CN113840827A - 金刚烷类化合物 - Google Patents
金刚烷类化合物 Download PDFInfo
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- CN113840827A CN113840827A CN202080034347.1A CN202080034347A CN113840827A CN 113840827 A CN113840827 A CN 113840827A CN 202080034347 A CN202080034347 A CN 202080034347A CN 113840827 A CN113840827 A CN 113840827A
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- ORILYTVJVMAKLC-UHFFFAOYSA-N Adamantane Natural products C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 title claims abstract description 62
- -1 Adamantane compound Chemical class 0.000 title claims description 48
- 239000013545 self-assembled monolayer Substances 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 58
- 239000002052 molecular layer Substances 0.000 claims description 28
- 229910052731 fluorine Inorganic materials 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 229910052801 chlorine Inorganic materials 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000004065 semiconductor Substances 0.000 claims description 15
- 238000000151 deposition Methods 0.000 claims description 13
- 150000003254 radicals Chemical class 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 125000004429 atom Chemical group 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000006850 spacer group Chemical group 0.000 claims description 9
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 239000002094 self assembled monolayer Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 2
- 229910005542 GaSb Inorganic materials 0.000 claims description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 2
- 229910000673 Indium arsenide Inorganic materials 0.000 claims description 2
- 229910015345 MOn Inorganic materials 0.000 claims description 2
- 229910004166 TaN Inorganic materials 0.000 claims description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000005194 alkoxycarbonyloxy group Chemical group 0.000 claims description 2
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 2
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 claims description 2
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000006413 ring segment Chemical group 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 125000005407 trans-1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])[C@]([H])([*:2])C([H])([H])C([H])([H])[C@@]1([H])[*:1] 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 45
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- 238000006243 chemical reaction Methods 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000002356 single layer Substances 0.000 description 7
- 238000004293 19F NMR spectroscopy Methods 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- YOKBFUOPNPIXQC-UHFFFAOYSA-N anti-tetramantane Chemical compound C1C(CC2C3C45)CC6C2CC52CC5CC7C2C6C13CC7C4C5 YOKBFUOPNPIXQC-UHFFFAOYSA-N 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- YRHJKRZYWYXDOS-UHFFFAOYSA-N C12(CC3CC(CC(C1)C3)C2)C1=C(C(=C(C=C1)O)F)F Chemical compound C12(CC3CC(CC(C1)C3)C2)C1=C(C(=C(C=C1)O)F)F YRHJKRZYWYXDOS-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000004873 anchoring Methods 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000004679 31P NMR spectroscopy Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BDDFKGBZOYSSIY-UHFFFAOYSA-N C(C)OP(=O)(OCC)CCCOC1=C(C(=C(C=C1)C12CC3CC(CC(C1)C3)C2)F)F Chemical compound C(C)OP(=O)(OCC)CCCOC1=C(C(=C(C=C1)C12CC3CC(CC(C1)C3)C2)F)F BDDFKGBZOYSSIY-UHFFFAOYSA-N 0.000 description 3
- NMXKFAFLFVBADT-UHFFFAOYSA-N C12(CC3CC(CC(C1)C3)C2)C1=C(C(=C(OCCCCCCCCCCCO)C=C1)F)F Chemical compound C12(CC3CC(CC(C1)C3)C2)C1=C(C(=C(OCCCCCCCCCCCO)C=C1)F)F NMXKFAFLFVBADT-UHFFFAOYSA-N 0.000 description 3
- CWTAVWASLIJNIG-UHFFFAOYSA-N C12(CC3CC(CC(C1)C3)C2)C1=C(C(=C(OCCCCCCCCCCCP(O)(O)=O)C=C1)F)F Chemical compound C12(CC3CC(CC(C1)C3)C2)C1=C(C(=C(OCCCCCCCCCCCP(O)(O)=O)C=C1)F)F CWTAVWASLIJNIG-UHFFFAOYSA-N 0.000 description 3
- IGVKIFVPGXPBHZ-UHFFFAOYSA-N C12(CC3CC(CC(C1)C3)C2)C1=C(C(=C(OCCCP(O)(O)=O)C=C1)F)F Chemical class C12(CC3CC(CC(C1)C3)C2)C1=C(C(=C(OCCCP(O)(O)=O)C=C1)F)F IGVKIFVPGXPBHZ-UHFFFAOYSA-N 0.000 description 3
- OCDMZCJJFWVITC-UHFFFAOYSA-N C12(CC3CC(CC(C1)C3)C2)COC1=C(C(=C(C=C1)O)F)F Chemical compound C12(CC3CC(CC(C1)C3)C2)COC1=C(C(=C(C=C1)O)F)F OCDMZCJJFWVITC-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000006411 Negishi coupling reaction Methods 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
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- ZICQBHNGXDOVJF-UHFFFAOYSA-N diamantane Chemical compound C1C2C3CC(C4)CC2C2C4C3CC1C2 ZICQBHNGXDOVJF-UHFFFAOYSA-N 0.000 description 3
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- WYURNTSHIVDZCO-SVYQBANQSA-N oxolane-d8 Chemical compound [2H]C1([2H])OC([2H])([2H])C([2H])([2H])C1([2H])[2H] WYURNTSHIVDZCO-SVYQBANQSA-N 0.000 description 3
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
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- VQHPRVYDKRESCL-UHFFFAOYSA-N 1-bromoadamantane Chemical compound C1C(C2)CC3CC2CC1(Br)C3 VQHPRVYDKRESCL-UHFFFAOYSA-N 0.000 description 2
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- VLLNJDMHDJRNFK-UHFFFAOYSA-N adamantan-1-ol Chemical compound C1C(C2)CC3CC2CC1(O)C3 VLLNJDMHDJRNFK-UHFFFAOYSA-N 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
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- 230000000052 comparative effect Effects 0.000 description 2
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- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- 238000007127 saponification reaction Methods 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- MABNMNVCOAICNO-UHFFFAOYSA-N selenophene Chemical compound C=1C=C[se]C=1 MABNMNVCOAICNO-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- FESBVLZDDCQLFY-UHFFFAOYSA-N sete Chemical compound [Te]=[Se] FESBVLZDDCQLFY-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- LBJQKYPPYSCCBH-UHFFFAOYSA-N spiro[3.3]heptane Chemical compound C1CCC21CCC2 LBJQKYPPYSCCBH-UHFFFAOYSA-N 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- SKRWFPLZQAAQSU-UHFFFAOYSA-N stibanylidynetin;hydrate Chemical compound O.[Sn].[Sb] SKRWFPLZQAAQSU-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 150000003518 tetracenes Chemical class 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- NMFKEMBATXKZSP-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical compound S1C=CC2=C1C=CS2.S1C=CC2=C1C=CS2 NMFKEMBATXKZSP-UHFFFAOYSA-N 0.000 description 1
- ARVUQMCWMBTJPX-UHFFFAOYSA-N thieno[3,2-e][1,2,3]benzothiadiazole Chemical compound N1=NSC2=C1C=1C=CSC=1C=C2 ARVUQMCWMBTJPX-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- IBOKZQNMFSHYNQ-UHFFFAOYSA-N tribromosilane Chemical compound Br[SiH](Br)Br IBOKZQNMFSHYNQ-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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Abstract
本发明涉及式I的金刚烷类化合物D1‑ZD‑(A1‑Z1)r‑B1‑(Z2‑A2)s‑Sp‑G(I),其中出现的基团和参数具有权利要求1中所给的含义,本发明涉及其用于形成分子层,特别是自组装单层(SAM)的用途,涉及制作用于包括所述分子层的忆阻器件的切换元件的方法,以及涉及包括所述切换元件的忆阻器件。
Description
本发明涉及金刚烷类(diamondoid)化合物,涉及其用于形成分子层,特别是自组装单层(SAM)的用途,涉及制作用于包括所述分子层的忆阻器件的切换元件的方法以及涉及包括所述切换元件的忆阻器件。
在计算机技术中,需要能够快速写入和读取访问存储在其中的信息的存储介质。固态存储器或半导体存储器能够实现特别快速和可靠的存储介质,因为完全不需要活动件。目前,主要使用动态随机访问存储器(DRAM)。DRAM允许快速访问存储的信息,但这种信息必须定期更新,意味着当切断电源时,存储的信息丢失。
现有技术也公开了非易失性半导体存储器,如闪存或磁阻随机存取存储器(MRAM),其中即使在切断电源后也保留信息。闪存的一个缺点在于写入访问进行得较慢并且闪存的存储单元无法无限期擦除。闪存的寿命通常限于最多一百万次读取/写入周期。MRAM可以类似于DRAM的方式使用并具有长寿命,但这种类型的存储器由于困难的生产过程还无法确立自身的地位。
另一替代物是在忆阻器(memristor)的基础上工作的存储器。术语忆阻器是词语“记忆体”和“电阻器”的缩写并且是指能在高电阻和低电阻之间可再现地改变其电阻的部件。即使没有供给电压,也保持相应的状态(高电阻或低电阻),意味着用忆阻器可实现非易失性存储器。
WO 2012/127542 A1和US 2014/008601 A1例如公开了具有两个电极和布置在两个电极之间的有源区(active region)的有机分子存储器。该有源区具有导电芳族炔的分子层,该导电芳族炔的电导率可在电场的影响下改变。在US 2005/0099209 A1中提出了基于氧化还原活性的联吡啶鎓(bipyridinium)化合物的类似部件。
基于电导率或电阻的变化的已知存储器具有缺点在于,通过电流流过分子层中的分子形成的自由基中间体原则上容易发生降解过程,这对部件的寿命具有不利影响。
在WO 2018/007337 A2中,描述了一种改进的切换层,该切换层利用非氧化还原活性分子层,该分子层包含通过脂族间隔基连接到基底的偶极化合物,其中所述化合物通过施加电场可逆地切换,该电场导致分子偶极子的重新取向,从而可取决于分子各自的取向实现低阻态和高阻态。
为了从具有构象柔性偶极的有机化合物获得可电切换隧道结,需要在两个导电电极之间形成一个分子层作为三明治。该分子层在电极上的沉积可通过旋涂或从有机溶剂中浸涂来实现。所得存储器器件的基本原理描述于WO 2016/110301 A1和WO 2018/007337 A2中。为了限制顶部电极和底部电极之间短路的形成,单层必须尽可能紧密,在沉积过程中没有允许顶部电极材料渗透的针孔。对于在极短的沉积时间内形成可接受质量的分子层的材料也有强烈的需求。
对结构化电极而言,常使用光刻法。目前最新的分子层的主要问题是其疏水性,其显示通常约104°的水接触角(CWA)。大多数光致抗蚀剂要求基底的CWA低于该值。由于在光致抗蚀剂溶液旋涂期间增加的CWA抗湿润以不受控的方式发生,导致不均匀的沉积。这妨碍了分子层顶上的电极结构的结构化。对光致抗蚀剂与剥离抗蚀剂(lift-off resists)的均匀分布与良好粘合而言,要求CWA显著低于100°。同时分子层表面应当具有致密堆积以及低的类烷(alkane-like)化学反应性。
待通过本发明解决的问题为提供用于制作可切换分子层的改进材料,其与半导体工业常用的工艺相容。
为了解决该问题,提供下文所示的式I化合物,其包含与极性环单元连接的末端金刚烷类部分结构,该极性环单元可以借助经由柔性间隔基连接至极性环的锚固基团而自组装至基底上。
本发明进一步涉及一种制备切换元件的方法,该切换元件包含可由一种或多种式I化合物获得的分子层。本发明进一步涉及包含该切换元件的忆阻器件。
优选实施方案为从属权利要求的主题且也可从说明书得出。
本发明涉及式I化合物
D1-ZD-(A1-Z1)r-B1-(Z2-A2)s-Sp-G (I)
其中
D1表示金刚烷类(diamondoid)基团,优选源自低级金刚烷类,非常优选选自由金刚烷基、二金刚烷基和三金刚烷基组成的组,其中一个或多个H原子可被F,具有至多12个C原子的每种情况下任选氟化的烷基、烯基或烷氧基替代,特别是
A1、A2在每次出现时相同或不同地表示具有4至25个环原子的芳族、杂芳族、脂环族或杂脂族环,其也可含有稠环且其可被Y单取代或多取代,
Y在每次出现时相同或不同地表示F、Cl、CN、SCN、SF5或具有1至12个C原子的直链或支化的、在每种情况下任选氟化的烷基、烷氧基、烷基羰基、烷氧基羰基、烷基羰基氧基或烷氧基羰基氧基,
B1表示
其中这些基团可朝两个方向取向,
L1至L5相互独立地表示F、Cl、Br、I、CN、SF5、CF3或OCF3,优选Cl或F,其中L3也可以表示H,
Z1、Z2在每次出现时相同或不同地表示单键、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-CH2O-、-OCH2-、-C(O)O-、-OC(O)-、-C(O)S-、-SC(O)-、-(CH2)n1-、-(CF2)n2-、-CF2-CH2-、-CH2-CF2-、-CH=CH-、-CF=CF-、-CF=CH-、-CH=CF-、-(CH2)n3O-、-O(CH2)n4-、-C≡C-、-O-、-S-、-CH=N-、-N=CH-、-N=N-、-N=N(O)-、-N(O)=N-或-N=C-C=N-,
n1、n2、n3、n4相同或不同地为1、2、3、4、5、6、7、8、9或10,
ZD具有Z1与Z2或Sp的含义之一,优选具有Z1与Z2的含义之一,
Sp表示间隔基团或单键,优选间隔基团,
G表示CH=CH2、-OH、-CH(CH2OH)2、-C(CH2OH)3、-SH、-SO2OH、-OP(O)(OH)2、-PO(OH)2、-C(OH)(PO(OH)2)2、-COOH、-B(OH)2、-Si(ORx)3或-SiCl3、-SO2ORV、-OP(O)(ORV)2、-PO(ORV)2、-C(OH)(PO(ORV)2)2、-COORV或-Si(ORV)3,
RV表示具有1至20个C原子的直链或支化的烷基,优选具有至多20个C原子的仲或叔烷基,
Rx表示具有1至6个C原子的直链或支化的烷基,和
r和s相互独立地表示0、1、2或3,
其中r+s≤4,
条件是,如果Sp表示单键,则Z2不为O、S、CH2或CF2。
由式I化合物获得的分子层的显著之处在于致密堆积和低CWA,从而使得能够制作用于忆阻器件的切换元件,所述器件可通过光刻法使用标准工业工艺图案化。此外,该分子层的进一步的显著之处在于高的击穿偏压(break down bias)。
附图简述:
附图显示
图1忆阻存储元件的层结构的示意图,
图2具有电阻型切换存储元件的存储器件的示例性实施方案中,所测量电流密度值对所施加电压的示例性对数曲线,
术语“金刚烷类”是指金刚烷系列的被取代和未被取代的笼状化合物,包括金刚烷、二金刚烷、三金刚烷、四金刚烷、五金刚烷、六金刚烷、七金刚烷、八金刚烷等,包括其所有异构体和立体异构体。化合物具有“金刚烷类”拓扑结构,此意味着其碳原子排列可迭加于面心立方金刚石晶格的片段上。来自该系列的第一部分的取代的金刚烷类优选具有1至4个独立选择的烷基或烷氧基取代基。
如所述术语在本文中所定义,金刚烷类包括“低级金刚烷类”和“高级金刚烷类”,以及低级和高级金刚烷类的任何组合的混合物。术语“低级金刚烷类”是指金刚烷、二金刚烷和三金刚烷,以及金刚烷、二金刚烷和三金刚烷的任一和/或所有未被取代和被取代的衍生物。
这些低级金刚烷类组分显示没有异构体或手性且易于合成,它们与“高级金刚烷类”不同。术语“高级金刚烷类”是指任一和/或所有被取代和未被取代的四金刚烷组分;任一和/或所有被取代和未被取代的五金刚烷组分;任一和/或所有被取代和未被取代的六金刚烷组分;任一和/或所有被取代和未被取代的七金刚烷组分;任一和/或所有被取代和未被取代的八金刚烷组分;以及上述的混合物以及四金刚烷、五金刚烷、六金刚烷、七金刚烷和八金刚烷的异构体和立体异构体。金刚烷化学已由Fort,Jr.等人综述于“Adamantane:Consequences of the Diamondoid Structure,”Chem.Rev.第64卷,第277-300页(1964)中。金刚烷是金刚烷类系列的最小成员且可视为单笼结晶子单元。二金刚烷含有两个子单元,三金刚烷含有三个子单元,四金刚烷含有四个子单元,诸如此类。尽管金刚烷、二金刚烷和三金刚烷仅存在一种异构形式,但四金刚烷存在四种不同异构体(其中两种代表镜像异构对),即四个金刚烷子单元的四种不同的可能排列方式。可能异构体的数量随金刚烷类系列的各高级成员五金刚烷、六金刚烷、七金刚烷、八金刚烷等而非线性地增加。金刚烷是市售的且已被广泛研究。研究已指向一些领域,如热力学稳定性、官能化、与含金刚烷材料的性质。例如,Schreiber等人,New J.Chem.,2014,38,28-41描述合成并施加经官能化的金刚烷类以在银与金表面上形成大面积SAM。在K.T.Narasimha等人,Nature Nanotechnology11,2016年3月,第267-273页中,由于金属的功函显著减少,金刚烷类单层被描述成将加强的场发射性能有效地赋予金属表面。
如本文所用,锚固基团为这样的官能基团:化合物借助该官能基团通过物理吸附、化学吸附或通过化学反应而吸附到或结合到基底表面上。
间隔基团在本发明的意义上是在偶极结构部分和锚固基团之间的柔性链,其造成这些子结构之间的分隔并由于其柔性,同时改进偶极结构部分在结合到基底上之后的迁移率。
间隔基团可以是支化或直链的。手性间隔基是支化和任选活性的。
在本文中,烷基为直链或支化的且具有1至15个C原子,优选为直链且除非另有说明,否则具有1、2、3、4、5、6或7个C原子,因此优选为甲基、乙基、丙基、丁基、戊基、己基或庚基。
在本文中,烷氧基为直链或支化的且含有1至15个C原子。其优选为直链,且除非另有说明,否则具有1、2、3、4、5、6或7个C原子,因此优选为甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基或庚氧基。
在本文中,烯基优选为具有2至15个C原子的烯基,其为直链或支化的且含有至少一个C-C双键。其优选为直链且具有2至7个C原子。因此,其优选为乙烯基、丙-1-烯基或丙-2-烯基、丁-1-烯基、丁-2-烯基或丁-3-烯基、戊-1-烯基、戊-2-烯基、戊-3-烯基或戊-4-烯基、己-1-烯基、己-2-烯基、己-3-烯基、己-4-烯基或己-5-烯基、庚-1-烯基、庚-2-烯基、庚-3-烯基、庚-4-烯基、庚-5-烯基或庚-6-烯基。如果C-C双键的两个C原子被取代,则烯基可呈E和/或Z异构体(反式/顺式)的形式。一般而言,各E异构体优选。在所述烯基中,丙-2-烯基、丁-2-烯基和丁-3-烯基以及戊-3-烯基和戊-4-烯基为特别优选的。
在本文中,炔基是指具有2至15个C原子的炔基,其为直链或支化的且含有至少一个C-C三键。1-丙炔基和2-丙炔基以及1-丁炔基、2-丁炔基和3-丁炔基为优选的。
在式I中,优选芳基例如衍生自母体结构苯、萘、四氢萘、9,10-二氢菲、芴、茚和二氢茚。
在式I中,优选的杂芳基是例如五元环,例如呋喃、噻吩、硒吩、噁唑、异噁唑、1,2-噻唑、1,3-噻唑、1,2,3-噁二唑、1,2,4-噁二唑、1,2,5-噁二唑、1,3,4-噁二唑、1,2,3-噻二唑、1,2,4-噻二唑、1,2,5-噻二唑和1,3,4-噻二唑,六元环,例如吡啶、哒嗪、嘧啶、吡嗪、1,3,5-三嗪、1,2,4-三嗪和1,2,3-三嗪,或稠环,例如吲哚、异吲哚、中氮茚、吲唑、苯并咪唑、苯并三唑、嘌呤、萘并咪唑、苯并噁唑、萘并噁唑、苯并噻唑、苯并呋喃、异苯并呋喃、二苯并呋喃、噻吩并[2,3b]噻吩、噻吩并[3,2b]噻吩、二噻吩并噻吩、异苯并噻吩、二苯并噻吩、苯并噻二唑并噻吩、2H-色烯(2H-1-苯并吡喃)、4H-色烯(4H-1-苯并吡喃)和香豆素(2H-色烯-2-酮),或这些基团的组合。
在式I中,优选的脂环族基团是环丁烷、环戊烷、环己烷、环己烯、环庚烷、十氢萘、双环[1.1.1]戊烷、双环[2.2.2]辛烷、螺环[3.3]庚烷和八氢-4,7-亚甲基二氢茚。
在式I中,优选的杂脂族基团是四氢呋喃、二氧戊环、四氢噻吩、吡喃、二氧杂环己烷、二噻烷、硅杂环己烷(silinane)、哌啶和吡咯烷。
A1和A2在每次出现时相同或不同,更优选选自以下组:
a)1,4-亚苯基,其中,此外,一个或两个CH基团可被N替代,并且其中,此外,一个或多个H原子可被Y替代,
b)由反式-1,4-亚环己基和1,4-亚环己烯基组成的组,其中,此外,一个或多个不相邻CH2基团可被-O-和/或-S-替代,并且其中,此外,一个或多个H原子可被Y替代,和
c)由1,3-二氧戊环-2,4-二基、四氢呋喃-2,5-二基、环丁烷-1,3-二基、1,4-双环[2.2.2]辛烷二基、哌啶-1,5-二基和噻吩-2,5-二基组成的组,其中,此外,一个或多个H原子可被Y替代,
其中Y具有上文在式I下所给的含义,优选表示F、Cl、CN或CF3。
在式I中,优选间隔基团Sp选自式Sp'-X',从而使基团G-Sp-对应于式G-Sp'-X'-以及使基团D1-Sp-对应于式D1-Sp’-X’,其中
Sp’表示具有1至20个,优选1至12个C原子的直链或支化的亚烷基,其任选被F、Cl、Br、I或CN单取代或多取代,且其中,此外,一个或多个非相邻CH2基团可各自相互独立地被-O-、-S-、-NH-、-NR0-、-SiR00R000-、-CO-、-COO-、-OCO-、-OCO-O-、-S-CO-、-CO-S-、-NR0-CO-O-、-O-CO-NR0-、-NR0-CO-NR0-、-CH=CH-或-C≡C-以O和/或S原子相互不直接连接的方式替代,
X’表示-O-、-S-、-CO-、-COO-、-OCO-、-O-COO-、-CO-NR00-、-NR00-CO-、-NR00-CO-NR00-、-OCH2-、-CH2O-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-CF2CH2-、-CH2CF2-、-CF2CF2-、-CH=N-、-N=CH-、-N=N-、-CH=CR00-、-CYx=CYx‘-、-C≡C-、-CH=CH-COO-、-OCO-CH=CH-或单键,
R0、R00
和R000各自相互独立地表示H或具有1至12个C原子的烷基,和
Yx和Yx‘各自相互独立地表示H、F、Cl或CN。
X’优选为-O-、-S-、-CO-、-COO-、-OCO-、-O-COO-、-CO-NR0-、-NR0-CO-、-NR0-CO-NR0-或单键。
优选基团Sp’为-(CH2)p1-、-(CF2)p1-、-(CH2CH2O)q1-CH2CH2-、-(CF2CF2O)q1-CF2CF2-、-CH2CH2-S-CH2CH2-、-CH2CH2-NH-CH2CH2-或-(SiR00R000-O)p1-,其中p1为1至12的整数,q1为1至3的整数,且R00和R000具有上文所示的含义。
特别优选基团-X’-Sp’-为-(CH2)p1-、-O-(CH2)p1-、-(CF2)p1-、-O(CF2)p1-、-OCO-(CH2)p1-和-OC(O)O-(CH2)p1-,其中p1具有上文所示的含义。
在每种情况下,特别优选基团Sp’为例如直链亚乙基、亚丙基、亚丁基、亚戊基、亚己基、亚庚基、亚辛基、亚壬基、亚癸基、亚十一烷基、亚十二烷基、亚十八烷基、全氟亚乙基、全氟亚丙基、全氟亚丁基、全氟亚戊基、全氟亚己基、全氟亚庚基、全氟亚辛基、全氟亚壬基、全氟亚癸基、全氟亚十一烷基、全氟亚十二烷基、全氟亚十八烷基、亚乙基氧基亚乙基、亚甲基氧基亚丁基、亚乙基硫代亚乙基、亚乙基-N-甲基亚氨基亚乙基、1-甲基亚烷基、亚乙烯基、亚丙烯基和亚丁烯基。
特别优选基团X’为-O-或单键。
式I的特别优选的子式为子式Ia至If:
D1-ZD-B1-Sp-G Ia
D1-ZD-(A1-Z1)-B1-Sp-G Ib
D1-ZD-(A1-Z1)2-B1-Sp-G Ic
D1-ZD-B1-(Z2-A2)-Sp-G Id
D1-ZD-B1-(Z2-A2)2-Sp-G Ie
D1-ZD-(A1-Z1)-B1-(Z2-A2)-Sp-G If
其中D1、A1、A2、B1、ZD、Z1、Z2、Sp和G具有上文所示含义。
在式I及其子式中,非常优选
A1和A2相同或不同地表示
B1表示
D1表示金刚烷基或二金刚烷基,特别是金刚烷基,
L1和L2相互独立地表示Cl或F,其中基团L1和L2中至少一个表示F,
L3表示F,
Y1和Y2相互独立地表示H、Cl或F,
ZD表示单键、-C≡C-、-C(O)O-、-OC(O)-、-OCH2-、-CH2O-、-CH2CH2-、-CH2CH2CH2-或-CH2CH2CH2CH2-,
Z1、Z2相互独立地表示单键、-C(O)O-、-OC(O)-、-CF2O-、-OCF2-、-CH2O-、-OCH2-、-CH2CH2-,特别优选单键,
Sp表示具有1、2、3、4、5、6、7、8、9、10、11或12个C原子的未支化的1,ω-亚烷基,
G表示-OP(O)(OH)2、-PO(OH)2或-COH(PO(OH)2)2。
在另一优选实施方案中,在式Ia至If的化合物中,
Sp表示具有1至12个C原子的未支化的1,ω-全氟亚烷基,
其中D1、A1、A2、B1、Z1、Z2和G具有上文所示含义。
非常特别优选式I的子式为式Ia、Ib和Id的子式,特别是如下化合物:
其中D1、ZD和G具有上文所给含义,优选
D1表示金刚烷基或二金刚烷基,
ZD表示-CH2O-、-C≡C-或单键,
G表示-P(O)(OH)2或-COH(P(O)(OH)2)2,
以及其中
v为1至12的整数,优选2至7的整数。
本说明书还包括式I化合物,其中在子式Ia-1至Ia-12、Ib-1至Ib-24和Id-1至Id-18中,基团-CvH2v-被-CvF2v-替代。
根据本发明的另一方面,提供了手性非外消旋的式I化合物。
由手性式I化合物获得的分子层能使忆阻器件具有显著降低的随机噪声和更快的切换,从而降低读取和写入错误率,这对能量效率具有正面效应。另外,观察到增加的隧道电流,这允许整合为较小的接尺寸。
优选地,手性化合物具有50%以上,优选80%、90%、95%以上,更优选97%以上,特别是98%以上的对映异构过量(ee)。
手性为通过具有一个或多个,优选一个或两个,非常优选一个不对称取代碳原子(或:不对称碳原子,C*)的以上式I的支化手性基团Sp(在下文中称为Sp*)实现。
在Sp*中,不对称碳原子优选连接至两个不同取代的碳原子、一个氢原子和一个选自以下的取代基:卤素(优选F、Cl或Br),在每种情况下具有1至5个碳原子的烷基或烷氧基,以及CN。
手性有机基团Sp*优选具有下式
其中
X’具有上文对式I的所定义的含义,优选表示-CO-O-、-O-CO-、-O-CO-O-、-CO-、-O-、-S-、-CH=CH-、-CH=CH-COO-或单键,更优选-CO-O-、-O-CO-、-O-或单键,非常优选-O-或单键,
Q和Q’相同或不同地表示单键或具有1至10个碳原子的任选氟化亚烷基,其中未与X’连接的CH2基团也可被-O-、-CO-、-O-CO-、-CO-O-或-CH=CH-替代,优选具有1至5个碳原子的亚烷基或单键,特别优选–(CH2)n5-或单键,
n5为1、2、3、4、5或6,
Y表示具有1至15个碳原子的任选氟化烷基,其中一个或两个非相邻CH2基团也可被-O-、-CO-、-O-CO-、-CO-O-和/或-CH=CH-替代;进一步表示CN或卤素,优选具有1至7个C原子的任选氟化烷基或烷氧基、-CN或Cl,特别优选-CH3、-C2H5、-CF3或Cl,
在其中式I中的ZD为手性非外消旋间隔基团的实施方案中,基团D1-Sp*优选具有下式
其中所出现的基团具有上文所给的含义。
通式I的化合物通过本身已知的方法制备,如文献(例如在权威著作中,例如Houben-Weyl,Methoden der organischen Chemie[有机化学方法],Georg-Thieme-Verlag,Stuttgart)中所述,需要确切地在已知且适于所述反应的反应条件下进行。在本文中可使用本身已知的变型,但此处未更详细地描述。手性基团R*和Sp*阐述于A.Taugerbeck,Ch.Booth,Design and Synthesis of Chiral Nematic Liquid Crystals,于:Handbook of Liquid Crystals,第3卷,第III部分,第14章,Wiley VCH,Weinheim,2014中,优选可根据本文所述或本文引用的参考文献所述的合成方法来合成。
需要的话,起始材料也可通过不将其从反应混合物分离而原位形成,而是立即将其进一步转化成通式I的化合物。
本发明化合物的优选合成途径显示于以下方案中,并通过工作实施例进一步说明。可通过选择合适的起始材料以使合成适于通式I的特定期望化合物。
金刚烷类结构部分的合适前体为相应的金刚烷醇和羟基烷基衍生物,其通过下列所述的方法可容易地获得:H.Schwertfeger等人,Angew.Chem.Int.Ed.2008,47,1022-1036;W.L.Yang等人,Science 2007,316,1460-1462;W.A.Clay等人,Nano Lett.2009,9,57-61;等,Langmuir 2013,29,9790-9797;K.T.Narasimha等人,Nat.Nanotechnol.2015,11,267-272;A.A.Fokin等人,Synthesis 2017,49,2003-2008;M.A.Gunawan等人,Nanoscale 2015,7,1956-1962;P.Kahl等人,Synthesis2014,46,787-798;N.A.Fokina等人,Synthesis2012,44,259-264;A.A.Fokin等人,Chem.Eur.J.2009,15,3851-3862。
金刚烷类结构部分连接到单层前体的主结构可以通过如下方法实现:用金刚烷类叔醇将酚直接衍生化(参见A.Koperniku等人,Lett.Org.Chem.2016,13,171-176);芳基卤化物与金刚烷类锌经由Negishi偶合的反应(参见C.等人,Org.Lett.2014,16,2418-2421);或酚与活化的烷基金刚烷类经由亲核取代(参见R.G.Booth等人,J.Med.Chem.1987,30,1218-1224;Angew.Chem.Int.Ed.,2014,53,9669-9673)。
在如下方案中,上述合成途径使用金刚烷衍生物的实例举例说明。反应也适合于高级金刚烷类的转变。
通常优选的构建单位(building block)例如由金刚烷基卤化物1(方案1),优选金刚烷基溴获得,其可以与酚反应以得到金刚烷基酚(3)。根据Ch.等人,Org.Lett.2014,16,2418-2421,金刚烷基卤化物也用于形成锌试剂(4)。这些试剂与大量公知的芳族化合物经受Negishi偶合反应以得到金刚烷基芳基衍生物5。
方案1
易获得的金刚烷醇6可以经由Friedel-Crafts反应在三氟乙酸存在下转变为芳基衍生物5(参见Koperniku,Ana等人,Letters in Organic Chemistry,13(3),171-176;2016)。在Williamson醚合成法中醇7可以用于例如将酚衍生化以得到化合物8。
方案2
已知的炔9(方案3)也可以经由上述Negishi偶合转变为苯乙炔10且为用于进一步公知的例如转变为酚11的通用构建单位。
方案3
酚3经由氢化提供环己基衍生物(方案4)。
方案4
锚固基团可以通过上文引用的现有技术已知的优选转变连接至构建单元,以及显示在工作实施例中。其他典型转变示例于方案5,例如酚3可以通过与ω-溴羧酸酯烷基化,然后皂化以得到具有羧酸锚固基团的化合物(14),或与受保护醇如(2,2-二甲基-1,3-二噁烷-5-基)甲醇醚化产生醇如化合物16。
方案5
本发明进一步涉及一种制备本发明的切换元件的方法,其包括至少以下步骤:
a)制备具有表面的第一电极,
b)在该第一电极的表面上沉积包含一种或多种式I化合物的单层,
c)施加第二电极。
单层的沉积使用纯物质或由溶液,优选由溶液进行。合适的沉积方法和溶剂对本领域技术人员是已知的;实例为旋涂或浸涂。
根据本发明的另一方面,由一种或多种式I化合物制作单层,其中在式I化合物中锚固基团G表示-SO2ORV、-OP(O)(ORV)2、-PO(ORV)2、-C(OH)(PO(ORV)2)2、-COORV或-Si(ORV)3,其中RV表示具有1至20个C原子的烷基,优选具有至多20个C原子的仲或叔烷基。这些化合物的显著之处在于特别高的溶解度,且特别适于工业工艺,例如旋涂。另外,可通过气相沉积加工这些化合物。所述化合物用作相应游离酸的前体,其中在沉积于第一电极上之后通过对化合物进行热处理而原位获得游离酸。然后将第一电极加热至60℃至300℃,优选100℃至250℃,特别是140℃至180℃的温度。
在优选实施方案中,在沉积分子层之后,使基底退火。退火在高于20℃且低于300℃,优选高于50℃且低于200℃,特别优选高于90℃且低于150℃的温度下进行。退火的持续时间为1至48h,优选4至24h,特别优选8至16h。
本发明的分子层为电绝缘、非导电和非半导电有机化合物的层。
分子层优选包含式I的分子,或特别优选由式I的分子组成。
层的厚度优选为10nm或以下,特别优选5nm或以下,非常特别优选2nm或以下。
分子层可由一个、两个、三个或更多个包含式I化合物的分子层组成。
根据本发明所采用的分子层优选为分子单层。
在一个实施方案中,分子层为自组装单层(SAM)。
自组装单层的制备对本领域技术人员是已知的;综述例如在A.Ulman,Chem.Rev.1996,96,1533-1554中给出。
在另一实施方案中,分子层通过化学吸附,特别是加成反应或缩合反应结合至基底。
在另一实施方案中,分子层通过物理吸附结合至基底。
基底的覆盖度优选为90%至100%,特别优选95%或更高至100%,非常特别优选98%或更高至100%。
在另一实施方案中,分子层覆盖有1至10,优选1至5,特别优选1至3个有机或无机吸附物的其他层。合适的层包括例如电介质,例如氧化、氟化或氮化材料,例如TiO2、Al2O3、HfO2、SiO2、LiF和Si3N4;或金属,例如Pt、Pd、Pb、Au、Ag、Cu、Al和Mg,及其共晶(eutectic)化合物,例如PdAu 20:80。所述层可通过限定的且高精密度的沉积,例如通过ALD(原子层沉积)工艺以几纳米的厚度构建。
分子层的分子优选共价结合至基底。结合通过本领域技术人员熟知的已知方法进行,例如通过式I化合物的加成反应或利用位于基底表面上的羟基酯化而进行。
对于加成反应,合适的基底,优选硅表面在用NH4F水溶液进行相应预处理之后可例如经处理以获得氢封端的表面。然后,以此方式处理的表面可在升高温度下在排除氧的情况下直接用式I的合适的液体化合物或式I化合物于合适的溶剂中的溶液进行处理。根据本发明的此方面,式I中的基团G优选表示-CH=CH2。
对于缩合反应,合适的基底,优选硅表面可例如用氧等离子体处理,以获得充满羟基的亲水氧化表面。然后,以此方式处理的表面可在升高温度下直接与式I的合适的液体化合物或式I化合物于合适的溶剂中的溶液反应。很显然,此类型的氧化表面仅用于表面改性,目的为可经由缩合反应进行衍生,而并不代表真正意义上的绝缘层。由于约1nm的低厚度,因此穿过此氧化表面的隧道电流可足够大。
在本发明的切换元件中,分子层的分子结合至基底或位于分子单层与基底之间的中间层。取决于切换元件的结构,本发明的基底可执行各种功能。例如,导电基底可用作第一电极。同样,基底可为二极管的层。
合适的基底对本领域技术人员是已知的。尤其合适的基底选自:
-单质半导体,例如Si、Ge、C(金刚石、石墨、石墨烯、富勒烯)、α-Sn、B、Se和Te;
-化合物半导体,优选
-III-V族半导体,特别是GaAs、GaP、InP、InSb、InAs、GaSb、GaN、TaN、TiN、MoN、WN、AlN、InN、AlxGa1-xAs和InxGa1-xNi,
-II-VI族半导体,特别是ZnO、ZnS、ZnSe、ZnTe、CdS、CdSe、CdTe、Hg(1-x)Cd(x)Te、BeSe、BeTex和HgS;
-III-VI族半导体,特别是GaS、GaSe、GaTe、InS、InSex和InTe,
-I-III-VI族半导体,特别是CuInSe2、CuInGaSe2、CuInS2和CuInGaS2,
-IV-IV族半导体,特别是SiC和SiGe,
-IV-VI族半导体,特别是SeTe;
-有机半导体,特别是聚噻吩、并四苯、并五苯、酞菁、PTCDA、MePTCDI、喹吖啶酮、吖啶酮、阴丹酮(indanthrone)、黄士酮(flavanthrone)、紫环酮(perinone)、AlQ3和混合体系,特别是PEDOT:PSS和聚乙烯基咔唑/TLNQ络合物;
-金属,特别是Ta、Ti、Co、Mo、Pt、Ru、Au、Ag、Cu、Al、W和Mg;
-导电氧化物材料,特别是氧化铟锡(ITO)、氧化铟镓(IGO)、InGa-α-ZnO(IGZO)、铝掺杂氧化锌(AZO)、锡掺杂氧化锌(TZO)、氟掺杂氧化锡(FTO)和氧化锑锡。
分子层也可任选结合至位于基底上的薄(优选0.5-5nm厚)氧化或氟化中间层,例如TiO2、Al2O3、HfO2、SiO2或LiF。
对电极或第二电极由导电或半导电材料或多种这些材料的组合(层堆叠)而组成。实例为作为基底材料提及的材料。优选的是Hg、In、Ga、InGa、Ag、Au、Cr、Pt、PdAu、Pb、Al、Mg、W、Yb、Zn、CNT(碳纳米管)、石墨烯和导电聚合物(例如PEDOT:PSS)。
电极的制备和结构化通过本领域技术人员已知的方法进行。包含由一种或多种式I化合物获得的分子层的切换元件的制作和电表征根据WO 2016/110301 A1和WO 2018/007337 A2中阐述的程序进行。
实施例
合成实施例1:3-[4-(1-金刚烷基)-2,3-二氟-苯氧基]丙基膦酸
步骤1:4-(1-金刚烷基)-2,3-二氟苯酚
在50℃和氮气下将1-溴金刚烷(98.8g,0.459mol)经5分钟分批加至熔融2,3-二氟苯酚(478g,3.67mol)中,并在120℃加热过夜。将反应混合物冷却至80℃并倒入热水(4L)中,搅拌30分钟,冷却至50℃,过滤并干燥以得到灰白色固体。在55℃在水(1.5L)中搅拌该固体1小时,过滤,用热水(3×500mL)洗涤,由乙腈再结晶,以得到呈白色固体的4-(1-金刚烷基)-2,3-二氟苯酚。
1H NMR(400MHz,CHCl3-d)δppm 1.78(6H,t,J=2.9Hz),2.01(6H,d,J=2.4Hz),2.09(3H,br s),6.71(1H,td,J=8.5Hz,2.1Hz),6.86(1H,td,J=8.6Hz,2.3Hz)。
13C NMR(400MHz,DMSO-d)δppm 28.3,35.6(dd,J=2.9Hz,1.5Hz),36.3,41.0(d,J=3.7Hz),111.9(m),120.1(dd,J=7.0Hz,4.0Hz),128.4(dd,J=8.1Hz,2.2Hz),140.4(dd,J=241.4,16.1Hz),144.6(dd,J=9.5Hz,2.9Hz),150.5(d,J=246.9Hz,10.7Hz)。
19F NMR(400MHz,CHCl3-d)δppm-164.38(1F,d,J=19.1Hz),-136.19(1F,d,J=19.1Hz)。
步骤2:1-[4-(3-二乙氧基磷酰丙氧基)-2,3-二氟-苯基]金刚烷
将碳酸钾(11.97g,86.6mmol)添加至4-(1-金刚烷基)-2,3-二氟苯酚(5.72g,21.65mmol)与(3-溴丙基)膦酸二乙酯(6.2g,22.73mmol)的甲乙酮(73mL)溶液中,并将混合物在回流下加热过夜,冷却至40℃,过滤,用丙酮洗涤固体。将滤液真空浓缩至干以得到无色油,在硅石上用乙酸乙酯/DCM(0至50%)纯化该油以得到呈无色固体的1-[4-(3-二乙氧基磷酰丙氧基)-2,3-二氟-苯基]金刚烷。
1H NMR(400MHz,CHCl3-d)δppm 1.32(6H,t,J=7.0Hz),1.77(6H,m),1.90-2.14(13H,m),4.06-4.16(6H,m),6.62-6.67(1H,m),6.84(1H,td,J=8.4Hz,2.4Hz)。
19F NMR(400MHz,CHCl3-d)δppm-159.52(1F,d,J=17.7Hz),-136.00(1F,d,J=17.7Hz)。
31P NMR(400MHz,CHCl3-d)δppm 31.55
步骤3:3-[4-(1-金刚烷基)-2,3-二氟-苯氧基]丙基膦酸
将三甲基溴硅烷(19.1g,125.0mmol)经10分钟滴加至1-[4-(3-二乙氧基磷酰丙氧基)-2,3-二氟-苯基]金刚烷(5.53g,12.50mmol)在二氯甲烷(83.0mL)中的溶液中,并在室温下将溶液搅拌过夜。将反应混合物浓缩至干,添加二氯甲烷(110mL)与甲醇(55mL)并慢慢除去二氯甲烷。一旦不再蒸出溶剂,就在室温下搅拌残余溶液并在冷却时沉淀出固体。在0至5℃搅拌混合物1小时,然后滤出固体并用甲醇洗涤以得到呈白色固体的3-[4-(1-金刚烷基)-2,3-二氟-苯氧基]丙基膦酸。
1H NMR(400MHz,THF-d)δppm 1.78-1.86(8H,m),2.03-2.10(11H,m),4.10(2H,t,J=6.4Hz),6.77-6.82(1H,m),6.87-6.92(1H,m)。
19F NMR(400MHz,THF-d)δppm-162.95(1F,d,J=17.7Hz),-139.85(1F,d,J=17.7Hz)。
31P NMR(400MHz,THF-d)δppm 29.69。
ES(-ve)MS:m/z=385.1382,100%[M-H]-,C19H24F2O4P-要求385.1380。
合成实施例2
步骤1:11-[4-(1-金刚烷基)-2,3-二氟-苯氧基]十一烷-1-醇
将碳酸钾(14.6g,105.9mmol)分批添加至4-(1-金刚烷基)-2,3-二氟苯酚(7.0g,26.5mmol)与11-溴十一醇(7.0g,27.8mmol)的甲乙酮(88mL)溶液中,并将混合物在回流下加热过夜。用丙酮洗涤固体并在40℃将滤液真空浓缩至干以得到白色固体(11.8g)。经由庚烷再结晶产生呈白色固体的11-[4-(1-金刚烷基)-2,3-二氟-苯氧基]十一烷-1-醇。
1H NMR(400MHz,CHCl3-d)δppm 1.25-1.40(12H,m),1.42-1.49(4H,m),1.58(2H,m),1.78-1.84(8H,m),2.01(6H,d,J=2.3Hz),2.09(3H,br s),3.65(2H,t,J=6.5Hz),4.01(2H,t,J=6.5Hz),6.65(1H,m),6.85(1H,td,J=8.7Hz,2.4Hz)。
13C NMR(400MHz,CHCl3-d)δppm 25.68,25.84,28.80,29.14,29.27,29.37,29.45,29.47,29.53,32.66,36.21(dd,J=3.3Hz,1.8Hz),36.74,41.28(d,J=3.7Hz),63.01,69.66,108.57(d,J=2.2Hz),119.58(dd,J=7.3Hz,4.4Hz),131.24(dd,J=8.4,1.8Hz),142.0(dd,J=246Hz,15.8Hz),146.38(dd,J=8.1Hz,2.9Hz),151.1(dd,J=250Hz,10.3Hz)。
19F NMR(400MHz,CHCl3-d)δppm-159.38(1F,d,J=17.7Hz),-136.25(1F,d,J=17.7Hz)。
步骤2:1-[4-(11-溴十一烷氧基)-2,3-二氟-苯基]金刚烷
将11-[4-(1-金刚烷基)-2,3-二氟-苯氧基]十一烷-1-醇(10.5g,24.16mmol)与三苯膦(8.81g,26.58mmol)在二氯甲烷(105mL)中冷却至2℃。将四溴化碳(8.81g,26.58mmol)经10分钟分批加入并在室温下将反应搅拌过夜。将另外的三苯膦(1.90g)与四溴化碳(2.4g)紧接着一次全部加入。将反应混合物浓缩至干,添加庚烷(250mL)并在50℃搅拌45分钟。滤出固体及并用热庚烷洗涤。合并滤液并在50℃真空浓缩以得到固体。添加庚烷(140mL)并通过硅石垫过滤,用热庚烷(700mL)洗涤硅石垫。将滤液浓缩至干以得到固体。将固体由庚烷再结晶以得到呈灰白色固体的1-[4-(11-溴十一烷氧基)-2,3-二氟-苯基]金刚烷。
1H NMR(400MHz,CHCl3-d)δppm 1.25-1.38(10H,m),1.39-1.51(4H,m),1.76-1.91(10H,m),2.01(6H,d,J=2.5Hz),2.09(3H,br.s.),3.42(2H,t,J=6.9Hz),4.01(2H,t,J=6.5Hz),6.65(1H,m),6.85(1H,td,J=8.7,2.5Hz)。
13C NMR(400MHz,CHCl3-d)δppm 25.84,28.13,28.72,28.81,29.15,29.28,29.37,29.40,29.44,32.80,33.99,36.22(dd,J=2.9Hz,1.5Hz),36.76,41.29(d,J=2.9Hz),69.66,108.58(m),119.58(dd,J=7.3,4.4Hz),131.24(dd,J=8.8,2.2Hz),142.00(dd,J=245.8Hz,16.1Hz),146.39(dd,J=8.4,2.6Hz),151.09(dd,J=249.4Hz,11.0Hz)。
19F NMR(400MHz,CHCl3-d)δppm-159.76(d,J=17.71Hz),-136.24(d,J=17.71Hz)
步骤3:11-[4-(1-金刚烷基)-2,3-二氟-苯氧基]十一烷基膦酸
在135℃和氮气下将1-[4-(11-溴十一烷氧基)-2,3-二氟-苯基]金刚烷(8.2g,16.5mmol)与亚磷酸三乙酯(8.21g,49.45mmol)加热70小时。添加另一份亚磷酸三乙酯(1.4g,8.3mmol)并在145℃加热反应过夜。添加另外的亚磷酸三乙酯(1.4g,8.3mmol)并加热反应混合物24小时。将反应减压蒸发,将粗制1-[4-(11-二乙氧基磷酰十一烷氧基)-2,3-二氟-苯基]金刚烷溶于二氯甲烷(137mL),经15分钟滴加三甲基溴硅烷(75.7g,494mmol)并将溶液搅拌过夜。将反应真空浓缩至干。将二氯甲烷(180mL)与甲醇(90mL)加至固体并慢慢除去二氯甲烷直到不再蒸出溶剂。将溶液冷却至-5℃并搅拌30分钟。滤出沉淀物,用冷甲醇洗涤并干燥以得到呈白色固体的11-[4-(1-金刚烷基)-2,3-二氟-苯氧基]十一烷基膦酸,将其由THF/庚烷再结晶。
1H NMR(400MHz,THF-d8)δppm 1.25-1.43(12H,m),1.43-1.52(2H,m),1.52-1.65(4H,m),1.75-1.85(8H,m),1.97-2.12(9H,m),4.01(2H,t,J=6.5Hz),6.73-6.81(1H,m),6.89(1H,td,J=8.8Hz,2.3Hz)。
19F NMR(400MHz,THF-d8)δppm-161.2(1F,d,J=17.7Hz),-138.1(1F,d,J=17.7Hz)。
31P NMR(400MHz,THF-d8)δppm 32.5。
ES(-ve)MS:m/z=497.2623,100%[M-H]-,C27H40F2O4P-要求497.2632。
合成实施例3
步骤1:甲磺酸1-金刚烷基甲酯
将1-金刚烷基甲醇(163g,0.98mol)溶于二氯甲烷(1.9L),然后在冰冷却下添加甲磺酰氯(124g,1.08mol)。滴加三乙胺(198g,1.98mol)。将反应混合物温热至室温并搅拌过夜。过滤混合物并用二氯甲烷洗涤白色固体。将滤液与HCl(81mL,37%,稀释成1L)搅拌30分钟,然后分离出有机物并用Na2CO3水溶液(500mL)搅拌过夜。分离出有机相,用MgSO4干燥,过滤并移除溶剂以产生呈灰白色固体的甲磺酸1-金刚烷基甲酯。
1H NMR(400MHz,CHCl3-d)δppm 1.57(d,J=2.32Hz,6H)1.62-1.68(m,3H)1.71-1.78(m,3H)2.02(br.s.,3H)3.00(s,3H)3.78(s,2H)
步骤2:1-[(4-溴-2,3-二氟-苯氧基)甲基]金刚烷
将4-溴-2,3-二氟苯酚(50g,240mmol)溶于二甲基甲酰胺(500mL)。添加K2CO3(66g,480mmol),接着添加甲磺酸金刚烷-1-基甲酯(70g,288mmol)并在120℃下将反应搅拌36小时。将混合物倒在水(1L)中并用二氯甲烷萃取。用盐水洗涤有机层,经MgSO4干燥,过滤并移除溶剂。通过硅石用庚烷过滤粗材料以得到呈无色固体的1-[(4-溴-2,3-二氟-苯氧基)甲基]金刚烷。
步骤3:[4-(1-金刚烷基甲氧基)-2,3-二氟-苯基]硼酸
在-70℃和氮气下将正丁基锂(2.5M,76mL,183mmol)经1小时滴加至在THF(600ml)中的1-[(4-溴-2,3-二氟-苯氧基)甲基]金刚烷(59.3g,116mmol)中。在-70℃下将反应搅拌1小时,然后添加硼酸三甲酯(24mL,216mmol),让反应慢慢温热至室温并搅拌过夜。添加水(200mL)并将混合物倒入稀HCl并搅拌30分钟。分离出有机相并用MTB醚(200mL)萃取水相。用盐水洗涤合并的有机层,经MgSO4干燥,过滤并除去溶剂。将粗材料悬浮于二氯甲烷中并通过层析法在硅石上用二氯甲烷,然后用THF中的5%甲醇纯化。获得呈黄色无定形固体的[4-(1-金刚烷基甲氧基)-2,3-二氟-苯基]硼酸。
1H NMR(400MHz,CHCl3-d)δppm 1.67(d,J=2.08Hz,6H)1.69-1.74(m,3H)1.75-1.81(m,3H)2.04(br.s.,3H)3.55(s,2H)6.62-6.69(m,1H)7.18(ddd,J=9.14,7.12,2.32Hz,1H)
步骤4:4-(1-金刚烷基甲氧基)-2,3-二氟苯酚
将[4-(1-金刚烷基甲氧基)-2,3-二氟-苯基]硼酸(43g,133mmol)溶于THF(400mL),然后添加在40ml水中的乙酸(16mL,280mmol)并搅拌5分钟。经10分钟滴加过氧化氢(30.3mL,30%溶液)并在室温下将反应搅拌过夜。添加亚硫酸氢盐溶液(270mmol,600mL)。将混合物冷却至室温并分离出有机相。用MTB醚(200mL)萃取水相并用稀亚硫酸氢盐溶液、水与盐水洗涤合并的有机物,经MgSO4干燥。除去溶剂并将粗材料由二氯甲烷/庚烷再结晶以得到4-(1-金刚烷基甲氧基)-2,3-二氟苯酚。
1H NMR(400MHz,CDCl3-d)δppm 1.67(d,J=2.32Hz,6H)1.68-1.74(m,3H)1.74-1.80(m,3H)2.03(br.s.,3H)3.52(s,2H)4.76(br.s.,1H)6.50-6.80(m,2H)。
步骤5:1-[[4-(3-溴丙氧基)-2,3-二氟-苯氧基]甲基]金刚烷
将碳酸钾(2.20g,15.9mmol),然后将1,3-二溴丙烷(6.90mL,67.9mmol)添加至4-(1-金刚烷基甲氧基)-2,3-二氟苯酚(4.00g,13.6mmol)在丙酮(50mL)中的溶液中。将混合物在回流下加热15小时,过滤并将滤液减压浓缩。通过硅胶层析法用增加量的二氯甲烷纯化残留物以得到呈浅黄色油的1-[[4-(3-溴丙氧基)-2,3-二氟-苯氧基]甲基]金刚烷。
步骤6:1-[[4-(3-双叔丁氧基磷酰丙氧基)-2,3-二氟-苯氧基]甲基]金刚烷
将氢化钠(在矿物油中的60%悬浮物;581mg,14.5mmol)分批添加至THF(30mL)中的亚磷酸双叔丁酯(2.9mL,14.5mmol)中,并在室温下将混合物搅拌45分钟。添加1-[[4-(3-溴丙氧基)-2,3-二氟-苯氧基]甲基]-金刚烷(3.45g,8.30mmol)于THF(30mL)中的溶液,并将混合物在回流下加热15小时,冷却并用水淬灭。添加MTB醚(200mL)与水(200mL)并分离层。用MTB醚萃取水层,合并有机层,并用水、盐水洗涤,经MgSO4干燥,过滤和减压浓缩。在50℃与10毫巴下由Kugelrohr蒸馏除去过量亚磷酸双叔丁酯并通过硅胶层析法使用CH2Cl2中的0%至100%EtOAc作为洗脱液纯化粗产品。获得呈蜡质无色固体的1-[[4-(3-双叔丁氧基磷酰丙氧基)-2,3-二氟-苯氧基]甲基]金刚烷。
类似于合成实施例1,获得下列化合物:
应用实施例
接触角测量
通过下列步骤进行测试芯片的制备:
1.制备待测化合物的THF溶液(c=1mmol/l),
2.O2等离子体清洁/氧化具有30nm Al的8×8mm硅芯片(p<0.3毫巴O2,t=1分钟,150W(W=50%)),
3.将芯片在步骤1的化合物溶液中浸渍72小时,
4.在N2气流中干燥,
5.在N2气氛中烘烤(120℃)1小时,
6.通过用THF快速漂洗而清洁,
7.在N2气流中干燥。
研究下列化合物:
所有金刚烷基衍生物的接触角显著低于100°。
对比例
为进行比较,使用如下现有技术化合物测量接触角并获得下表所示的接触角:
可以看出对比例的接触角高于100°。
根据本发明的金刚烷衍生物的接触角几乎对于全部实施例均相同,然而参考化合物对于较短的链接长度而言倾向具有较低接触角。
包含一种或多种本发明化合物的SAM具有更好的加工稳定性,原因在于其表面能更接近于大多数光致抗蚀剂配制剂的设计范围。这确保了涂覆过程中润湿与成膜的较高再现性。
制备开关器件
由合成实施例2(11-[4-(1-金刚烷基)-2,3-二氟-苯氧基]十一烷基膦酸,PA-11O-Y-Ada)制备分子层,为了对比,由11-[2,3-二氟-4-(4-戊基环己基)苯氧基]十一烷基膦酸(PA-11O-YC-5,化合物实施例19,WO2018/007337A2的第63页)制备另外的分子层,其中如下制备:
1)制备基底:起始材料为直径为6英寸的绝缘体上硅晶圆(“SOI晶圆”),其在具有525μm的厚度和[100]取向的轻度掺杂硼的硅晶圆上的厚度为200nm的氧化硅层上具有厚度为110nm且具有[100]取向的硅层且电阻率为约20Ω·cm。
上部硅层通过离子注入高度硼掺杂(掺杂浓度c~5×1019cm-3,电阻率ρ~1.4mΩ·cm)。掺杂后,将晶圆分成测量为8mm×8mm的正方形部分(“芯片”)。在每种情况下,芯片首先在丙酮中洗涤,随后在异丙醇中在超声浴中洗涤10min。
2)膦酸层的沉积
在超声浴中在丙酮和异丙醇中再次将如上新鲜制备的芯片在每种情况下洗涤5分钟,随后用水虎鱼(piranha)溶液在70℃下处理。在用去离子水漂洗后,用氧等离子体处理芯片(200W,7分钟),在硅导电轨道上产生具有羟基的二氧化硅层,其使得表面亲水化并使表面对膦酸呈反应性。
对沉积膦酸层而言,用250μM相应膦酸在四氢呋喃中的溶液浸涂芯片,然后在烘箱中在120℃下加热过夜,然后用乙醇洗涤。该方法基本上对应于文献中已知的“TBAG”方法并得到自组装单层。
根据WO2018/007337A2第72至75页所述的程序使用汞滴电极测定分子层的击穿电压。获得下列值:
PA-11O-Y-Ada:+5.38±0.68V
PA-11O-YC-5:+3.90±0.32V。
可以看出本发明的金刚烷基衍生物出乎意料地产生了具有显著更高的击穿电压的器件。
包含分子层140的切换器件100(图1)的电表征利用纳米探针(Hitachi HighTechnologies Nano-Probe N-6000SS,探针尺寸约1μm)和Agilent B1500器件分析仪在SEM控制下进行,该分子层由化合物PA-11O-Y-Ada获得并夹在硅基底110上的TiN第一电极130(厚度50nm)与具有金触点160(80nm)的Ti第二电极150(10nm)之间。器件由与上述相同硅基底开始制备。测试器件的制备按照工业上典型的标准程序。氮化钛第一电极130通过反应溅射而沉积(Ti靶材,在N2气氛中)。
具有氧化硅中间层120的硅晶圆110通过反应性溅射沉积50nm厚的TiN层而涂覆,通过臭氧/UV处理(110W/300s)而活化,随后在膦酸[PA-11O-Y-Ada(参见上文)于四氢呋喃(THF)中的1mM溶液中浸渍24h。将芯片从浸渍浴中取出,用氮气吹干并在氮气和120℃下退火60min。然后,将芯片在旋涂机上用THF漂洗,随后在氮气和120℃下再次退火5min。使用标准工艺通过溅射施加钛顶部电极150和金触点160。
器件100的电表征结果示于图2。正向扫描210以0V开始且电压增加至+3.5V;反向扫描220然后返回至0V,进一步直至-3.5V,然后返回至0V。扫描速度为300mV/s。测量所得电流且结果示于图2。器件具有有利地大存储窗。
Claims (12)
1.一种式I化合物
D1-ZD-(A1-Z1)r-B1-(Z2-A2)s-Sp-G (I)
其中
D1表示金刚烷类基团,
A1、A2在每次出现时相同或不同地表示具有4至25个环原子的芳族、杂芳族、脂环族或杂脂族环,其也可含有稠环以及其可被Y单取代或多取代,
Y在每次出现时相同或不同地表示F、Cl、CN、SCN、SF5或具有1至12个C原子的直链或支化的、在每种情况下任选氟化的烷基、烷氧基、烷基羰基、烷氧基羰基、烷基羰基氧基或烷氧基羰基氧基,
B1表示
其中这些基团可朝两个方向取向,
L1至L5相互独立地表示F、Cl、Br、I、CN、SF5、CF3或OCF3,优选Cl或F,其中L3也可以表示H,
Z1、Z2在每次出现时相同或不同地表示单键、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-CH2O-、-OCH2-、-C(O)O-、-OC(O)-、-C(O)S-、-SC(O)-、-(CH2)n1-、-(CF2)n2-、-CF2-CH2-、-CH2-CF2-、-CH=CH-、-CF=CF-、-CF=CH-、-CH=CF-、-(CH2)n3O-、-O(CH2)n4-、-C≡C-、-O-、-S-、-CH=N-、-N=CH-、-N=N-、-N=N(O)-、-N(O)=N-或-N=C-C=N-,
n1、n2、n3、n4相同或不同地为1、2、3、4、5、6、7、8、9或10,
Sp表示间隔基团或单键,
ZD具有Z1与Z2或Sp的含义之一,
G表示CH=CH2、-OH、-CH(CH2OH)2、-C(CH2OH)3、-SH、-SO2OH、-OP(O)(OH)2、-PO(OH)2、-C(OH)(PO(OH)2)2、-COOH、-B(OH)2、-Si(ORx)3或-SiCl3、-SO2ORV、-OP(O)(ORV)2、-PO(ORV)2、-C(OH)(PO(ORV)2)2、-COORV或-Si(ORV)3,
RV表示具有1至20个C原子的直链或支化的烷基,
Rx表示具有1至6个C原子的直链或支化的烷基,和
r和s相互独立地表示0、1、2或3,
其中r+s≤4,
条件是,如果Sp表示单键,则Z2不为O、S、CH2或CF2。
2.根据权利要求1的化合物,其中D1选自由金刚烷基、二金刚烷基和三金刚烷基组成的组,它们中的每一个中的一个或多个H原子可被F,或具有至多12个C原子的每种情况下任选氟化的烷基、烯基或烷氧基替代。
3.根据权利要求1或2的化合物,其中A1和A2在每次出现时相同或不同地选自以下组:
a)1,4-亚苯基,其中一个或两个CH基团可被N替代且其中,此外,一个或多个H原子可被Y替代,
b)由反式-1,4-亚环己基和1,4-亚环己烯基组成的组,其中一个或多个非相邻CH2基团可被-O-和/或-S-替代且其中,此外,一个或多个H原子可被Y替代,和
c)由以下组成的组:1,3-二氧戊环-2,4-二基、四氢呋喃-2,5-二基、环丁烷-1,3-二基、1,4-二环[2.2.2]辛烷二基、哌啶-1,5-二基和噻吩-2,5-二基,其中一个或多个H原子可被Y替代,
其中Y具有权利要求1中所给的含义。
4.根据权利要求1-3中任一项或多项的化合物,其中基团Sp表示Sp'-X',从而使基团G-Sp-表示G-Sp'-X'-,其中
Sp’表示具有1至20个,优选1至12个C原子的直链或支化的亚烷基,其任选被F、Cl、Br、I或CN单取代或多取代,且其中,此外,一个或多个非相邻CH2基团可各自相互独立地被-O-、-S-、-NH-、-NR0-、-SiR00R000-、-CO-、-COO-、-OCO-、-OCO-O-、-S-CO-、-CO-S-、-NR0-CO-O-、-O-CO-NR0-、-NR0-CO-NR0-、-CH=CH-或-C≡C-以O和/或S原子相互不直接连接的方式替代,
X’表示-O-、-S-、-CO-、-COO-、-OCO-、-O-COO-、-CO-NR00-、-NR00-CO-、-NR00-CO-NR00-、-OCH2-、-CH2O-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-CF2CH2-、-CH2CF2-、-CF2CF2-、-CH=N-、-N=CH-、-N=N-、-CH=CR00-、-CYx=CYx‘-、-C≡C-、-CH=CH-COO-、-OCO-CH=CH-或单键,
R0、R00
和R000各自相互独立地表示H或具有1至12个C原子的烷基,和
Yx和Yx‘各自相互独立地表示H、F、Cl或CN。
6.根据权利要求1-5中任一项或多项的化合物,其中G表示-P(O)(OH)2、-OP(O)(OH)2或-C(OH)(PO(OH)2)2。
7.根据权利要求1-6中任一项或多项的化合物,其中ZD表示单键、-C≡C-、-C(O)O-、-OC(O)-、-OCH2-、-CH2O-、-CH2CH2-、-CH2CH2CH2-或-CH2CH2CH2CH2-。
8.一种制备切换元件的方法,其包括至少以下步骤:
a)制备具有表面的第一电极,
b)在该第一电极的表面上沉积包含一种或多种式I化合物的分子层,
c)施加第二电极。
9.根据权利要求8的方法,其中该第一电极包括选自以下的材料:单质半导体Si、Ge、C、Sn和Se;化合物半导体GaAs、InAs、InP、GaSb、TaN、TiN、MoN、WN和GaN、CdSe和ZnS;金属Au、Ag、Cu、Al、W、Ta、Ti、Co、Mo、Pt、Ru和Mg;以及导电氧化物材料ITO、IGO、IGZO、AZO和FTO。
10.一种可通过根据权利要求8的方法获得的切换元件,其包括夹在第一电极与第二电极之间的分子层。
11.根据权利要求10的切换元件,其中该分子层为自组装单层。
12.一种忆阻器件,其包括根据权利要求10或11的切换元件。
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2020
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