CN111944125B - Terpolymer of triphenylamine donor group containing alkoxy, electric memory device and preparation thereof - Google Patents
Terpolymer of triphenylamine donor group containing alkoxy, electric memory device and preparation thereof Download PDFInfo
- Publication number
- CN111944125B CN111944125B CN202010663322.XA CN202010663322A CN111944125B CN 111944125 B CN111944125 B CN 111944125B CN 202010663322 A CN202010663322 A CN 202010663322A CN 111944125 B CN111944125 B CN 111944125B
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- China
- Prior art keywords
- terpolymer
- monomer
- storage device
- triphenylamine
- alkoxy
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- 229920001897 terpolymer Polymers 0.000 title claims abstract description 52
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 125000003545 alkoxy group Chemical group 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000003860 storage Methods 0.000 claims abstract description 43
- 239000012044 organic layer Substances 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 26
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 239000011232 storage material Substances 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims description 48
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 26
- 239000010410 layer Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 17
- -1 C 6 Alkyl radical Chemical class 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000003785 benzimidazolyl group Chemical class N1=C(NC2=C1C=CC=C2)* 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 150000002940 palladium Chemical class 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- YORKZQSDEFMBPF-UHFFFAOYSA-N (7-borono-9h-fluoren-2-yl)boronic acid Chemical compound OB(O)C1=CC=C2C3=CC=C(B(O)O)C=C3CC2=C1 YORKZQSDEFMBPF-UHFFFAOYSA-N 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 2
- 239000011630 iodine Chemical group 0.000 claims description 2
- 229910052740 iodine Chemical group 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 125000005620 boronic acid group Chemical group 0.000 claims 1
- 125000004185 ester group Chemical group 0.000 claims 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 230000004044 response Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000021615 conjugation Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 150000001642 boronic acid derivatives Chemical group 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 9
- 150000001556 benzimidazoles Chemical class 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000012043 crude product Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000015654 memory Effects 0.000 description 6
- 239000010408 film Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 4
- 229920000547 conjugated polymer Polymers 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 3
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000013500 data storage Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000005619 boric acid group Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000075 oxide glass Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920002098 polyfluorene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical group O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 125000006617 triphenylamine group Chemical group 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 1
- UCCUXODGPMAHRL-UHFFFAOYSA-N 1-bromo-4-iodobenzene Chemical compound BrC1=CC=C(I)C=C1 UCCUXODGPMAHRL-UHFFFAOYSA-N 0.000 description 1
- KAYXDWIILRESPY-UHFFFAOYSA-N 2-[7-(1,3,2-dioxaborinan-2-yl)-9,9-dioctylfluoren-2-yl]-1,3,2-dioxaborinane Chemical compound C1=C2C(CCCCCCCC)(CCCCCCCC)C3=CC(B4OCCCO4)=CC=C3C2=CC=C1B1OCCCO1 KAYXDWIILRESPY-UHFFFAOYSA-N 0.000 description 1
- RGAMLRMKIJBQGL-UHFFFAOYSA-N 2h-benzo[h]isoquinolin-1-one Chemical compound C1=CC=CC2=C3C(=O)NC=CC3=CC=C21 RGAMLRMKIJBQGL-UHFFFAOYSA-N 0.000 description 1
- VPMJBJSLTPBZLR-UHFFFAOYSA-N 3,6-dibromobenzene-1,2-diamine Chemical compound NC1=C(N)C(Br)=CC=C1Br VPMJBJSLTPBZLR-UHFFFAOYSA-N 0.000 description 1
- HRHKMWYKKCLJPP-UHFFFAOYSA-N 5,8-dibromo-3,10-diazapentacyclo[10.7.1.02,10.04,9.016,20]icosa-1(19),2,4,6,8,12,14,16(20),17-nonaen-11-one Chemical compound BrC1=CC=C(C2=C1N1C(C=3C=CC=C4C3C(C1=O)=CC=C4)=N2)Br HRHKMWYKKCLJPP-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GRSMWKLPSNHDHA-UHFFFAOYSA-N Naphthalic anhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=CC3=C1 GRSMWKLPSNHDHA-UHFFFAOYSA-N 0.000 description 1
- PYTZYWGTYYJLCM-UHFFFAOYSA-N OCCCO.OCCCO.C1=C(B(O)O)C=C2C(CCCCCCCC)(CCCCCCCC)C3=CC(B(O)O)=CC=C3C2=C1 Chemical compound OCCCO.OCCCO.C1=C(B(O)O)C=C2C(CCCCCCCC)(CCCCCCCC)C3=CC(B(O)O)=CC=C3C2=C1 PYTZYWGTYYJLCM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005264 electron capture Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 125000003106 haloaryl group Chemical group 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000006386 memory function Effects 0.000 description 1
- 230000007334 memory performance Effects 0.000 description 1
- 230000005055 memory storage Effects 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 230000007935 neutral effect Effects 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
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- 239000010409 thin film Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
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- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/011—Manufacture or treatment of multistable switching devices
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- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/801—Constructional details of multistable switching devices
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
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- C08G2261/124—Copolymers alternating
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/141—Side-chains having aliphatic units
- C08G2261/1412—Saturated aliphatic units
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention belongs to the technical field of organic electric storage materials, and discloses an alkoxy-containing triphenylamine donor group terpolymer, an electric storage device and preparation thereof. The terpolymer has the following structure, wherein R is alkoxy; r is 1 Is an alkyl group; m is an integer of 20 to 300; n is an integer of 20 to 300. The electric memory device comprises an organic layer, wherein the organic layer is the terpolymer; also included are a substrate, a cathode, and an anode. The invention also discloses preparation methods of the terpolymer and the electric storage device. The terpolymer of the invention has stronger conjugation degree and hole transmission capability, reduces the starting voltage, improves the on-off current ratio and the storage density, and is easy to form a film. The prepared electric storage device has low starting voltage, low energy consumption, high switching current ratio, high resolution ratio, low misreading rate, quick response, repeated cycle reading and writing and excellent performance.
Description
Technical Field
The invention belongs to the technical field of organic storage materials, and particularly relates to an alkoxy-containing terpolymer of triphenylamine donor groups and a synthetic method thereof, and an electric storage device using the polymer as an organic layer and a preparation method thereof.
Background
With the coming of the information age, the amount of information facing the daily life of people increases, and the traditional storage technology is difficult to meet the basic requirement of information storage. Therefore, an electric memory with more excellent performance is indispensable. The technology of preparing an electrical memory device by using a traditional inorganic semiconductor material is mature, so that the electrical memory device can be fully applied to various information fields. As the demand for mobile applications has increased to drive the development of memory technologies and devices, there has been an increasing demand for memories having high capacity, good system performance, low power consumption, smaller size, and lower cost. However, the size miniaturization of the inorganic semiconductor memory that is currently mainstream is limited by a large number of materials and cost factors. The development of new memory storage structures and materials is facing new opportunities.
Recently, polymer electric memory devices have attracted considerable attention as an emerging field in organic electronics. Organic electronic memory devices store data according to high and low conductivity response changes and exhibit bistability. The special properties of polymer materials are of great interest. Compared with the traditional inorganic semiconductor storage material, the polymer is taken as a leader of a new electric storage material device, and has the advantages of simple manufacture, stable storage, low cost, high storage density, high mechanical flexibility and the like, so that the polymer has wider development space and wide application prospect in information storage.
Currently, most electrical memory devices exhibit memory states that are limited to conventional binary storage consisting of "0" and "1" output signals. In such a storage system, the total data storage capacity is 2 n And is quite different from the demand for high-density information storage. In recent years, the design and development of multi-level electrical memory devices, which have multi-level electrical storage characteristics and can store data densely, have shown great potential in improving data storage capacityThe degree is increased to several hundred million times of that of the binary system. However, the multilevel data storage materials reported at present are complex in manufacturing process or expensive, and the multilevel storage yield of some devices is low.
In view of the above problems, it is desirable to develop a conductive conjugated polymer which is easy to synthesize and can be industrially used, and a memory device prepared therefrom is required to have a high on-off current ratio and a low on-voltage, and can realize high-density storage.
Disclosure of Invention
In order to solve the above problems, the present invention provides an alkoxy group-containing triphenylamine donor group terpolymer and a method for preparing the same. The terpolymer is prepared by polymerizing halogenated triphenylamine monomers, halogenated benzimidazole monomers and fluorene monomers. The terpolymer disclosed by the invention is simple in synthesis method and easy to process into a film, the prepared electric storage device has ternary electric storage performance, the starting voltage is low, the switching current ratio is high, and the preparation process of the device is simple and low in cost.
Another object of the present invention is to provide an electrical memory device and a method of fabricating the same. The electric storage device comprises the terpolymer. The terpolymer acts as an organic layer of an electrical memory device.
The purpose of the invention is realized by the following technical scheme:
an alkoxy-containing triphenylamine donor group terpolymer, the conjugated polymer having the structure:
wherein R is alkoxy, preferably methoxy or ethoxy; r in the same repeating unit 1 Same or different, R 1 Is an alkyl group, preferably C 6 Alkyl radical, C 7 Alkyl or C 8 An alkyl group; the fluorene structures in different repeating units are the same;
m is an integer of 20 to 300, preferably an integer of 30 to 200, more preferably an integer of 30 to 100; n is an integer of 20 to 300, preferably an integer of 30 to 200, more preferably an integer of 30 to 100.
Preferably, m and n have the same value.
The preparation method of the terpolymer comprises the following steps:
1) in a solvent, heating and reacting halogenated triphenylamine monomers, halogenated benzimidazole monomers and fluorene monomers, and performing subsequent treatment to obtain the terpolymer.
The structural formula of the halogenated triphenylamine monomer is as follows:
wherein X 1 Selected from chlorine, bromine or iodine, R 2 As the alkoxy group, preferred is an alkoxy group of 1 to 5 carbon atoms such as methoxy and ethoxy, and, for example, halogenated triphenylamine monomers are N, N-bis (4-bromophenyl) -N- (4-methoxy) aniline, N-bis (4-bromophenyl) -N- (4-ethoxy) aniline monomers.
The halogenated benzimidazole monomer is a halogenated benzimidazole benzo isoquinolinone monomer, and the structural formula of the halogenated benzimidazole monomer is as follows:
wherein, the halogenated group X is selected from chlorine, bromine and iodine, preferably bromine or iodine; r is 3 And R 4 Each independently is hydrogen. In a preferred mode of the invention, the compound is 9, 12-dibromo-7H-benzimidazole [2,1-a ]]Benzo [ de ]]Isoquinoline-7-ketone is used as a halogenated benzimidazole monomer containing naphthalene to participate in polymerization.
The fluorene monomer is a 9, 9-dialkyl fluorene-2, 7-diboronate monomer, which means that the 9 position of the fluorene monomer is provided with two substituted alkyls, and the 2 and 7 positions are provided with boric acid group groups or boric acid ester group groups;
the boric acid group or the borate group is an alkyl borate group, an aryl borate group, an alkenyl borate group, an alkyl borate group, an aryl borate group or an alkenyl borate group, preferably an alkyl borate group, an aryl borate group or an alkenyl borate group, more preferably an alkyl borate group such as 9, 9-dioctylfluorene-2, 7-diboronic acid bis (1, 3-propanediol) ester.
The reaction is carried out under catalysis of a catalyst. The catalyst is selected from palladium salts, such as palladium chloride or palladium acetate, palladium on carbon, palladium on inorganic oxides, such as Pd/Al 2 O 3 Or Pd/MgO, palladium complexes, e.g. Pd (AsPh) 3 ) 4 、Pd(n-Bu 3 P) 4 、Pd((MeO) 3 P) 4 、Pd(PPh 3 ) 4 Preferably a palladium salt or a palladium complex, more preferably a palladium complex, such as tetrakis (triphenylphosphine) palladium.
The solvent is an organic solvent selected from petroleum ether, toluene, xylene, dimethyl sulfoxide and N, N-dimethylformamide, preferably toluene, xylene or dimethyl sulfoxide, and more preferably toluene or xylene. In the invention, in order to better dissolve and disperse the palladium catalyst in the solvent, the used solvent has the function of a water-carrying agent while dissolving the reactants, and the catalyst can be better dissolved in the reaction system to play a catalytic role by reducing the water content in the solvent.
Preferably, a solution of an alkaline substance selected from soluble carbonates, acetates, phosphates or hydroxides, preferably from alkali metal carbonates or alkali metal acetates, more preferably alkali metal carbonates such as potassium carbonate or sodium carbonate, is added to the reaction.
In a preferred mode of the invention, during the reaction, after the halogenated triphenylamine monomer and the halogenated benzimidazole monomer react with the palladium catalyst, the halogenated triphenylamine monomer and the halogenated benzimidazole monomer are converted into an intermediate product in an alkaline environment, and meanwhile, the fluorene monomer migrates to the metal center Pd of the intermediate product, and is subjected to reactive coupling to obtain the polymer. The polymerization reaction has the advantages of mild conditions, high catalytic efficiency, high selectivity and few byproducts.
The reaction temperature is 80-130 ℃, preferably 90-120 ℃, and more preferably 105-110 ℃.
The reaction time is 20-80 h, preferably 35-65 h, and more preferably 45-55 h.
The molar ratio of the halogenated triphenylamine monomer to the fluorene monomer is 1 (1-4), and the molar ratio of the halogenated benzimidazole monomer to the fluorene monomer is 1 (1-4).
The molar ratio of the fluorene monomer to the catalyst is 1 (0.005-0.04).
The molar volume ratio of the fluorene monomer to the solvent is 0.4mmol (4-10) mL.
The concentration of the alkaline substance solution is 1.5-5 mol/L, preferably 2.5-4 mol/L. Too strong basicity will cause the haloaryl group to self-couple.
The volume ratio of the solvent to the alkaline substance solution is 1 (0.1-2).
The reaction is carried out under a protective gas environment, wherein the protective gas is nitrogen or argon, and nitrogen is preferred.
An electrical storage material comprising the above terpolymer.
The electrical storage material is used to make an electrical storage device.
An electrical memory device includes an organic layer, which is an electrical memory material.
The electrical storage device further includes a substrate, a cathode, and an anode; the cathode is disposed on a substrate.
The preparation method of the electric storage device comprises the following steps:
step a, cleaning a substrate layer; a cathode is attached to the substrate layer;
b, dissolving the terpolymer in a solvent to obtain a terpolymer solution;
step c, attaching the terpolymer solution to a cathode to form an organic layer;
and d, attaching an anode on the organic layer to obtain the organic electric storage device.
The cathode is selected from tin oxide glass (ITO), conductive polymers, graphene or well-conducting metals such as Al, Cu, Au, preferably ITO or conductive metals, more preferably ITO or Al.
The cathode is vacuum evaporated on the substrate. The substrate is a glass substrate.
The substrate layer cleaning is to clean the substrate layer with the cathode by using a solvent (such as ultrasonic cleaning).
The solvent is more than one of water, methanol, absolute ethyl alcohol and acetone, preferably one or more of water, absolute ethyl alcohol and acetone, and more preferably, the substrate layer is sequentially cleaned by the sequence of water, acetone and absolute ethyl alcohol to remove impurity substances on the substrate. The substrate layer after cleaning is preserved in absolute ethyl alcohol.
The solvent in step b is an organic solvent, preferably selected from at least one of aromatic solvents (such as toluene, xylene, etc.), ethers (such as petroleum ether, etc.), sulfones (such as dimethyl sulfoxide, etc.), and preferably selected from aromatic solvents.
The concentration of the terpolymer solution in the step b is 1-30 mg/mL, preferably 3-15 mg/mL, and more preferably 3-10 mg/mL. The concentration of the polymer solution directly affects the thickness of the organic layer, if the concentration of the polymer solution is too high, the polymer is not well dispersed, and a uniform organic film is not easily formed, and if the concentration of the polymer solution is too low, the thickness of the formed organic film is thinner, which affects the performance of the electric storage device.
The step of attaching the terpolymer solution to the cathode in step c means that the terpolymer solution is coated on the cathode by spin coating, spray coating, dipping, roll coating or ink injection printing, preferably spin coating, roll coating or spray coating, and more preferably spin coating.
After coating, vacuum drying is carried out to remove the solvent.
The thickness of the organic layer is 100 to 300nm, preferably 150 to 280nm, and more preferably 220 to 260 nm. If the organic layer is too thick, the potential barrier is too high, charge carriers are difficult to inject into the whole organic layer, and the charge transport capability in the thin film is weakened. The organic layer is too thin, resulting in a low barrier and difficult electron capture.
In the step d, the anode is made of metal, preferably Al, Cu, Au or Pt, and more preferably Al in consideration of conductivity and manufacturing cost.
The anode is prepared by a vacuum evaporation method.
The thickness of the anode is 120-600 nm, preferably 200-500 nm, and more preferably 250-350 nm.
The area of the anode is 0.1-8 mm 2 Preferably 0.25 to 5mm in thickness 2 More preferably 0.5 to 3mm 2 。
The invention has the following beneficial effects:
(1) the triphenylamine group in the copolymer has good hole transmission capability, and not only has good electron supply capability, but also can improve the thermodynamic and electrochemical stability of the copolymer.
(2) The benzimidazole group in the copolymer has electron accepting and electron transmitting capacity, and can play a role in improving carrier injection balance in a device structure.
(3) The polyfluorene in the copolymer is usually used as an electron donor and a charge transport material, has higher carrier mobility, is a good photoelectric material because the carrier is transported along a conjugated main chain, and can improve the HOMO energy level by introducing an electron-donating group into the polyfluorene.
(4) The fluorenyl, triphenylamine and benzimidazole structures can enhance the conjugation degree and the hole transmission capability of the conjugated polymer, further reduce the turn-on voltage, improve the on-off current ratio and improve the storage density, and the copolymer is easy to form a film and improves the processability of the polymer.
(5) The prepared electric storage device has low starting voltage, low energy consumption, high switching current ratio, high resolution ratio, low misreading rate, quick response, repeated cycle reading and writing and excellent performance.
(6) The terpolymer synthesis method is simple, the preparation process of the electric storage device is easy to realize, and industrial production can be realized.
Drawings
FIG. 1 is a schematic diagram of the structure of an electrical memory device of the present invention;
FIG. 2 is a NMR chart of the terpolymer of example 1 according to the present invention;
FIG. 3 is a test chart of a current-voltage characteristic curve of an electric memory device in embodiment 2 of the present invention;
FIG. 4 is a test chart of a switching current ratio-voltage characteristic curve of the electric memory device in embodiment 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example 1 preparation of terpolymer:
(1) preparation of monomer M1(9, 12-dibromo-7H-benzimidazolo (2,1-a) benzo (de) isoquinolin-7-one): in N 2 Adding 1, 8-naphthalic anhydride and 3, 6-dibromo-1, 2-phenylenediamine according to a molar ratio of 1:1 in a three-neck flask under the atmosphere, placing 10mL of glacial acetic acid in the three-neck flask, stirring and heating until the solution flows back, carrying out constant-temperature reaction for 6h, cooling the reaction to room temperature, filtering after a crude product is separated out, washing the crude product to be neutral by using deionized water, placing the obtained crude product in a vacuum drying oven for drying, and separating and purifying the dried crude product by using column chromatography to obtain a monomer M1; the temperature of the vacuum drying is 80-85 ℃, the time of the vacuum drying is 12 hours, and the pressure of the vacuum drying is-30 to-29 KPa;
(2) preparation of monomer M2(N, N-bis (4-bromophenyl) -N- (4-methoxy) aniline): 1.70g (13.83mmol) of 4-methoxyaniline, 8.08g (28.56mmol) of 1-bromo-4-iodobenzene, 0.12g (0.13mmol) of tris (dibenzylideneacetone) dipalladium (C) 51 H 42 O 3 Pd 2 ) 0.30g (0.54mmol) of 1,1' -bis (diphenylphosphino) ferrocene (DPPF), 3.92g (40.79mmol) of sodium tert-butoxide (t-BuONa) and 25mL of refined toluene are sequentially added into a 100mL Schlenk bottle, after the medicine is dissolved, vacuum pumping and nitrogen filling are carried out, and after the reaction is carried out for three times, the nitrogen is continuously introduced to keep the reaction in an anaerobic state; starting constant-temperature magnetic stirring, slowly heating to 110 ℃ for reaction for 6h (along with the reaction, the solution is dark brown, gray solid appears on the bottle wall after the reaction starts for 1h, the reaction is finished after 6h, the solution in the bottle is layered, the upper layer is a dark brown organic phase, and the lower layer is a gray mud-like substance); removing toluene by rotary evaporation of the mixed solution, dissolving the mixture with dichloromethane, transferring to a separating funnel, adding deionized water, extracting for several times until the upper water phase is clarified to finish extraction, rotary evaporating the organic phase to obtain brown viscous liquid, and separating with silica gel chromatographic column to obtain crude extractPurifying the product, wherein the leacheate is dichloromethane petroleum ether (1:3), and the final product is light yellow solid, namely the target product monomer M2;
(3) synthesizing a terpolymer of triphenylamine donor groups containing methoxyl groups: 0.2mmol of monomer M1, 0.2mmol of monomer M2, 0.4mmol of bis (1, 3-propanediol) 9, 9-dioctylfluorene-2, 7-diboronate and 0.0046g of palladium tetratriphenylphosphine (Pd (PPh) 3 ) 4 ) And 1mL of 3M K 2 CO 3 Adding 7mL of toluene serving as a solvent into a 50mL Schlenk bottle, repeatedly vacuumizing and filling nitrogen for three times, continuously introducing the nitrogen, slowly heating to 105 ℃ in an oil bath under magnetic stirring, reacting for 48h, cooling to room temperature after the reaction is finished, pouring into a separating funnel, washing for several times by deionized water until a water phase is clear, slowly dropping an organic phase into ice methanol, separating out a solid, performing vacuum filtration to obtain a crude product, performing Soxhlet extraction on the crude product by using acetone for 48h after the crude product is vacuum-dried, and performing vacuum drying to obtain a final product, namely the terpolymer.
The structure of the terpolymer is:
wherein m is an integer of 20 to 300, and n is an integer of 20 to 300.
The terpolymer prepared in this example was subjected to hydrogen nuclear magnetic resonance spectroscopy using an INOVA400MHz high resolution nuclear magnetic resonance spectrometer (TMS as internal standard), CDCl 3 As a solvent, the spectrum is shown in FIG. 2.
As can be seen from the figure, the aromatic hydrogen characteristic peak is obtained in the chemical shift range of 8.88-6.57, the methoxyl characteristic peak is obtained in 3.71, and the alkyl chain hydrogen characteristic peak is obtained in the chemical shift range of 1.89-0.65. The successful synthesis of the target product, a terpolymer of triphenylamine donor groups containing methoxyl groups is demonstrated.
EXAMPLE 2 use of terpolymers for the preparation of Electrical memory devices
In the present invention, an electrical memory device was prepared using the terpolymer prepared in example 1 as an organic layer. The electric storage device is shown in a schematic structural diagram in fig. 1 and comprises a substrate layer, a cathode layer, an organic layer and an anode layer, wherein the cathode is arranged on the substrate, the organic layer is arranged on the cathode, and the anode is arranged on the organic layer.
The organic layer of the present invention was formed from the terpolymer prepared in example 1, which was used to fabricate a memory material for an electrical storage device. In the terpolymer, an electron-rich fluorenyl group and a triphenylamine group are used as excellent electron donor elements, an electron-donating group is introduced into a main chain of a polymer, so that the hole transmission capability of the polymer can be effectively improved, the copolymer has lower working voltage, a benzimidazole group is introduced as an excellent electron-deficient receptor element, the benzimidazole group has intramolecular charge transfer, and the path is from benzimidazole to benzisoquinolinone, so that the benzimidazole monomer serves as two different receptor units in the copolymer structure, intramolecular charge transfer can be carried out, and the band gap of the conjugated polymer is effectively reduced.
An electrical memory device with a terpolymer as the organic layer exhibits ternary Flash-type non-volatile electrical memory performance. In the ground state, it is difficult to obtain sufficient energy for carriers to pass through and inject into the barrier, and the electric memory device is in the OFF state; when the charge obtains enough energy under the action of an electric field and jumps from an electron donor to an electron acceptor, the electron-withdrawing capability of benzimidazole is weak, the generated charge trap is filled first, and the device reaches an ON1 state; when the electric field intensity is further enhanced, deeper charge traps generated by a benzisoquinoline (indole) ketone group with stronger electron-withdrawing ability are completely filled up to reach an ON2 state; when the voltage is turned off, the polymer can still remain in the on state. When an opposite voltage is applied to the electric storage device, holes which are trapped by the traps can be attracted to the interface of the electrode and the polymer again to be compounded with electrons, so that the polymer is restored to the original state, and the aim of erasing is fulfilled.
The preparation method of the electric storage device comprises the following steps:
a, cleaning a substrate layer to remove impurity substances on the substrate, and storing the cleaned substrate layer in absolute ethyl alcohol; a cathode layer is attached to the substrate layer; the cathode layer is selected from tin oxide glass (ITO), and the cathode layer is coated on the glass substrate by vacuum evaporation;
the substrate layer cleaning is to carry out ultrasonic cleaning on the substrate layer with the cathode layer in the sequence of deionized water, acetone and absolute ethyl alcohol;
step b, dispersing the terpolymer prepared in the embodiment 1 into toluene to obtain a terpolymer solution; the toluene can well dissolve and disperse the terpolymer and is easy to remove; the concentration of the copolymer solution was 3 mg/mL;
step c, spin-coating the terpolymer solution on the cathode layer, and performing vacuum drying to form an organic layer; the drying temperature is 50-130 ℃, preferably 70-120 ℃, and more preferably 80-115 ℃; the vacuum drying time is 5-30 h, preferably 8-20 h, and more preferably 10-15 h; the pressure of vacuum drying is-80 to-10 KPa, preferably-50 to-20 KPa, and more preferably-35 to-25 KPa; the thickness of the organic layer is 253 nm;
d, attaching an anode layer on the organic layer to obtain an organic electric storage device; the anode layer is Al and is prepared by a vacuum evaporation method.
The thickness and area of the anode layer were 300nm and 1.0mm, respectively 2 。
The electric storage device prepared in example 2 was subjected to an electric storage performance test, and a current-voltage characteristic curve (I-V) is shown in fig. 3 and a switching current ratio-voltage diagram is shown in fig. 4.
As can be seen from FIG. 3, the first voltage sweep of the memory device has two current increasing states in the voltage region of 0V to-6V. A current increase jump occurs at a voltage of-0.70V, which can be considered to be a transition from the high resistance state (OFF state) to the intermediate resistance state (ON1 state), a second current increase jump occurs at a voltage of-1.05V, and the electrical memory device transitions from the intermediate resistance state (ON1 state) to the low resistance state (ON2), and then the device is always in the low resistance state in a second 0V to-6V scan, indicating that the device can implement the ternary memory function. The third step scans the memory device over a voltage range of 0V to 6V, and when the voltage is increased to 3.85V, the device is brought from a high conduction state (ON2) to a low conduction state (OFF) to be restored to the OFF state, at which time the electrical memory device data is erased. The memory device can still keep a stable state after repeated voltage scanning for 200 min. Therefore, the memory device in the illustrated invention is a ternary Flash type memory device.
As can be seen from fig. 4, the maximum switching current ratio of the memory device is: OFF 1 ON2 1:10 1.6 :10 4.7 The device has high storage density, can accurately control the on and off states, and has low error rate.
In summary, organic layers prepared using the terpolymers of the present invention have good thermal stability and film formation. The prepared electric storage device has low starting voltage (NO1 state can reach-0.70V), low energy consumption, prolonged service life, and high switching current ratio (OFF: ON1: ON2 can reach 1: 10) 1.6 :10 4.7 ) The storage density is greatly improved, the resolution ratio is high, the misreading rate is low, the quick response can be realized, the repeated cycle reading and writing can be carried out, and the performance is excellent.
The invention has been described in detail with reference to specific embodiments and/or illustrative examples and the accompanying drawings, which, however, should not be construed as limiting the invention. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention.
Claims (10)
1. An alkoxy-containing terpolymer of triphenylamine donor groups, characterized in that: has the following structure:
wherein R is 2 Is an alkoxy group; r in the same repeating unit 1 Same or different, R 1 Is an alkyl group; the fluorene structures in different repeating units are the same;
m is an integer of 20 to 300; n is an integer of 20 to 300.
2. The terpolymer of alkoxy-containing triphenylamine donor groups according to claim 1, wherein: r is 2 Is methoxy or ethoxy; r is 1 Is C 6 Alkyl radical, C 7 Alkyl or C 8 An alkyl group; m is an integer of 30 to 200; n is an integer of 30 to 200; m and n have the same value.
3. The method of preparing a terpolymer of alkoxy-containing triphenylamine donor groups according to claim 1, wherein: the method comprises the following steps: in a solvent, heating and reacting halogenated triphenylamine monomers, halogenated benzimidazole monomers and fluorene monomers, and performing subsequent treatment to obtain a terpolymer;
the structural formula of the halogenated triphenylamine monomer is as follows:
wherein, X 1 Selected from chlorine, bromine or iodine, R 2 Is an alkoxy group;
the halogenated benzimidazole monomer is a halogenated benzimidazole benzo isoquinolinone monomer, and the structural formula of the halogenated benzimidazole monomer is as follows:
wherein X is selected from chlorine, bromine and iodine; r 3 And R 4 Each independently is hydrogen;
the fluorene monomer is a 9, 9-dialkyl fluorene-2, 7-diboronate monomer, which means that the 9 position of the fluorene monomer has two substituted alkyl groups R 1 And boronic acid groups or boronic ester groups are present at the 2 and 7 positions.
4. A method of preparing an alkoxy group-containing terpolymer of triphenylamine donor groups according to claim 3, wherein the method comprises: the reaction is carried out under the catalysis of a catalyst; the catalyst is a palladium catalyst selected from palladium salt, palladium carbon and an inorganic oxide supported palladium or a palladium complex;
the solvent is an organic solvent and is selected from more than one of petroleum ether, toluene, xylene, dimethyl sulfoxide and N, N-dimethylformamide;
adding an alkaline substance solution into the reaction;
the reaction temperature is 80-130 ℃; the reaction time is 20-80 h;
the molar ratio of the halogenated triphenylamine monomer to the fluorene monomer is 1 (1-4), and the molar ratio of the halogenated benzimidazole monomer to the fluorene monomer is 1 (1-4);
the reaction is carried out under a protective gas environment.
5. An electrical storage material, characterized by: comprising a terpolymer of alkoxy-containing triphenylamine donor groups according to claim 1 or 2.
6. Use of an electrical storage material according to claim 5, wherein: the electrical storage material is used to make an electrical storage device.
7. An electrical memory device, characterized by: comprising an organic layer which is an electrical storage material as defined in claim 5.
8. The electrical storage device of claim 7, wherein: the thickness of the organic layer is 100-300 nm.
9. The electrical storage device of claim 7, wherein: the electrical storage device further includes a substrate, a cathode, and an anode; the cathode is disposed on the substrate, the organic layer is disposed on the cathode, and the anode is disposed on the organic layer.
10. A method of fabricating an electrical storage device according to any one of claims 7 to 9, wherein: the method comprises the following steps:
step a, cleaning a substrate layer; a cathode is attached to the substrate layer;
b, dissolving the terpolymer in a solvent to obtain a terpolymer solution; the terpolymer is a terpolymer of alkoxy-containing triphenylamine donor groups of claim 1 or 2;
step c, attaching the terpolymer solution to a cathode to form an organic layer;
and d, attaching an anode on the organic layer to obtain the organic electric storage device.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004006064A (en) * | 2002-03-22 | 2004-01-08 | Nippon Kayaku Co Ltd | Light-emitting element |
| CN101376686A (en) * | 2008-09-28 | 2009-03-04 | 南京邮电大学 | Bulk heterojunction solar battery polymer donor material, synthesis and use method |
| CN103396533A (en) * | 2013-08-14 | 2013-11-20 | 黑龙江大学 | Methoxytriphenylamine-fluorene-containing copolymer, and preparation method and application thereof |
| CN105070830A (en) * | 2015-08-10 | 2015-11-18 | 黑龙江大学 | Fluorine-triphenylamine conjugated polymer electric storage material and preparation method of electric storage device |
| CN111349217A (en) * | 2020-04-23 | 2020-06-30 | 黑龙江大学 | Terpolymer and preparation method of electric storage device thereof |
-
2020
- 2020-07-10 CN CN202010663322.XA patent/CN111944125B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004006064A (en) * | 2002-03-22 | 2004-01-08 | Nippon Kayaku Co Ltd | Light-emitting element |
| CN101376686A (en) * | 2008-09-28 | 2009-03-04 | 南京邮电大学 | Bulk heterojunction solar battery polymer donor material, synthesis and use method |
| CN103396533A (en) * | 2013-08-14 | 2013-11-20 | 黑龙江大学 | Methoxytriphenylamine-fluorene-containing copolymer, and preparation method and application thereof |
| CN105070830A (en) * | 2015-08-10 | 2015-11-18 | 黑龙江大学 | Fluorine-triphenylamine conjugated polymer electric storage material and preparation method of electric storage device |
| CN111349217A (en) * | 2020-04-23 | 2020-06-30 | 黑龙江大学 | Terpolymer and preparation method of electric storage device thereof |
Non-Patent Citations (2)
| Title |
|---|
| A novel host material with high thermal stability for green electrophosphorescent device;Wenqing Liang et al.;《Tetrahedron》;20160129;第72卷;第1505-1510页 * |
| Ternary Memory Devices Based on Bipolar Copolymers with Naphthalene Benzimidazole Acceptors and Fluorene/Carbazole Donors;Hongyan Zhang et al.;《Macromolecules》;20191126;第52卷;第9364-9375页 * |
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