CN114634732A - Two-dimensional material water-based ink and preparation method and application thereof - Google Patents
Two-dimensional material water-based ink and preparation method and application thereof Download PDFInfo
- Publication number
- CN114634732A CN114634732A CN202210275934.0A CN202210275934A CN114634732A CN 114634732 A CN114634732 A CN 114634732A CN 202210275934 A CN202210275934 A CN 202210275934A CN 114634732 A CN114634732 A CN 114634732A
- Authority
- CN
- China
- Prior art keywords
- nanosheets
- sulfide
- selenide
- diselenide
- disulfide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000002135 nanosheet Substances 0.000 claims abstract description 163
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical group S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- CXRFFSKFQFGBOT-UHFFFAOYSA-N bis(selanylidene)niobium Chemical compound [Se]=[Nb]=[Se] CXRFFSKFQFGBOT-UHFFFAOYSA-N 0.000 claims abstract description 5
- FBGGJHZVZAAUKJ-UHFFFAOYSA-N bismuth selenide Chemical compound [Se-2].[Se-2].[Se-2].[Bi+3].[Bi+3] FBGGJHZVZAAUKJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 45
- 239000013078 crystal Substances 0.000 claims description 41
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- -1 chromium sulfur phosphorus copper Chemical compound 0.000 claims description 24
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 14
- ROUIDRHELGULJS-UHFFFAOYSA-N bis(selanylidene)tungsten Chemical compound [Se]=[W]=[Se] ROUIDRHELGULJS-UHFFFAOYSA-N 0.000 claims description 13
- 150000001768 cations Chemical class 0.000 claims description 13
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- VRSMQRZDMZDXAU-UHFFFAOYSA-N bis(sulfanylidene)niobium Chemical compound S=[Nb]=S VRSMQRZDMZDXAU-UHFFFAOYSA-N 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- CUYHGAIVHCHFIA-UHFFFAOYSA-N bis(selanylidene)rhenium Chemical compound [Se]=[Re]=[Se] CUYHGAIVHCHFIA-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 11
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 11
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 11
- ALRFTTOJSPMYSY-UHFFFAOYSA-N tin disulfide Chemical compound S=[Sn]=S ALRFTTOJSPMYSY-UHFFFAOYSA-N 0.000 claims description 11
- USWJSZNKYVUTIE-UHFFFAOYSA-N bis(sulfanylidene)rhenium Chemical compound S=[Re]=S USWJSZNKYVUTIE-UHFFFAOYSA-N 0.000 claims description 10
- YQIVQBMEBZGFBY-UHFFFAOYSA-M tetraheptylazanium;bromide Chemical compound [Br-].CCCCCCC[N+](CCCCCCC)(CCCCCCC)CCCCCCC YQIVQBMEBZGFBY-UHFFFAOYSA-M 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- MHWZQNGIEIYAQJ-UHFFFAOYSA-N molybdenum diselenide Chemical compound [Se]=[Mo]=[Se] MHWZQNGIEIYAQJ-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- JAAVTMIIEARTKI-UHFFFAOYSA-N [S--].[S--].[Ta+4] Chemical compound [S--].[S--].[Ta+4] JAAVTMIIEARTKI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 claims description 5
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 claims description 5
- QIHHYQWNYKOHEV-UHFFFAOYSA-N 4-tert-butyl-3-nitrobenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1[N+]([O-])=O QIHHYQWNYKOHEV-UHFFFAOYSA-N 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- CHQKVCSVJIMMRE-UHFFFAOYSA-N [Pb]=S.[Sn] Chemical compound [Pb]=S.[Sn] CHQKVCSVJIMMRE-UHFFFAOYSA-N 0.000 claims description 4
- LNMGXZOOXVAITI-UHFFFAOYSA-N bis(selanylidene)hafnium Chemical compound [Se]=[Hf]=[Se] LNMGXZOOXVAITI-UHFFFAOYSA-N 0.000 claims description 4
- IYJABVNLJXJBTP-UHFFFAOYSA-N bis(selanylidene)tantalum Chemical compound [Se]=[Ta]=[Se] IYJABVNLJXJBTP-UHFFFAOYSA-N 0.000 claims description 4
- KBPGBEFNGHFRQN-UHFFFAOYSA-N bis(selanylidene)tin Chemical compound [Se]=[Sn]=[Se] KBPGBEFNGHFRQN-UHFFFAOYSA-N 0.000 claims description 4
- WCQOLGZNMNEYDX-UHFFFAOYSA-N bis(selanylidene)vanadium Chemical compound [Se]=[V]=[Se] WCQOLGZNMNEYDX-UHFFFAOYSA-N 0.000 claims description 4
- HKXPEFKCXYKSFA-UHFFFAOYSA-N bis(selanylidene)zirconium Chemical compound [Se]=[Zr]=[Se] HKXPEFKCXYKSFA-UHFFFAOYSA-N 0.000 claims description 4
- HITXEXPSQXNMAN-UHFFFAOYSA-N bis(tellanylidene)molybdenum Chemical compound [Te]=[Mo]=[Te] HITXEXPSQXNMAN-UHFFFAOYSA-N 0.000 claims description 4
- ZNDWMUJQNKFBMN-UHFFFAOYSA-N bis(tellanylidene)rhenium Chemical compound [Te]=[Re]=[Te] ZNDWMUJQNKFBMN-UHFFFAOYSA-N 0.000 claims description 4
- NNLOHLDVJGPUFR-UHFFFAOYSA-L calcium;3,4,5,6-tetrahydroxy-2-oxohexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(=O)C([O-])=O.OCC(O)C(O)C(O)C(=O)C([O-])=O NNLOHLDVJGPUFR-UHFFFAOYSA-L 0.000 claims description 4
- PPUZYFWVBLIDMP-UHFFFAOYSA-K chromium(3+);triiodide Chemical compound I[Cr](I)I PPUZYFWVBLIDMP-UHFFFAOYSA-K 0.000 claims description 4
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 4
- UIPVMGDJUWUZEI-UHFFFAOYSA-N copper;selanylideneindium Chemical compound [Cu].[In]=[Se] UIPVMGDJUWUZEI-UHFFFAOYSA-N 0.000 claims description 4
- ZZEMEJKDTZOXOI-UHFFFAOYSA-N digallium;selenium(2-) Chemical compound [Ga+3].[Ga+3].[Se-2].[Se-2].[Se-2] ZZEMEJKDTZOXOI-UHFFFAOYSA-N 0.000 claims description 4
- XIMIGUBYDJDCKI-UHFFFAOYSA-N diselenium Chemical compound [Se]=[Se] XIMIGUBYDJDCKI-UHFFFAOYSA-N 0.000 claims description 4
- JPIIVHIVGGOMMV-UHFFFAOYSA-N ditellurium Chemical compound [Te]=[Te] JPIIVHIVGGOMMV-UHFFFAOYSA-N 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- NRJVMVHUISHHQB-UHFFFAOYSA-N hafnium(4+);disulfide Chemical compound [S-2].[S-2].[Hf+4] NRJVMVHUISHHQB-UHFFFAOYSA-N 0.000 claims description 4
- AKUCEXGLFUSJCD-UHFFFAOYSA-N indium(3+);selenium(2-) Chemical compound [Se-2].[Se-2].[Se-2].[In+3].[In+3] AKUCEXGLFUSJCD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- MUSFRELEIXGPKU-UHFFFAOYSA-N selanylidenepalladium Chemical compound [Pd]=[Se] MUSFRELEIXGPKU-UHFFFAOYSA-N 0.000 claims description 4
- LYZMBUYUNBCSMW-UHFFFAOYSA-N selenium(2-);tin(2+) Chemical compound [Se-2].[Sn+2] LYZMBUYUNBCSMW-UHFFFAOYSA-N 0.000 claims description 4
- HQZPMWBCDLCGCL-UHFFFAOYSA-N tantalum telluride Chemical compound [Te]=[Ta]=[Te] HQZPMWBCDLCGCL-UHFFFAOYSA-N 0.000 claims description 4
- DZXKSFDSPBRJPS-UHFFFAOYSA-N tin(2+);sulfide Chemical compound [S-2].[Sn+2] DZXKSFDSPBRJPS-UHFFFAOYSA-N 0.000 claims description 4
- SWFBFRDZBFXEHJ-UHFFFAOYSA-N titanium diselenide Chemical compound [Se]=[Ti]=[Se] SWFBFRDZBFXEHJ-UHFFFAOYSA-N 0.000 claims description 4
- XWPGCGMKBKONAU-UHFFFAOYSA-N zirconium(4+);disulfide Chemical compound [S-2].[S-2].[Zr+4] XWPGCGMKBKONAU-UHFFFAOYSA-N 0.000 claims description 4
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 3
- UNQZZHKBDVCPHA-UHFFFAOYSA-N [Mo].[W].[Se] Chemical compound [Mo].[W].[Se] UNQZZHKBDVCPHA-UHFFFAOYSA-N 0.000 claims description 3
- HDJLCPMPTBFPCJ-UHFFFAOYSA-N [Mo].[W]=S Chemical compound [Mo].[W]=S HDJLCPMPTBFPCJ-UHFFFAOYSA-N 0.000 claims description 3
- WALCGGIJOOWJIN-UHFFFAOYSA-N iron(ii) selenide Chemical compound [Se]=[Fe] WALCGGIJOOWJIN-UHFFFAOYSA-N 0.000 claims description 3
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 claims description 3
- RINGIGAJUKLHET-UHFFFAOYSA-N selanylidene(sulfanylidene)molybdenum Chemical compound S=[Mo]=[Se] RINGIGAJUKLHET-UHFFFAOYSA-N 0.000 claims description 3
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 claims description 3
- WFGOJOJMWHVMAP-UHFFFAOYSA-N tungsten(iv) telluride Chemical compound [Te]=[W]=[Te] WFGOJOJMWHVMAP-UHFFFAOYSA-N 0.000 claims description 3
- SYYDNLBOFQOSGT-UHFFFAOYSA-N [Bi]=O.[Se] Chemical compound [Bi]=O.[Se] SYYDNLBOFQOSGT-UHFFFAOYSA-N 0.000 claims description 2
- CEYNXXRGMKQAGT-UHFFFAOYSA-N chromium sulfanylidenecopper Chemical compound [Cu]=S.[Cr] CEYNXXRGMKQAGT-UHFFFAOYSA-N 0.000 claims description 2
- LCUOIYYHNRBAFS-UHFFFAOYSA-N copper;sulfanylideneindium Chemical compound [Cu].[In]=S LCUOIYYHNRBAFS-UHFFFAOYSA-N 0.000 claims description 2
- UMUKXUYHMLVFLM-UHFFFAOYSA-N manganese(ii) selenide Chemical compound [Mn+2].[Se-2] UMUKXUYHMLVFLM-UHFFFAOYSA-N 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims 4
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 claims 2
- VMJRMGHWUWFWOB-UHFFFAOYSA-N nickel tantalum Chemical compound [Ni].[Ta] VMJRMGHWUWFWOB-UHFFFAOYSA-N 0.000 claims 2
- SDDGNMXIOGQCCH-UHFFFAOYSA-N 3-fluoro-n,n-dimethylaniline Chemical compound CN(C)C1=CC=CC(F)=C1 SDDGNMXIOGQCCH-UHFFFAOYSA-N 0.000 claims 1
- MKKCJTYKJLHFJO-UHFFFAOYSA-N [Bi].S=O Chemical compound [Bi].S=O MKKCJTYKJLHFJO-UHFFFAOYSA-N 0.000 claims 1
- YBXVYDUWVUPIDL-UHFFFAOYSA-N [Cu]=S.[In]=S Chemical compound [Cu]=S.[In]=S YBXVYDUWVUPIDL-UHFFFAOYSA-N 0.000 claims 1
- WADNUIHBLWBJQY-UHFFFAOYSA-N chromium germanium Chemical compound [Cr].[Ge] WADNUIHBLWBJQY-UHFFFAOYSA-N 0.000 claims 1
- HQASLXJEKYYFNY-UHFFFAOYSA-N selenium(2-);titanium(4+) Chemical compound [Ti+4].[Se-2].[Se-2] HQASLXJEKYYFNY-UHFFFAOYSA-N 0.000 claims 1
- 239000012046 mixed solvent Substances 0.000 abstract description 22
- 238000007639 printing Methods 0.000 abstract description 13
- 238000001035 drying Methods 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 238000009835 boiling Methods 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 32
- 239000004065 semiconductor Substances 0.000 description 22
- 230000002687 intercalation Effects 0.000 description 11
- 238000009830 intercalation Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 238000011161 development Methods 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- NZIHMSYSZRFUQJ-UHFFFAOYSA-N 6-chloro-1h-benzimidazole-2-carboxylic acid Chemical compound C1=C(Cl)C=C2NC(C(=O)O)=NC2=C1 NZIHMSYSZRFUQJ-UHFFFAOYSA-N 0.000 description 2
- 229920000832 Cutin Polymers 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000002508 contact lithography Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- SCCCLDWUZODEKG-UHFFFAOYSA-N germanide Chemical compound [GeH3-] SCCCLDWUZODEKG-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007647 flexography Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000007648 laser printing Methods 0.000 description 1
- 238000001459 lithography Methods 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
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- HVFOPASORMIBOE-UHFFFAOYSA-N tellanylidenechromium Chemical compound [Te]=[Cr] HVFOPASORMIBOE-UHFFFAOYSA-N 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses two-dimensional material water-based ink and a preparation method and application thereof. The two-dimensional material water-based ink prepared by the invention comprises an ink active component and a solvent; the ink active component is a molybdenum disulfide nanosheet, a black phosphorus nanosheet, a niobium diselenide nanosheet or a bismuth selenide nanosheet and other two-dimensional material nanosheets; the solvent is water or an aqueous solution added with an organic solvent; the mass fraction of the ink active component in the ink is 0.01-20%; the thickness of the two-dimensional material nanosheet is less than 100 nm, and the transverse dimension of the nanosheet is greater than 5 nm. According to the invention, different solvents are used, the boiling points are different, the volatilization rates are different, and the two-dimensional nano material has good dispersibility in the mixed solvent, so that marangoni flow is formed in the droplet drying process, thereby inhibiting the occurrence of coffee rings and facilitating the printing. Compared with the prior art, the two-dimensional material water-based ink prepared by the invention has the characteristics of environmental protection, simple preparation process and low post-treatment temperature; may be used in an integrated circuit.
Description
Technical Field
The invention belongs to the technical field of semiconductor printing materials, and particularly relates to two-dimensional material water-based ink and a preparation method and application thereof.
Background
In the future, electronic devices will be developed towards flexibility, intelligence and functionality. As electronic products and devices develop in the directions of portability, flexibility, bendability, and the like, flexible electronic devices attract more and more people. Flexible electronic devices have a wide range of applications, such as flexible touch screens, electronic paper, sensors, radio frequency identification tags, photovoltaic cells, solar cells, conductive traces, and the like. At present, it is most common to combine a substrate carrying a large number of field effect transistors with a product by a transfer method or to directly grow the field effect transistors on a target substrate through a flow of multiple coating, curing and lithography. However, the method has complex steps and high cost, and is not suitable for large-scale popularization and application of flexible electronic devices. New printing techniques can better address this problem. The novel printing technology is used for manufacturing electronic devices and circuits by means of the printing technology, is simple and convenient in process and low in cost, can reduce waste of raw materials, is suitable for different substrates, and has the advantages of making the technology stand out in flexible electronic manufacturing. The printed electronic technology includes a series of modes such as gravure printing, flexography printing, inkjet printing, contact printing, silk screen printing, laser printing and the like. Among them, the contact printing technology has obvious advantages in the preparation of large-area flexible electronic devices, and is applied to printing a series of different electronic components, such as transistors, photovoltaic devices, organic light emitting diodes, display screens and the like, because of its simple process, wide application range and high printing precision.
Ink preparation and performance play a crucial role for new printing technologies. Conductive inks have been developed relatively mature, as opposed to semiconductor inks, which have not received sufficient attention. The semiconductor ink is a semiconductor composite material composed of a semiconductor material and a mixed solvent. In the semiconductor ink, numerous semiconductor particles are uniformly dispersed in a solvent and are in an insulating state, and after drying, the solvent is volatilized, so that a printed product has semiconductor properties. With the rapid development of nanotechnology and the increasing maturity of printing technology, it is important to develop a semiconductor ink with stable and excellent performance in order to prepare multifunctional circuits more conveniently and rapidly.
Two-dimensional material nanosheets have attracted considerable attention in recent years in the field of semiconductor devices as a novel semiconductor material with a two-dimensional structure. With the rapid development of science and technology, the number of transistors on a chip always meets the development law of moore's law in the last decades, and every 18-24 months, the number of components which can be accommodated on an integrated circuit is doubled on the premise of keeping the price unchanged, but as the processing precision of the chip reaches below 10 nm, the chip gradually approaches the physical limit of the traditional silicon-based semiconductor device, and the processing difficulty is increased more and more. In order to further reduce the device size, the development of moore's law is continued, and it is a feasible approach to explore a new semiconductor material to replace the traditional silicon-based semiconductor material. Recently, the application of two-dimensional nano-micro chips represented by molybdenum disulfide in semiconductor devices is receiving more and more attention, and molybdenum disulfide, as a typical transition metal sulfide, has excellent semiconductor properties and excellent short channel effect resistance, and has attracted great interest to researchers in the field of novel semiconductors. Research shows that molybdenum disulfide has extremely strong potential in the field of semiconductor device manufacturing. At present, the main preparation method of the two-dimensional material semiconductor device is to prepare a two-dimensional material nanosheet by a CVD or mechanical transfer method and then evaporate an electrode through a mask plate to obtain the two-dimensional material semiconductor device. The development of semiconductor devices by printing techniques is limited because the research on semiconductor inks is still relatively deficient. Therefore, it is necessary to develop a new formulation and preparation method to meet the requirements of printed electronic devices.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide the two-dimensional material water-based ink which is green and environment-friendly and does not contain a surfactant.
In order to achieve the above object, the present invention provides a two-dimensional aqueous ink, which comprises an ink active component and a solvent; the ink active component is a two-dimensional material nanosheet; the solvent is water or an aqueous solution added with an organic solvent.
According to the invention, the organic solvent is selected from one or more of ethanol, isopropanol, butanol, ethylene glycol, acetonitrile and N, N-dimethylformamide.
According to the invention, the mass fraction of the two-dimensional material nanosheet in the ink is 0.01-20%.
According to the invention, the two-dimensional material nanosheets are molybdenum disulfide nanosheets, black phosphorus nanosheets, bismuth selenide oxide nanosheets, bismuth sulfide nanosheets, bismuth selenide nanosheets, bismuth telluride nanosheets, chromium telluride germanide nanosheets, chromium triiodide nanosheets, chromium sulfur phosphate copper nanosheets, indium selenide copper nanosheets, indium sulfur phosphate copper nanosheets, copper sulfide nanosheets, iron sulfide phosphide nanosheets, iron selenide phosphide nanosheets, gallium selenide nanosheets, germanium selenide nanosheets, hafnium disulfide nanosheets, hafnium diselenide nanosheets, hafnium ditelluride nanosheets, indium selenide nanosheets, manganese sulfide nanosheets, manganese selenide nanosheets, molybdenum selenide sulfide nanosheets, molybdenum ditelluride nanosheets, tungsten sulfide nanosheets, tungsten molybdenum selenide nanosheets, niobium disulfide nanosheets, niobium diselenide nanosheets, nickel phosphide nanosheets, tin lead sulfide nanosheets, tin palladium selenide nanosheets, palladium diselenide nanosheets, One or more of rhenium disulfide nanosheets, rhenium diselenide nanosheets, rhenium telluride nanosheets, stannous sulfide nanosheets, tin disulfide nanosheets, stannous selenide nanosheets, tin diselenide nanosheets, nickel sulfide tantalum nanosheets, nickel selenide tantalum nanosheets, nickel telluride tantalum nanosheets, tantalum disulfide nanosheets, tantalum diselenide nanosheets, tantalum ditelluride nanosheets, titanium disulfide nanosheets, titanium diselenide nanosheets, vanadium diselenide nanosheets, tungsten disulfide nanosheets, tungsten diselenide nanosheets, tantalum sulfide tungsten nanosheets, tungsten ditelluride nanosheets, zirconium disulfide nanosheets, zirconium trisulfide nanosheets, zirconium diselenide nanosheets and zirconium triselenide nanosheets.
According to the invention, the two-dimensional material nanosheets are lamellar in morphology.
According to the invention, the thickness of the two-dimensional material nanosheet is less than 100 nm, and the lateral dimension is greater than 5 nm.
According to the invention, the two-dimensional material nanosheet is prepared by the following method:
1) fixing a two-dimensional material to a cathode of an electrolytic cell in a two-electrode electrochemical system; the graphite rod is used as an anode, and the distance between the two-dimensional material layers is increased and the volume is expanded through electrolysis;
2) and (3) obtaining the two-dimensional material nanosheet through ultrasonic stripping and centrifugal screening by a centrifugal machine in a gradient manner.
The two-dimensional material is molybdenum disulfide, black phosphorus, bismuth oxysele, bismuth sulfide, bismuth selenide, bismuth telluride, chromium germanide telluride, chromium triiodide, chromium copper sulfide, indium copper selenide, indium copper sulfide, iron sulfide phosphide, iron selenide phosphide, gallium selenide, germanium selenide, hafnium disulfide, hafnium diselenide, hafnium ditelluride, indium selenide, manganese sulfide phosphide, manganese phosphide, molybdenum selenide sulfide, molybdenum ditelluride, tungsten molybdenum sulfide, tungsten molybdenum selenide, niobium disulfide, niobium diselenide, nickel phosphide sulfide, tin lead sulfide, tin palladium selenide, palladium diselenide, rhenium disulfide, rhenium diselenide, rhenium telluride, stannous sulfide, tin disulfide, stannous selenide, tin diselenide, nickel tantalum sulfide, nickel tantalum selenide, nickel telluride, tantalum disulfide, tantalum diselenide, tantalum telluride, titanium disulfide, titanium diselenide, vanadium diselenide, tungsten disulfide, tungsten sulfide, tungsten diselenide, tungsten diselenide, tungsten diselenide, One or more of crystals of zirconium disulfide, zirconium trisulfide, zirconium diselenide and zirconium triselenide.
The electrolyte of the bipolar electrochemical system in the step 1) is selected from one or more of ethanol, propanol, butanol, acetonitrile, propionitrile and carbon tetrachloride.
One or more macromolecular cations can also be added into the electrolyte of the double-electrode electrochemical system in the step 1).
The macromolecular cation is selected from tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide and tetraheptylammonium bromide.
The voltage of the electrolysis in the step 1) is-0.01V-100V, and the time is 1 min-72 h.
The rotating speed of the centrifugal machine in the step 2) is 1000 rpm-10000 rpm.
The invention also aims to provide a preparation method of the two-dimensional material water-based ink, which comprises the following steps:
s1) dispersing the two-dimensional material nanosheets in a solvent, and obtaining a mixed solution after ultrasonic dispersion;
s2) centrifuging and screening the mixed solution by a centrifuge at 1000-5000 rpm to obtain the two-dimensional material water-based ink.
It is a further object of the present invention to provide the use of aqueous inks of two-dimensional materials in integrated circuits.
Compared with the prior art, the invention has the following beneficial effects:
1) the two-dimensional material water-based ink has a good printing effect, can be prepared at normal temperature and normal pressure, saves energy, has simple equipment, wide raw material sources and low cost, can be prepared in large quantities, is completely nontoxic and harmless, and can be widely applied to the preparation of other two-dimensional material inks; the method is suitable for industrial production and has practical application value in the field of two-dimensional materials;
2) according to the invention, different solvents are used, the boiling points are different, the volatilization rates are different, and the two-dimensional nano material has good dispersibility in the mixed solvent, so that marangoni flow is formed in the droplet drying process, thereby inhibiting the occurrence of coffee rings and facilitating the printing.
Drawings
FIG. 1 is a TEM spectrogram of a molybdenum disulfide nanosheet prepared in example 1 of the present invention;
FIG. 2 is a photograph of a molybdenum disulfide ink prepared in example 1 of the present invention;
figure 3 is an optical microscope photograph of a molybdenum disulfide film printed with molybdenum disulfide ink prepared in example 1 of the present invention.
Detailed Description
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
Example 1
A large block of molybdenum disulfide crystals was fixed to the cathode of a two-electrode electrolytic cell, using a graphite rod as the anode. Acetonitrile solution of tetramethylammonium bromide at a concentration of 5 mg/ml was used as an electrolyte. The applied voltage was set to 5V and the reaction time lasted 60 min. In the intercalation reaction process, cations of tetramethyl ammonium bromide enter gaps of molybdenum disulfide crystals under the driving of negative potential, so that the spacing of the molybdenum disulfide crystal layers is enlarged, and the volume is expanded violently. The expanded molybdenum disulfide crystals were then washed several times with anhydrous ethanol to remove residual tetramethylammonium bromide salt. Ultra-thin molybdenum disulfide nanosheets (thickness less than 100 nm and transverse dimension greater than 5 nm) can be obtained by ultrasonic exfoliating and centrifuging. Mixing the components in a volume ratio of 7: 1: 1: 0.5: 0.5 g of water, ethanol, isopropanol, ethylene glycol and butanol was prepared as a mixed solvent, and 5mg of molybdenum disulfide nanosheets was dispersed in 4.995g of the mixed solvent. And then centrifuging and screening the mixed solution by a centrifuge at 1000rpm to obtain the molybdenum disulfide aqueous ink. The result shows that the ultrathin molybdenum disulfide nanosheet can be obtained after intercalation and ultrasonic treatment; and the molybdenum disulfide nanosheet ink has good dispersibility and no precipitate.
Example 2
A large block of tungsten disulfide crystals was fixed at the cathode of a two-electrode electrolytic cell, using a graphite rod as the anode. An ethanol solution having a tetraethylammonium bromide concentration of 10 mg/ml was used as an electrolyte. The applied voltage was set to 10V and the reaction time lasted 60 min. In the intercalation reaction process, cations of tetraethyl ammonium bromide enter gaps of tungsten disulfide crystals under the driving of negative potential, so that the spacing of tungsten disulfide crystal layers is increased, and the volume is expanded violently. The expanded tungsten disulfide crystals were then rinsed several times with anhydrous ethanol to remove residual tetraethylammonium bromide salt. Ultra-thin tungsten disulfide nanosheets (with the thickness less than 100 nm and the transverse dimension greater than 5 nm) can be obtained by ultrasonic exfoliating and centrifuging. Mixing the components in a volume ratio of 7: 1.5: 1.5, preparing a mixed solvent from water, ethanol and isopropanol, and dispersing 10 mg of tungsten disulfide nanosheets in 4.990g of the mixed solvent to obtain the tungsten disulfide aqueous ink.
Example 3
A large block of molybdenum diselenide crystals was fixed at the cathode of a two-electrode electrolytic cell, using a graphite rod as the anode. An acetonitrile solution having a tetrapropylammonium bromide salt concentration of 5 mg/ml was used as an electrolyte. The applied voltage was set at 20V and the reaction time lasted 60 min. In the intercalation reaction process, cations of tetrapropylammonium bromide enter gaps of the molybdenum diselenide crystals under the driving of negative potential, so that the spacing of the molybdenum diselenide crystal layers is enlarged, and the volume is expanded violently. The expanded molybdenum diselenide crystals were then washed several times with anhydrous ethanol to remove residual tetrapropyl ammonium bromide salt. Ultra-thin molybdenum diselenide nanosheets (thickness less than 100 nm and transverse dimension greater than 5 nm) can be obtained by ultrasonic exfoliating and centrifuging. Mixing the components in a volume ratio of 3: 7, preparing water and ethylene glycol into a mixed solvent, and dispersing 15 mg of molybdenum diselenide nanosheets into 4.985g of the mixed solvent to obtain the molybdenum diselenide aqueous ink.
Example 4
A large block of tungsten diselenide crystal is fixed at the cathode of a double-electrode electrolytic cell, and a graphite rod is used as the anode. An ethanol solution having a tetrabutylammonium bromide concentration of 5 mg/ml was used as an electrolyte. The applied voltage was set at 25V and the reaction time lasted 60 min. In the intercalation reaction process, cations of tetrabutylammonium bromide enter gaps of tungsten diselenide crystals under the driving of negative potential, so that the spacing of the tungsten diselenide crystal layers is enlarged, and the volume is expanded violently. The expanded tungsten diselenide crystals were then washed several times with anhydrous ethanol to remove residual tetrabutylammonium bromide salt. Ultra-thin tungsten diselenide nanosheets (with the thickness less than 100 nm and the transverse dimension greater than 5 nm) can be obtained through ultrasonic cutin removal and centrifugal treatment. Mixing the components in a volume ratio of 6: 2: 1: 0.5: 0.5 of water, ethanol, isopropanol, ethylene glycol and butanol are prepared into a mixed solvent, and 20 mg of tungsten diselenide nanosheet is dispersed in 4.980g of the mixed solvent, so that the tungsten diselenide aqueous ink can be obtained.
Example 5
A large block of niobium disulfide crystals was fixed at the cathode of a bipolar cell using a graphite rod as the anode. A carbon tetrachloride solution having a tetraheptyl ammonium bromide concentration of 5 mg/ml was used as an electrolyte. The applied voltage was set at 30V and the reaction time lasted 60 min. In the intercalation reaction process, cations of tetraheptyl ammonium bromide enter gaps of niobium disulfide crystals under the driving of negative potential, so that the spacing of niobium disulfide crystal layers is increased, and the volume is expanded violently. The expanded niobium disulfide crystals were then washed several times with anhydrous ethanol to remove residual tetraheptyl ammonium bromide salt. Ultra-thin niobium disulfide nanosheets (thickness less than 100 nm and transverse dimension greater than 5 nm) can be obtained by ultrasonic exfoliating and centrifuging. Mixing the components in a volume ratio of 7.5: 2.5, water and ethanol are prepared into a mixed solvent, and 50 mg of niobium disulfide nanosheet is dispersed in 4.950g of the mixed solvent, so that the niobium disulfide aqueous ink can be obtained.
Example 6
A large block of rhenium disulfide crystals was fixed at the cathode of a two-electrode electrolytic cell, using a graphite rod as the anode. An acetonitrile solution having a tetramethylammonium bromide concentration of 2.5 mg/ml and a tetraethylammonium bromide concentration of 2.5 mg/ml was used as an electrolyte. The applied voltage was set at 35V and the reaction time lasted 60 min. During the intercalation reaction, cations of tetramethyl ammonium bromide salt and tetraethyl ammonium bromide enter gaps of rhenium disulfide crystals under the driving of negative potential, so that the spacing between rhenium disulfide crystals is enlarged, and the volume is expanded violently. The expanded rhenium disulfide crystals were then washed several times with anhydrous ethanol to remove residual tetramethylammonium bromide and tetraethylammonium bromide salts. Ultra-thin rhenium disulfide nanosheets (the thickness is less than 100 nm, and the transverse dimension is more than 5 nm) can be obtained through ultrasonic exfoliating and centrifugal treatment. Mixing the components in a volume ratio of 2: 7: 1, preparing a mixed solvent from water, glycol and butanol, and dispersing 70 mg of niobium disulfide nanosheets in 4.930g of the mixed solvent to obtain the rhenium disulfide aqueous ink.
Example 7
A large block of tin disulfide crystals was fixed at the cathode of a two-electrode electrolytic cell, using a graphite rod as the anode. Acetonitrile solution having a tetramethylammonium bromide concentration of 2.5 mg/ml and a tetrapropylammonium bromide concentration of 2.5 mg/ml was used as the electrolyte. The applied voltage was set at 40V and the reaction time lasted 60 min. In the intercalation reaction process, cations of tetramethyl ammonium bromide and tetrapropyl ammonium bromide enter gaps of tin disulfide crystals under the driving of negative potential, so that the spacing between tin disulfide crystal layers is enlarged, and the volume is expanded violently. The expanded tin disulfide crystals were then washed several times with anhydrous ethanol to remove residual tetramethylammonium bromide and tetrapropylammonium bromide. Ultra-thin tin disulfide nanosheets (thickness less than 100 nm, transverse dimension greater than 5 nm) can be obtained by ultrasonic exfoliating and centrifuging. Mixing the components in a volume ratio of 8: 1: 1, and dispersing 80 mg of tin disulfide nanosheets in 4.920g of the mixed solvent to obtain the tin disulfide aqueous ink.
Example 8
A bulk rhenium diselenide crystal was fixed at the cathode of a two-electrode electrolytic cell, using a graphite rod as the anode. Acetonitrile solution having a tetramethylammonium bromide concentration of 2.5 mg/ml and a tetrabutylammonium bromide concentration of 2.5 mg/ml was used as an electrolyte. The applied voltage was set at 45V and the reaction time lasted 60 min. During the intercalation reaction, cations of tetramethyl ammonium bromide and tetrabutyl ammonium bromide enter gaps of rhenium diselenide crystals under the driving of negative potential, so that the spacing of the rhenium diselenide crystal layers is enlarged, and the volume is expanded violently. The expanded rhenium diselenide crystals were then washed several times with anhydrous ethanol to remove residual tetramethylammonium bromide and tetrabutylammonium bromide salts. Ultra-thin rhenium diselenide nanosheets (with the thickness less than 100 nm and the transverse dimension greater than 5 nm) can be obtained by ultrasonic cutin removal and centrifugal treatment. Mixing the components in a volume ratio of 2: 0.5: 7: 0.5 of water, isopropanol, glycol and butanol are prepared into a mixed solvent, and 90 mg of rhenium diselenide nanosheet is dispersed in 4.910g of the mixed solvent, so that the rhenium diselenide aqueous ink can be obtained.
Example 9
The large black phosphorus crystal is fixed on the cathode of the double-electrode electrolytic cell, and the graphite rod is used as the anode. An acetonitrile solution having a tetramethylammonium bromide salt concentration of 2.5 mg/ml and a tetraheptylammonium bromide salt concentration of 2.5 mg/ml was used as an electrolyte. The applied voltage was set at 50V and the reaction time lasted 60 min. In the intercalation reaction process, tetramethylammonium bromide and tetraheptylammonium bromide cations enter gaps of black phosphorus crystals under the driving of negative potential, so that the spacing between black phosphorus crystal layers is enlarged, and the volume is expanded violently. The swollen black phosphorus crystals were then washed several times with anhydrous ethanol to remove residual tetramethylammonium bromide and tetraheptylammonium bromide. Ultra-thin black phosphorus nanosheets (with the thickness less than 100 nm and the transverse dimension more than 5 nm) can be obtained by ultrasonic exfoliating and centrifuging. Mixing the components in a volume ratio of 2: 1: 1: 6, preparing a mixed solvent from water, ethanol, isopropanol and glycol, and dispersing 100 mg of black phosphorus nanosheets in 4.900g of the mixed solvent to obtain the black phosphorus aqueous ink.
Example 10
A large piece of manganese sulfide phosphide two-dimensional material crystal is fixed on the cathode of a double-electrode electrolytic cell, and a graphite rod is used as the anode. An acetonitrile solution having a tetramethylammonium bromide concentration of 1mg/ml, a tetraethylammonium bromide concentration of 1mg/ml, a tetrapropylammonium bromide concentration of 1mg/ml, a tetrabutylammonium bromide concentration of 1mg/ml, and a tetraheptylammonium bromide concentration of 1mg/ml was used as an electrolyte. The applied voltage was set to 5V and the reaction time lasted 60 min. In the intercalation reaction process, cations of tetramethyl ammonium bromide, tetraethyl ammonium bromide, tetrapropyl ammonium bromide, tetrabutyl ammonium bromide and tetraheptyl ammonium bromide enter gaps of the manganese phosphide two-dimensional material crystals under the driving of negative potential, so that the space between the crystal layers of the manganese phosphide two-dimensional material is increased, and the volume is expanded violently. The expanded manganese phosphosulfide two-dimensional material crystal is then washed several times with absolute ethyl alcohol to remove residual tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide and tetraheptylammonium bromide. Ultra-thin manganese sulfide phosphide two-dimensional material nanosheets (thickness less than 100 nm and transverse dimension greater than 5 nm) can be obtained by ultrasonic exfoliating and centrifugal treatment. Mixing the components in a volume ratio of 7: 2: 0.5: 0.5 of water, ethanol, isopropanol and ethylene glycol are prepared into a mixed solvent, and 100 mg of the two-dimensional material nanosheet is dispersed in 4.900g of the mixed solvent, so that the manganese phosphide sulfide two-dimensional material aqueous ink can be obtained.
The above description is only for the purpose of illustrating the preferred embodiments of the present application and is not to be construed as limiting the present application, and it is intended that various changes and modifications can be made by those skilled in the art without departing from the spirit and scope of the present application.
Claims (10)
1. The two-dimensional material water-based ink is characterized by comprising an ink active component and a solvent; the ink active component is a two-dimensional material nanosheet; the solvent is water or water solution added with organic solvent.
2. The two-dimensional aqueous ink according to claim 1, wherein the organic solvent is one or more selected from ethanol, isopropanol, butanol, ethylene glycol, acetonitrile and N, N-dimethylformamide.
3. The two-dimensional material aqueous ink according to claim 1, wherein the mass fraction of the two-dimensional material nanosheets in the ink is 0.01% to 20%.
4. The two-dimensional aqueous ink as claimed in claim 1, wherein the two-dimensional material nanosheets are molybdenum disulfide nanosheets, black phosphorus nanosheets, bismuth oxysulfide nanosheets, bismuth sulfide nanosheets, bismuth selenide nanosheets, bismuth telluride nanosheets, chromium triiodide nanosheets, chromium sulfur phosphorus copper nanosheets, indium copper selenide nanosheets, indium sulfur copper sulfide nanosheets, iron sulfide phosphide nanosheets, iron selenide phosphide nanosheets, gallium selenide nanosheets, germanium selenide nanosheets, hafnium disulfide nanosheets, hafnium diselenide nanosheets, hafnium ditelluride nanosheets, indium selenide nanosheets, manganese sulfide phosphide nanosheets, manganese selenide nanosheets, molybdenum ditelluride nanosheets, tungsten molybdenum sulfide nanosheets, tungsten molybdenum selenide nanosheets, niobium disulfide nanosheets, niobium diselenide nanosheets, nickel sulfide nanosheets, molybdenum selenide nanosheets, nickel sulfide nanosheets, and copper sulfide nanosheets, nickel sulfide nanosheets, and copper sulfide nanosheets, nickel sulfide nanosheets, and copper sulfide nanosheets, One or more of tin lead sulfide nanosheets, tin palladium selenide nanosheets, palladium diselenide nanosheets, rhenium disulfide nanosheets, rhenium diselenide nanosheets, rhenium telluride nanosheets, stannous sulfide nanosheets, tin disulfide nanosheets, stannous selenide nanosheets, tin diselenide nanosheets, nickel tantalum sulfide nanosheets, nickel tantalum selenide nanosheets, nickel tantalum telluride nanosheets, tantalum disulfide nanosheets, tantalum diselenide nanosheets, tantalum ditelluride nanosheets, titanium disulfide nanosheets, titanium diselenide nanosheets, vanadium diselenide nanosheets, tungsten disulfide nanosheets, tungsten diselenide nanosheets, tantalum tungsten sulfide nanosheets, tungsten ditelluride nanosheets, zirconium disulfide nanosheets, zirconium trisulfide nanosheets, zirconium diselenide nanosheets, and zirconium triselenide nanosheets.
5. The two-dimensional material aqueous ink according to claim 1, wherein the two-dimensional material nanosheets are lamellar in morphology, less than 100 nm in thickness and greater than 5 nm in lateral dimension.
6. The two-dimensional material aqueous ink according to claim 1, wherein the two-dimensional material nanosheet is prepared by a method comprising:
1) fixing a two-dimensional material to a cathode of an electrolytic cell in a two-electrode electrochemical system; the graphite rod is used as an anode, and the distance between the two-dimensional material layers is increased and the volume is expanded through electrolysis;
2) and (3) obtaining the two-dimensional material nanosheet through ultrasonic stripping and centrifugal screening by a centrifugal machine in a gradient manner.
7. The two-dimensional aqueous ink as claimed in claim 6, wherein the two-dimensional material in step 1) is selected from the group consisting of molybdenum disulfide, black phosphorus, bismuth oxide selenide, bismuth sulfide, bismuth selenide, bismuth telluride, chromium germanium telluride, chromium triiodide, chromium copper sulfide, indium copper selenide, indium copper sulfide, iron phosphide sulfide, iron phosphide, gallium selenide, germanium selenide, hafnium disulfide, hafnium diselenide, hafnium ditelluride, indium selenide, manganese phosphide, molybdenum selenide sulfide, molybdenum ditelluride, tungsten molybdenum sulfide, tungsten selenide, niobium disulfide, niobium diselenide, nickel phosphide sulfide, tin lead sulfide, tin palladium selenide, palladium diselenide, rhenium disulfide, rhenium diselenide, rhenium telluride, stannous sulfide, tin disulfide, stannous selenide, tin diselenide, nickel tantalum sulfide, nickel tantalum telluride, tantalum disulfide, tantalum diselenide, tantalum ditelluride, tantalum disulfide, titanium selenide, and the like, One or more of titanium diselenide, vanadium diselenide, tungsten disulfide, tungsten diselenide, tantalum tungsten sulfide, tungsten ditelluride, zirconium disulfide, zirconium trisulfide, zirconium diselenide and zirconium triselenide crystals.
8. The two-dimensional aqueous ink according to claim 6, wherein the electrolyte of the two-electrode electrochemical system in step 1) is selected from one or more of ethanol, propanol, butanol, acetonitrile, propionitrile and carbon tetrachloride; one or more macromolecular cations can be added into the electrolyte; the macromolecular cation is selected from tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide and tetraheptylammonium bromide; the voltage of the electrolysis in the step 1) is-0.01V-100V, and the time is 1 min-72 h; the rotating speed of the centrifugal machine in the step 2) is 1000 rpm-10000 rpm.
9. A method for preparing the two-dimensional aqueous ink according to claim 1, comprising the steps of:
s1) dispersing the two-dimensional material nanosheets in a solvent, and obtaining a mixed solution after ultrasonic dispersion;
s2) centrifuging and screening the mixed solution by a centrifuge at 1000-5000 rpm to obtain the two-dimensional material water-based ink.
10. The application of two-dimensional material water-based ink in integrated circuits.
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|---|---|---|---|---|
| CN115304405A (en) * | 2022-07-29 | 2022-11-08 | 广东精英无机材料有限公司 | Boehmite digital glaze ink and preparation method thereof |
| KR20230095139A (en) * | 2021-12-21 | 2023-06-29 | 성균관대학교산학협력단 | 2d material dispersion manufacturing method and large-area semiconductor device manufacturing method using same |
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| KR102680442B1 (en) | 2021-12-21 | 2024-07-02 | 성균관대학교산학협력단 | 2d material dispersion manufacturing method and large-area semiconductor device manufacturing method using same |
| CN115304405A (en) * | 2022-07-29 | 2022-11-08 | 广东精英无机材料有限公司 | Boehmite digital glaze ink and preparation method thereof |
| CN115304405B (en) * | 2022-07-29 | 2023-09-26 | 广东精英无机材料有限公司 | Boehmite digital glaze ink and preparation method thereof |
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