain the device 13.
Example 14
A method for improving the operation stability of a poly (benzodifurandione) conductive high polymer material solution comprises the following steps:
s1, mixing a PBFDO solution (the concentration is 15 mg/ml) and a silane coupling agent M9 (4.5% of the volume of the PBFDO solution) for 1.1h through magnetic stirring to obtain a conductive polymer solution;
the structural formula of the silane coupling agent M9 is
S2, cleaning the PI substrate in deionized water, acetone and isopropanol for 10min sequentially by an ultrasonic method, removing pollutants on the surface of the substrate, and placing the substrate in an oven for drying at 60 ℃ overnight; and (3) carrying out oxygen plasma treatment on the dried substrate for 4.5min, spin-coating the conductive polymer solution on the surface of the substrate by a solution spin-coating method, and carrying out vacuum drying at 50 ℃ for 12h to obtain the device 14.
Example 15
A method for improving the operation stability of a poly (benzodifurandione) conductive high polymer material solution comprises the following steps:
s1, mixing a PBFDO solution (the concentration is 15 mg/ml) and a silane coupling agent M10 (1.5% of the volume of the PBFDO solution) for 1.9 hours by magnetic stirring to obtain a conductive polymer solution;
the structural formula of the silane coupling agent M10 is
S2, cleaning the PI substrate in deionized water, acetone and isopropanol for 10min sequentially by an ultrasonic method, removing pollutants on the surface of the substrate, and placing the substrate in an oven for drying at 60 ℃ overnight; and (3) carrying out oxygen plasma treatment on the dried substrate for 4min, spin-coating the conductive polymer solution on the surface of the substrate by a solution spin-coating method, and carrying out vacuum drying at 45 ℃ for 12h to obtain the device 15.
Comparative example 1
The difference between this comparative example and example 1 is that: the procedure of example 1 was repeated except that the silane coupling agent M1 was replaced with 3-chloropropyl trimethoxysilane.
Comparative example 2
The difference between this comparative example and example 1 is that: the PBFDO solution was replaced with the same concentration of PEDOT: PSS, the formula was as follows, and the other steps and materials were the same as in example 1.
Comparative example 3
The difference between this comparative example and example 1 is that: replacement of the PBFDO solution with the same concentration
Other steps and materials were the same as in example 1.
Test case
The devices prepared in the above examples and comparative examples were subjected to performance tests.
The testing method comprises the following steps:
(1) The devices and blanks prepared in the examples (without coupling agent, other preparation methods were the same as in example 1) were placed on the surface of a hot bench and heated at 110℃for 10min in air. The electrochemical characteristics of the material are characterized by adopting a cyclic voltammetry, ITO/glass with a PBFDO film deposited on the surface is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a platinum wire electrode is used as a counter electrode, a 100mM sodium chloride solution is used as electrolyte for facilitating application in organisms, all the electrodes and the electrolyte are placed in a cuvette with the thickness of 1cm multiplied by 1cm, the cyclic voltammetry characterization is carried out on a sample by adopting a Switzerland Ten AUTOLAB PGSTATM204 electrochemical workstation as characterization equipment, and the sample sweeping speed is 50mV/s.
(2) The device was characterized by exposure to solvent for 1min and 3h using an ultraviolet-visible spectrometer Ocean optics QE65PRO, with a characterization range of 250nm to 1100nm.
Test results:
FIG. 2 shows a graph of the working morphology of an organic conductive polymer film under the action of an externally applied potential;
wherein, the liquid crystal display device comprises a liquid crystal display device,
fig. 2 (a) is a topography diagram of a blank after 1min of operation in a solution under the action of an applied potential;
fig. 2 (b) is a topography of the device 1 after 3 hours of operation in solution under the action of an applied potential;
fig. 2 (c) is a topography of device 1 (86 nm thickness) after 3h immersion in solution;
fig. 2 (d) is a morphology diagram of an organic conductive polymer thick film (with a thickness of 503 nm) after being immersed in a solution for 3 hours;
within the box of the figure are samples immersed in the solution.
As can be seen from fig. 2, for the conductive film without the coupling agent, it is difficult to obtain a spectrum and an electrochemical signal after one-time potential scanning, that is, falling off from the surface of the substrate, and the PBFDO film can stably operate for 3 hours in a solution state under the same condition after the silane coupling agent is introduced. After repeated oxidation-reduction reaction, the color of the film changes, and the PBFDO film is soaked in the solution under the condition that no potential is applied, so that the appearance and appearance of the PBFDO film are still kept intact. Even if the thickness of the film is increased, the morphology of the film is not changed.
Fig. 3 shows the uv-vis spectra of the organic conductive polymer film of device 1 after 0h and 3h operation in solution under the action of an applied potential.
The characteristic peak of the ultraviolet spectrum with the wavelength of about 550nm represents the vibration peak generated when the S0 state of the molecule transits to the S1 state. The working electrode (device 1) containing the PBFDO film was immersed in a 100mM sodium chloride solution for 3 hours, and the PBFDO material would undergo a doping/dedoping process, i.e., a redox process, with a cyclic redox voltage of-0.5V-1.0V applied. When the applied voltage is restored to the initial potential of-0.5V, compared with a sample which is not subjected to oxidation-reduction reaction and is soaked in the solution for 1min, the characteristic peak intensity of the material at the wavelength of about 550nm is not basically changed, which indicates that the material is subjected to repeated and long-time oxidation-reduction reaction in the solution, the internal molecular state of the material is still stable, and the state that the molecular structure of the crosslinked material is relatively stable in the solution is proved.
Fig. 4 shows cyclic voltammograms of the organic conductive polymer film of device 1 after 3 hours of operation in solution under the action of an applied potential, with a number of scans of 10.
Cyclic voltammetry can be used to characterize the capacitive properties of the conductive material itself and the redox stability of the electrode material in solution. As can be seen from FIG. 4, the working electrode PBFDO/ITO added with the silane coupling agent is soaked for 3 hours under the condition of applying bias voltage in the solution, and after 10 times of alternate oxidation-reduction reactions, the cyclic voltammetry characteristic curve of the working electrode PBFDO/ITO is basically unchanged, which indicates that the material maintains stable capacitance characteristic.
The results of the conductivity and solution stability tests of the devices prepared in examples and comparative examples are shown in table 1.
TABLE 1 device conductivity and solution stability test results
As can be seen from table 1, the introduction of a proper amount of the silane coupling agent containing a specific group does not cause a decrease in the conductivity of PBFDO, and the solution operation stability of PBFDO can be significantly improved. While the device of comparative example 1, the silane coupling agent containing Cl functional groups did not significantly improve the solution stability of PBFDO due to the difficulty of the group to interact with the functional groups in the PBFDO molecular chain, and therefore, although the silane coupling agent could bond well with the substrate, it was difficult to serve as an intermediate attachment point, improving the adhesion of the material on the substrate surface; further, it is illustrated that not any silane coupling agent can achieve the effects of the present invention; in comparative example 2, the silane coupling agent can improve the adhesion of PEDOT: PSS to the substrate, but the presence of the small molecule restricts the removal of the insulating molecule PSS in PEDOT: PSS, thus resulting in a significant decrease in device conductivity; comparative example 3 shows that the stability of the film is remarkably reduced by mixing the silane coupling agent with other materials instead of PBFDO molecules, and the same technical effects as in the examples cannot be obtained.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (10)
1. A method for improving the operation stability of a solution of a poly (benzodifurandione) conductive polymer material, which is characterized by comprising the following steps:
s1, stirring and mixing a poly (benzodifurandione) solution and a silane coupling agent to obtain a conductive polymer solution;
s2, washing and drying a substrate, performing oxygen plasma treatment, spin-coating the conductive polymer solution on the surface of the substrate, and drying to obtain a device;
the structural formula of the silane coupling agent is Y-R-SiX 3 ；
Wherein, the liquid crystal display device comprises a liquid crystal display device,
the X is selected from alkoxy, acetoxy or halogen;
the Y is selected from epoxy, mercapto, amino, vinyl or methacryloxy;
the R is selected from a hydrogen atom, an alkyl group, an alkyl derivative, an alkylene group or an alkylene derivative;
one or more carbons of the alkyl or alkylene derivative are substituted with one or more of oxygen, amino, sulfone, carbonyl, aryl, alkylene, alkynyl, ester, cyano, nitro;
and/or
One or more hydrogens on the alkyl or alkylene derivative are substituted with one or more of halogen, hydroxy, amino, carboxy, cyano, nitro, aryl, alkenyl, alkynyl.
2. The method for improving the operation stability of a solution of a poly (benzodifurandione) conductive polymer material according to claim 1, wherein Y is selected from the group consisting of-SH or-NH 2 。
3. The method for improving the operation stability of a solution of a poly (benzodifurandione) conductive polymer material according to claim 1, wherein X is selected from an alkoxy group or an acetoxy group having 1 to 6 carbon atoms.
4. The method for improving the operation stability of a poly (benzodifurandione) conductive polymer material solution according to claim 1, wherein the concentration of the poly (benzodifurandione) solution is 5-15mg/ml.
5. The method for improving the operation stability of a poly (benzodifurandione) conductive polymer material solution according to claim 1, wherein in the step S1, the volume ratio of the silane coupling agent to the poly (benzodifurandione) solution is 0.5% -5%.
6. The method of claim 1, wherein the substrate is selected from one of glass and ITO, PET, PI.
7. The method for improving the operation stability of a solution of a poly (benzodifurandione) conductive polymer material according to claim 1, wherein in the step S1, the stirring time is 1-2h.
8. The method for improving the operation stability of a solution of a poly (benzodifurandione) conductive polymer material according to claim 1, wherein in the step S2, the oxygen plasma treatment is performed for 1 to 5 minutes.
9. The method for improving the operation stability of a poly (benzodifurandione) conductive polymer material solution according to claim 1, wherein in the step S2, the conductive polymer solution is spin-coated on the surface of the substrate at a speed of 800-3000r/min, and then vacuum-dried at 45 ℃ for 5-12 hours.
10. Use of the method for improving the operation stability of a solution of a poly (benzodifurandione) conductive polymer material according to any of claims 1 to 9 in an optoelectronic device.
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