CN116429850B - Based on rare earth metal doped porphyrin COFs/carbon-based quantum dot/In 2 O 3 Composite film sensor and its making method and application - Google Patents
Based on rare earth metal doped porphyrin COFs/carbon-based quantum dot/In 2 O 3 Composite film sensor and its making method and application Download PDFInfo
- Publication number
- CN116429850B CN116429850B CN202310699713.0A CN202310699713A CN116429850B CN 116429850 B CN116429850 B CN 116429850B CN 202310699713 A CN202310699713 A CN 202310699713A CN 116429850 B CN116429850 B CN 116429850B
- Authority
- CN
- China
- Prior art keywords
- carbon
- porphyrin
- cofs
- based quantum
- composite film
- 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.)
- Active
Links
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 80
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000002096 quantum dot Substances 0.000 title claims abstract description 70
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 67
- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 53
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims description 15
- 239000000758 substrate Substances 0.000 claims abstract description 38
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- 239000011248 coating agent Substances 0.000 claims description 29
- 238000000576 coating method Methods 0.000 claims description 29
- 239000010410 layer Substances 0.000 claims description 27
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 26
- 238000004528 spin coating Methods 0.000 claims description 25
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 24
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- 239000003960 organic solvent Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 20
- 238000002425 crystallisation Methods 0.000 claims description 19
- 230000001105 regulatory effect Effects 0.000 claims description 19
- -1 rare earth metal salt Chemical class 0.000 claims description 18
- 230000008025 crystallization Effects 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 229910052738 indium Inorganic materials 0.000 claims description 13
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 13
- 229920002120 photoresistant polymer Polymers 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000001465 metallisation Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 8
- 230000001070 adhesive effect Effects 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- REPFNYFEIOZRLM-UHFFFAOYSA-N chembl376444 Chemical compound C1=CC(N)=CC=C1C(C1=CC=C(N1)C(C=1C=CC(N)=CC=1)=C1C=CC(=N1)C(C=1C=CC(N)=CC=1)=C1C=CC(N1)=C1C=2C=CC(N)=CC=2)=C2N=C1C=C2 REPFNYFEIOZRLM-UHFFFAOYSA-N 0.000 claims description 7
- 238000009792 diffusion process Methods 0.000 claims description 7
- 238000005516 engineering process Methods 0.000 claims description 7
- 238000007747 plating Methods 0.000 claims description 7
- 238000010025 steaming Methods 0.000 claims description 7
- 239000012790 adhesive layer Substances 0.000 claims description 6
- 230000004888 barrier function Effects 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 4
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical class O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000001259 photo etching Methods 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 150000002472 indium compounds Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical group Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000001771 vacuum deposition Methods 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000004140 cleaning Methods 0.000 description 18
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical group COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- 229910021389 graphene Inorganic materials 0.000 description 12
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 10
- 230000004044 response Effects 0.000 description 10
- 229910003437 indium oxide Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical group C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 6
- 230000001976 improved effect Effects 0.000 description 6
- 239000011540 sensing material Substances 0.000 description 6
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 6
- 239000012855 volatile organic compound Substances 0.000 description 6
- 208000005718 Stomach Neoplasms Diseases 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 206010017758 gastric cancer Diseases 0.000 description 5
- 229910000337 indium(III) sulfate Inorganic materials 0.000 description 5
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 description 5
- 201000011549 stomach cancer Diseases 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical group CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000003745 diagnosis Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000001939 inductive effect Effects 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000006557 surface reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- 229920000608 Polyaspartic Polymers 0.000 description 2
- 229920000805 Polyaspartic acid Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000008240 homogeneous mixture Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- JVTMLBYYQYMFLV-UHFFFAOYSA-N 2-methyl-1h-imidazole;zinc Chemical compound [Zn].CC1=NC=CN1 JVTMLBYYQYMFLV-UHFFFAOYSA-N 0.000 description 1
- UHZWVDHHMHBMDX-UHFFFAOYSA-N 5-fluorothiophene-2,3-dicarbaldehyde Chemical compound FC1=CC(C=O)=C(C=O)S1 UHZWVDHHMHBMDX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920001244 Poly(D,L-lactide) Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000013399 early diagnosis Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910001449 indium ion Inorganic materials 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- RMUKCGUDVKEQPL-UHFFFAOYSA-K triiodoindigane Chemical compound I[In](I)I RMUKCGUDVKEQPL-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2361/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention discloses a rare earth metal doped porphyrin COFs/carbon-based quantum dot/In based 2 O 3 Sensor of composite film, its preparation method and application, the sensor includes flexible substrate, flexible interdigital electrode and rare earth metal doped porphyrin COFs/carbon based quantum dot/In laminated In turn 2 O 3 The preparation method of the composite film comprises the following steps: (1) preparing a flexible interdigital electrode with a flexible substrate; (2) Preparation of Supported carbon-based Quantum dots/In 2 O 3 A flexible sensing device of the composite film; (3) Preparation of porphyrin-loaded COFs/carbon-based Quantum dot/In 2 O 3 A flexible sensing device of the composite film; (4) Preparation of rare earth metal doped porphyrin COFs/carbon-based quantum dot/In 2 O 3 A sensor of composite film. The sensor has the advantages of good stability, high sensitivity, capability of rapidly detecting at low temperature, and sensitivity and high selectivity to 2-Ding Tonggao.
Description
Technical Field
The invention relates to the technical field of sensors, in particular to a rare earth metal doped porphyrin COFs/carbon-based quantum dot/In-based porphyrin 2 O 3 A sensor of composite film, its preparing process and application are disclosed.
Background
Gastric cancer is taken as a high-rise tumor, new cases account for nearly half of the total world number each year, and current global policy is highly concerned about gastric cancer screening and early diagnosis and early treatment. At the same time, monitoring for specific volatile organics (such as 2-butanone) in the exhalation of cancer patients has become a leading study in today's world for the diagnosis of significant diseases, but still faces serious challenges.
The invention patent with publication number CN114076783 discloses a 2-Ding Tongchuan sensor based on ZnO nano-sensitive material and a preparation method thereof, wherein the sensor is prepared from Al with two parallel, annular and separated gold electrodes on the surface 2 O 3 Ceramic tube substrate coated on Al 2 O 3 APTES functionalized ZnO nano-sensitive material arranged on outer surface of ceramic tube and gold electrode and arranged on Al 2 O 3 A nickel-cadmium heating coil in the ceramic tube; the 2-methylimidazole zinc salt is selected as a self-sacrifice template, the porous ZnO nano material is obtained through high-temperature calcination, and the 3-aminopropyl triethoxysilane is modified on the surface of the ZnO nano material, so that the interaction between 2-butanone and sensitive materials is increased, and the response of the sensor to the 2-butanone is obviously improved. However, the sensor has the disadvantages of high operating temperature (260 ℃), low sensitivity to ultra-low concentration (ppb level) butanone, susceptibility to humidity, and the like.
Disclosure of Invention
The invention aims to: in order to solve the technical problems In the prior art, the invention aims to provide a rare earth metal doped porphyrin COFs/carbon-based quantum dot/In-based quantum dot based on rare earth metal doped porphyrin COFs/carbon-based quantum dot/In which has good stability and high sensitivity and can be rapidly detected at low temperature 2 O 3 The invention also provides a preparation method of the sensor and application of the sensor in detecting 2-butanone.
The technical scheme is as follows: the invention relates to a rare earth metal doped porphyrin COFs/carbon-based quantum dot/In-based porphyrin-doped graphene 2 O 3 The sensor of the composite film comprises a flexible substrate, a flexible interdigital electrode and a rare earth metal doped porphyrin COFs/carbon-based quantum dot/In which are sequentially laminated 2 O 3 And (3) a composite film.
Further, in the composite film 2 O 3 The molar ratio of the indium element in the inner layer, the carbon element in the carbon-based quantum dot, the porphyrin in the porphyrin COFs and the rare earth metal is 40-55%, 8-18%, 10-20% and 4-9% respectively; the carbon-based amountThe average particle size of the sub-dots is 3-5 nm.
The invention relates to a rare earth metal doped porphyrin COFs/carbon-based quantum dot/In-based porphyrin-doped graphene 2 O 3 The manufacturing method of the composite film sensor comprises the following steps:
(1) Preparing a flexible interdigital electrode with a flexible substrate;
(2) Immersing the flexible interdigital electrode with the flexible substrate In a colloidal solution containing carbon-based quantum dots and indium compounds for spin coating and coating, taking out and drying after finishing, and then carrying out steam-assisted crystallization treatment and glow treatment to obtain the loaded carbon-based quantum dots/In 2 O 3 A flexible sensing device of the composite film;
(3) Will load carbon-based quantum dot/In 2 O 3 Immersing the flexible sensing device of the composite film In a porphyrin COFs precursor solution for lifting and coating, taking out and drying after finishing, and then carrying out mixed organic solvent steam assisted crystallization treatment to obtain the supported porphyrin COFs/carbon-based quantum dots/In 2 O 3 A flexible sensing device of the composite film;
(4) Porphyrin-loaded COFs/carbon-based quantum dot/In 2 O 3 Immersing the flexible sensing device of the composite film In a rare earth metal salt mixed solution, carrying out metallization treatment, carrying out organic solvent heat steaming treatment and glow treatment after the metallization treatment is finished, and obtaining the rare earth metal doped porphyrin COFs/carbon-based quantum dots/In based on the rare earth metal doped porphyrin COFs/carbon-based quantum dots/In after the termination treatment 2 O 3 A sensor of composite film.
Further, in the step (1), the preparation method of the flexible interdigital electrode with the flexible substrate comprises the following steps: spin-coating an adhesive on the surface of a flexible substrate with silicon dioxide on the surface, then baking for the first time, spin-coating photoresist on the surface of the adhesive, baking for the second time, and performing photoetching treatment and third baking to form a substrate; the substrate is sprayed and developed by a developer, a metal layer is deposited by adopting a vacuum coating technology, an interdigital electrode consisting of a titanizing adhesive layer, a platinized diffusion barrier layer and a gold-plated conductive layer is constructed, and residual photoresist is removed by stripping treatment, so that the flexible interdigital electrode with the flexible substrate is obtained; the thicknesses of the titanizing adhesive layer, the platinizing diffusion barrier layer and the gold plating conductive layer are respectively 30-60 nm, 50-150 nm and 40-120 nm.
Further, the flexible substrate is ultrathin glass, polyimide film or polyvinylidene fluoride film; the adhesive is hexamethyldisilazane; the photoresist is JSR series negative photoresist; the developer is JSR series developer, the spraying time is 40-80 s, and deionized water is used for washing and removing the developer after spraying and developing; the temperature of the first baking is 80-100deg.C, and the time is 2-4 min; the temperature of the second baking is 100-120 ℃ and the time is 2-4 min; the temperature of the third baking is 90-120 ℃ and the time is 2-4 min; the spin coating parameters of the adhesive and the photoresist are as follows: the rotating speed is 3000-5000 rpm, and the time is 20-40 s; the parameters of the photoetching treatment are as follows: the light intensity is 2.4-8.4W/cm 2 The exposure time is 4-40 s; the stripping treatment comprises the following steps: treating 3-7. 7 h in N-methylpyrrolidone (NMP) at 50-80deg.C, and cleaning and drying.
Further, in the step (2), the preparation method of the colloidal solution containing the carbon-based quantum dots and the indium-containing compound comprises the following steps: dissolving an indium-containing compound and a carbon-based quantum dot in a solvent, sequentially adding a surfactant and hydrochloric acid, and mixing to obtain a colloidal solution of the carbon-based quantum dot and the indium-containing compound; the mass ratio of the carbon-based quantum dots to the indium-containing compound is 1.2-2.4:0.24-0.8, preferably 2-2.4:0.65-0.7; the spin-on coating parameters are as follows: under the condition of room temperature, the humidity is regulated to be 50-80%, the spin coating speed is 4000-6000 rpm, and the spin coating time is 40-80 s; the steam assisted crystallization treatment process comprises the following steps: introducing oxygen carrying water vapor into a furnace tube, wherein the temperature of the furnace tube is 180-200 ℃, and the partial pressure of the water vapor is 0.4-0.6; the glow treatment process comprises the following steps: the oxygen glow treatment is adopted, the frequency of the plasma cleaning machine is 13.56MHz, the power is 5-100W, and the time is 5-15 min.
Further, the carbon-based quantum dots are nitrogen-doped graphene quantum dots, sulfur-doped graphene quantum dots or graphene quantum dots; the indium-containing compound is indium chloride, indium sulfate or indium iodide; the solvent is N-methylmorpholine-N-oxide, tetrahydrofuran, anhydrous dimethylformamide or anhydrous dimethyl sulfoxide; the surfactant is a monomethoxy poly (ethylene glycol) -poly (D, L-lactic acid) diblock copolymer, polyethylene glycol-polyglycolic acid-polyethylene glycol or polyaspartic acid-polyethylene glycol-polyaspartic acid, and the dosage is 25-40% of the dosage of the indium-containing compound; the hydrochloric acid has the concentration of 10-12M, the molar ratio of chloride ions in the hydrochloric acid to indium ions in the indium-containing compound is 10-20:1, and the mixing mode of the hydrochloric acid is as follows: ultrasonic dispersion is adopted, and the dispersion time is 15-20 min.
Further, the step of performing the mixed organic solvent steam-assisted crystallization treatment further comprises the steps of cleaning and drying: cleaning by adopting a mixed solution of isopropanol, acetone and trichloroethylene, and then carrying out vacuumizing and drying treatment.
Further, in the step (3), the step of pulling up the plating film is as follows: depositing thiophenic aldehyde derivatives on the carbon-based quantum dots/In by using a lifting film plating machine 2 O 3 Depositing 5, 10, 15, 20-tetra (4-aminophenyl) porphyrin on the surface of the composite film to form a porphyrin COFs film layer; the ratio of the thiophene aldehyde derivative to the bridging unit of 5, 10, 15, 20-tetra (4-aminophenyl) porphyrin is 1:3-1:9, preferably 1:4-1:6, the ratio of the bridging unit has an effect on the crystallinity of the rare earth metal doped porphyrin COFs, the COFs can not be formed when the ratio is lower than 3:1, and the crystallinity of the COFs is obviously reduced when the ratio is higher than 9:1; the selectivity and humidity resistance of the sensor are significantly reduced without the inclusion of metalloporphyrin COFs. The carbon-based quantum dots play a role in conducting carrier transport between the metalloporphyrin COFs and indium oxide.
Further, the thiophenal derivative is 5-fluoro-2, 3-thiophenedicarboxyaldehyde or 4, 4-difluoro-thieno [3,2-b ] thiophene-2, 5-dicarboxaldehyde; the lifting speed of the lifting coating machine is 15-25 mm/min, the lifting times are 5-10 times, and the soaking time is 45-60 s.
Further, in the step (3), the mixed organic solvent is composed of ethanol, 1, 2-dichlorobenzene and acetic acid; the volume ratio of the ethanol to the 1, 2-dichlorobenzene to the acetic acid is 8-20:4-10:1-5, preferably 8-10:4-5:2-4; the process of the mixed organic solvent steam assisted crystallization treatment comprises the following steps: acetic acid in a mixed organic solvent is used as a reaction catalyst, and heated to 100-140 ℃ in protective gas to induce thiophene aldehyde derivatives and 5, 10, 15, 20-tetra (4-aminophenyl) porphyrin to carry out condensation reaction for 3-12 h.
Further, in the step (4), the preparation method of the rare earth metal salt mixed solution comprises the following steps: adding 50-100 mg rare earth metal salt into 6-10 ml organic solvent, stirring 4-8 h to form a uniform mixture; the metallization treatment method comprises the following steps: porphyrin-loaded COFs/carbon-based quantum dot/In 2 O 3 Immersing the flexible sensor of the composite film in the mixed solution of rare earth metal salt for 25-40 s, and then carrying out lifting coating at a speed of 10-20 mm/min by adopting a lifting coating machine for 5-10 times; after the film is coated by pulling, the average thickness of each layer of formed rare earth metal doped porphyrin COFs is 10-50 nm. After 6-8 times of coating, regulating the total thickness of the rare earth metal doped porphyrin COFs to be within 200 nm; the rare earth metal salt is neodymium chloride, cerium chloride or praseodymium chloride; the organic solvent heat steaming treatment comprises the following steps: exposing to organic solvent vapor with temperature of 120-150deg.C and pressure of 50-200 KPa under helium protection, and maintaining 24-48 h; the glow treatment comprises the following steps: argon plasma is adopted, the power is 20-100W, and the time is 5-20 min; the organic solvent is propylene glycol methyl ether.
Further, the organic solvent heat steaming treatment further comprises cleaning and drying: cleaning by adopting propylene glycol methyl ether, and then vacuumizing and drying; the glow treatment further comprises the steps of cleaning and drying: cleaning with a mixed solution of isopropanol, acetone and trichloroethylene, and vacuum drying 24-36 h.
The invention relates to a rare earth metal doped porphyrin COFs/carbon-based quantum dot/In-based porphyrin-doped graphene 2 O 3 The application of the composite film sensor in detecting ppb level 2-butanone.
The principle of the invention: in order to realize accurate detection of the ultra-low concentration gastric cancer exhalation marker 2-butanone, the development of the ultra-sensitive and high-selectivity metalloporphyrin-based covalent organic framework synergistic carbon-based quantum dot/indium oxide composite sensing device has important significance. According to the thought of constructing the high-quality van der Waals heterojunction, the invention explores a novel design principle and scheme aiming at the ultrasensitive composite material, develops a preparation method combining steam-assisted crystallization = plasma surface functionalization, explores a mechanism for enhancing gas sensitivity performance by a nano microstructure, reveals the influence rule of van der Waals heterojunction defect gradient distribution on adsorption performance and carrier transmission, and clarifies an evolution mechanism of composite material P-N type sensing characteristic conversion under a multi-interference environment. The achievement of the invention has important value for enriching research connotation of the porous sensing film and promoting the expiration diagnosis of gastric cancer.
The functional structural unit facing the sensing target is integrated by a steam-assisted crystallization method, and the metalloporphyrin can construct a covalent organic framework material with high conjugation and dense stacking. The combination of metalloporphyrin COFs and VOCs can induce the change of electronic structures, and the energy of leading-edge molecular orbitals and the combination energy can change differently according to different functional groups of the VOCs. Metalloporphyrin-based COFs have unique affinity for carbonyl VOCs, can provide a strong reactive center with 2-butanone, and can continuously maintain the reaction inertness to high-concentration carbon dioxide. Metalloporphyrin-based COFs offer two significant advantages: (1) can operate at room temperature; (2) The sensing properties can be tuned using a variety of chemical structures synthesized. The metalloporphyrin COFs-based gas sensor has strong affinity to 2-butanone at room temperature, shows good sensing response characteristics, but has the problem of longer recovery time because the desorption process is slower.
The metal porphyrin COFs/inorganic semiconductor sensing material based on the van der Waals heterojunction can improve response/recovery speed and reduce power consumption (the power consumption can be reduced to 2 nW). By constructing a novel van der Waals heterostructure, the richness of metalloporphyrin COFs/inorganic semiconductor structure can be optimized, and the functional diversity can be improved. The ordered conjugated periodic structure of the covalent organic framework structure can realize the generation of bicontinuous heterojunction under molecular precision, can provide a low-energy path for carrier transmission, and is the best choice for constructing the van der Waals inner gradient heterojunction. In addition, the vapor-assisted crystallization method can effectively improve the long-range order and carrier transmission characteristics of the organic semiconductor material. By compounding the metalloporphyrin COFs with the carbon-based/MOS nanomaterial, ultrasensitive and rapid response to VOCs gas under room temperature can be realized.
According to the invention, metalloporphyrin COFs with huge potential in the gas-sensitive sensing field are reasonably introduced, a series of van der Waals heterojunction sensing materials with brand new structure and combining carbon-based quantum dots/indium oxide are designed, and an ultrasensitive high-selectivity sensing device is designed. Breaks through the traditional material preparation method, combines the vapor assisted crystallization method with the plasma surface functionalization technology. Constructing a multi-interface energy level regulation structure, and inducing metalloporphyrin COFs to grow along the direction most favorable for carrier transmission, and forming an adjustable van Hough singular point peak between the metalloporphyrin COFs and the graphene quantum dots/indium oxide. Cutting the metal porphyrin COFs functional group and regulating and controlling the defect distribution synchronously. Component matching and defect gradient distribution of the van der Waals heterojunction are accurately regulated at the surface interface of the composite sensing material, the selectivity of the composite material is efficiently and accurately regulated, and the anti-interference performance is improved.
Working principle: the invention uses photoetching technology to manufacture flexible interdigital electrodes as a substrate for loading the composite sensing film. And smoothly embedding the functionalized carbon-based quantum dots into a liquid crystal template by adopting a sol-gel method, and realizing volatilization-induced self-assembly by adopting a spin coating method to prepare the carbon-based quantum dot/indium oxide sensing layer. And constructing a self-assembly body of the TAPP monomer and the bridging unit on the surface of the carbon-based quantum dot/indium oxide sensing device in situ by adopting a lifting coating technology. Organic/inorganic composite material is treated by using an organic mixed vapor auxiliary crystallization technology, and the surface affinity of the material is regulated and controlled by using vapor molecules with different polarities, so that the order and crystallinity of TAPP-COFs pore structure are regulated. And the energy level structure of the composite material is further regulated by using a plasma surface functionalization technology, so that the distribution of the interface defects of the gradient heterojunction surface in van der Waals is effectively regulated and controlled. The surface interface structure and the characterization test result are combined, so that the activation energy of the diffusion and reaction of the nanopore microstructure and the 2-butanone is reduced, the adsorption and desorption characteristics of the sensing material are improved, and the sensitivity of the sensing material is enhanced. The covalent organic framework material and the graphene quantum dots/indium oxide form a high-quality van der Waals heterojunction, the uniform dispersibility and the dispersion concentration of the graphene quantum dots are improved, the electron transmission capacity and the gas-sensitive activity are effectively improved, and the technical problems of low gas-sensitive activity and poor anti-interference capacity of the graphene quantum dots/indium oxide are solved, so that the sensing performance of high sensitivity and high selectivity on 2-butanone is realized.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: according to the invention, a van der Waals heterojunction structure is built, a sensing material consisting of a nano-pore rare earth metalloporphyrin COFs/carbon-based quantum dot/indium oxide composite film is prepared, energy level matching between double induction layers is realized, a high-quality van der Waals heterojunction is built, the gradient heterojunction defect is adjustable in van der Waals, the rapid transmission of charges of the double induction layers is facilitated, and an efficient sensing device suitable for a multi-interference environment is developed; in addition, the invention develops a gas-sensitive sensing test, promotes the consistency of van der Waals heterojunction component matching and sensing performance, realizes the sensing characteristic of the sensor that the ppb level 2-butanone performance is adjustable, and establishes an expiration diagnosis model of gastric cancer.
Drawings
FIG. 1 is a field emission scanning electron microscope (FEMS) of the composite film material prepared in example 1 of the present invention;
FIG. 2 is a graph showing the response of the sensor prepared in example 1 of the present invention to different 2-butanone gas concentrations;
FIG. 3 is a graph showing the sensing performance of the sensor prepared in example 1 of the present invention against 200 ppb 2-butanone at various humidities;
FIG. 4 is a graph showing the selectivity of the sensor prepared in example 1 of the present invention for different gases;
FIG. 5 is a graph showing the response of the sensor prepared in example 2 of the present invention to different 2-butanone gas concentrations.
Detailed Description
The invention will be further described with reference to specific examples and figures.
The invention relates to a rare earth metal doped porphyrin COFs/carbon-based quantum dot/In-based porphyrin-doped graphene 2 O 3 The composite film comprises a flexible substrate, a flexible interdigital electrode and rare earth metal/porphyrin COFs/carbon-based quantum dots/In which are sequentially laminated 2 O 3 A composite film, wherein In the composite film 2 O 3 In indium element and carbon-based quantum dotThe molar ratio of the carbon element to the porphyrin to the rare earth metal in the porphyrin COFs is 40-55%, 8-18%, 10-20% and 4-9% respectively; the average particle size of the carbon-based quantum dots is 3-5 nm, and the carbon-based quantum dots are nitrogen-doped graphene quantum dots, sulfur-doped graphene quantum dots or graphene quantum dots.
Example 1: the invention relates to a rare earth metal doped porphyrin COFs/sulfur doped graphene quantum dot/In based 2 O 3 The preparation method of the composite film sensor comprises the following steps:
(1) Preparing a flexible interdigital electrode with a flexible substrate, which comprises the following steps: to improve the adhesion of the photoresist to the surface silica-loaded polyimide flexible substrate, hexamethyldisilazane adhesive was spin coated onto the cleaned flexible substrate on a spin coater at 3000 rpm for 40 s a spin time. Baking the new coating on a heating plate at 80 ℃ for 3 min. Then, JSR series negative photoresist was spin-coated on the flexible substrate at 5000rpm for 20 s. Baking the new coating on a heating plate at 120 ℃ for 3 min. Performing lithography on a mask aligner with a regulated light intensity of 6.4W/cm 2 The exposure time was 25 s. After exposure, the flexible substrate was placed on a heating plate to be heated and baked at 110 ℃ to form a substrate. The substrate was placed on a spin coater and spray developed with JSR series developer for 60s. Next, the developer was removed by rinsing with deionized water. The metal layer is vacuum coated, firstly, the titanium-coated metal film layer is used as an adhesive layer, and the regulating thickness is 40 nm. Second, a platinum diffusion barrier layer was plated to control the thickness to 100 a nm a. Finally, the thickness of the gold-plated conductive layer is adjusted to 80 nm. Removing residual photoresist 5 h in NMP bath at 60deg.C, cleaning, and vacuum drying.
(2) According to indium chloride 2.0 g: sulfur-doped graphene quantum dots 0.64 g:10 ml of N-methylmorpholine-N-oxide (NMMO) is mixed to form a mixture, 0.5 g surfactant polyaspartic acid-polyethylene glycol-polyaspartic acid (PASP-b-PEG-b-PASP) is added to the mixture to be uniformly mixed, then 1.0 ml hydrochloric acid with the concentration of 12M is dripped into the mixture, ultrasonic dispersion is carried out by means of ultrasonic waves, and the ultrasonic dispersion time is 16 min, so that the colloidal solution of sulfur-containing doped graphene quantum dots and indium chloride is obtained.
Immersing the flexible interdigital electrode with the flexible substrate in a colloid solution containing sulfur-doped graphene quantum dots and indium chloride for spin coating, wherein the spin coating parameters are as follows: under the condition of room temperature, the humidity is regulated to 80%, the spin coating speed is 4000 rpm, the spin coating time is 40 s, the film is taken out and dried after the spin coating is finished, then steam assisted crystallization treatment and glow treatment are carried out, the temperature of the furnace tube is 185 ℃ by adopting oxygen to carry water vapor, the partial pressure of the water vapor is 0.45, the oxygen glow treatment is adopted, the frequency of a used plasma cleaning machine is 13.56MHz, the power is 45 watts, the time is 5 min, and the sulfur-loaded doped graphene quantum dot/In is obtained after the process is finished 2 O 3 Flexible sensor device of composite film.
(3) The sulfur-loaded doped graphene quantum dot/In 2 O 3 Immersing the flexible sensing device of the composite film In a porphyrin COFs precursor solution for lifting and coating, taking out and drying after finishing, and performing mixed organic solvent steam assisted crystallization treatment to obtain the supported porphyrin COFs/sulfur doped graphene quantum dots/In 2 O 3 The flexible sensing device of the composite film comprises the following components: using the mixed gas of hydrogen and nitrogen as protective gas, in the glove box filled with protective gas, firstly using a lifting film plating machine to make 4, 4-difluoro-thieno [3,2-b]Thiophene-2, 5-dicarboxaldehyde solution is deposited on the surface of the sulfur-doped graphene quantum dot/indium oxide composite film, and then 5, 10, 15, 20-tetra (4-aminophenyl) porphyrin (TAPP) solution is deposited. By using a bridging unit ratio of 1:6 control the coverage of TAPP-COFs at the interface growth. The number of impregnations was 6, the impregnation time was 50 s and the pull rate was 20 mm/min. The organic mixed solvent is a mixture of ethanol, 1, 2-dichlorobenzene and acetic acid, the volume ratio of the ethanol to the 1, 2-dichlorobenzene is 5, and the acetic acid is 4. Wherein acetic acid is a reaction catalyst. And vacuumizing the closed solution, filling protective gas, heating to 120 ℃, and inducing condensation reaction, wherein the reaction is 8 h. The sensor is cleaned by using organic solution prepared from isopropanol, acetone and trichloroethylene, and thenAnd (5) vacuumizing and drying.
(4) Porphyrin-loaded COFs/sulfur-doped graphene quantum dots/In 2 O 3 Immersing the flexible sensing device of the composite film In a rare earth metal salt mixed solution, carrying out metallization treatment, carrying out organic solvent heat steaming treatment and glow treatment after the metallization treatment is finished, and obtaining the rare earth metal doped porphyrin COFs/sulfur doped graphene quantum dots/In based on the rare earth metal doped porphyrin COFs/sulfur doped graphene quantum dots/In after the termination treatment 2 O 3 The composite film sensor specifically comprises: the preparation method of the rare earth metal salt mixed solution comprises the following steps: 60 mg neodymium chloride was added to 8 ml propylene glycol methyl ether and 8 h was stirred to form a homogeneous mixture. Immersing the sensing device in the mixture 30 s, carrying out lifting coating at a speed of 15 mm/min by using a lifting coating machine, wherein after lifting coating, the average thickness of each layer of formed rare earth metal doped porphyrin COFs is 10-50 nm, and after 6-8 times of coating, the total thickness of the rare earth metal doped porphyrin COFs is regulated to be within 200 nm; the sensing device is cleaned by propylene glycol methyl ether, and then vacuumized and dried. The sensor device was exposed to propylene glycol methyl ether vapor under helium protection at 140 ℃ under 40 KPa pressure, maintaining 36 h. The organic solution prepared from isopropyl alcohol, acetone and trichloroethylene was used for washing, followed by vacuum drying 30 to h. And cleaning the sensing device by adopting argon plasma. The frequency of the plasma cleaning machine is 13.56MHz, the power is 20W, and the plasma cleaning time is 10 min, thus obtaining the sensor.
Example 2: the invention relates to a rare earth metal doped porphyrin COFs/nitrogen doped graphene quantum dot/In based 2 O 3 The preparation method of the composite film sensor comprises the following steps:
(1) Preparing a flexible interdigital electrode with a flexible substrate, which comprises the following steps: to improve the adhesion of the photoresist to the surface silica-loaded polyimide flexible substrate, hexamethyldisilazane adhesive was spin coated onto the clean flexible substrate on a spin coater at 5000rpm for 20 s a spin time. The new coating was baked on a hot plate at 100℃for 2 minutes. Then, JSR series negative photoresist is spin-coated on the flexible substrate, the rotating speed is 3000 rpm, and the spin-coating time is 40s. The new coating was baked on a hot plate at 100℃for 4 min. Performing lithography on a mask aligner with a regulated light intensity of 3.6W/cm 2 The exposure time was 35 s. After exposure, the flexible substrate was placed on a heating plate to be heated and baked at 120 ℃ to form a substrate. The substrate was placed on a spin coater and spray developed with JSR series developer for a spray time of 80 s. Next, the developer was removed by rinsing with deionized water. The metal layer is vacuum coated, firstly, the titanium-coated metal film layer is used as an adhesive layer, and the regulating thickness is 60 nm. Second, a metal platinum diffusion barrier layer was plated to a thickness of 120 a nm a. Finally, the thickness of the gold-plated conductive layer is adjusted to be 100 nm. Removing residual photoresist 3 h in NMP bath at 80deg.C, cleaning, and vacuum drying.
(2) According to indium sulfate 2.4 g: nitrogen doped graphene quantum dots 0.7 g: and (3) forming a mixture by the proportion of 12 milliliters of Tetrahydrofuran (THF), adding 0.6 g surfactant polyethylene glycol-polyglycolic acid-polyethylene glycol (PEG-PLGA-PEG), uniformly mixing, then dripping hydrochloric acid with the concentration of 0.9 ml of 12M, carrying out ultrasonic dispersion by means of ultrasonic waves, and obtaining the colloidal solution of the nitrogen-doped graphene quantum dots and the indium sulfate, wherein the ultrasonic dispersion time is 15 minutes.
Immersing the flexible interdigital electrode with the flexible substrate in a colloid solution containing nitrogen-doped graphene quantum dots and indium sulfate for spin coating, wherein the spin coating parameters are as follows: under the condition of room temperature, the humidity is regulated to 50%, the spin coating speed is 6000 rpm, the spin coating time is 80 and s, the spin coating is finished, then the spin coating is taken out and dried, then the vapor assisted crystallization treatment and glow treatment are carried out, the vapor assisted crystallization treatment method adopts oxygen to carry vapor into a furnace tube, the temperature of the furnace tube is 200 ℃, the partial pressure of the vapor is 0.5, the oxygen glow treatment is adopted, the frequency of a used plasma cleaning machine is 13.56MHz, the power is 35W, the time is 15 min, and the loaded nitrogen doped graphene quantum dot/In is obtained after the spin coating is finished 2 O 3 Flexible sensor device of composite film.
(3) The loaded nitrogen doped graphene quantum dot/In 2 O 3 The flexible sensing device of the composite film is immersed in the porphyrin COFs precursor solution for carrying outPulling a coating film, taking out and drying after finishing, and performing mixed organic solvent steam assisted crystallization treatment to obtain the supported porphyrin COFs/nitrogen doped graphene quantum dots/In 2 O 3 The flexible sensing device of the composite film comprises the following components: and (3) using a mixed gas of hydrogen and nitrogen as a protective gas, depositing a 5-fluoro-2, 3-thiophene dicarboxaldehyde solution on the surface of the nitrogen-doped graphene quantum dot/indium sulfate composite film by using a lifting film plating machine in a glove box filled with the protective gas, and then depositing a 5, 10, 15, 20-tetra (4-aminophenyl) porphyrin (TAPP) solution. By using a bridging unit ratio of 1:4 control the coverage of TAPP-COFs at the interface growth. The dipping times are 8 times, the dipping time is 60s, the lifting speed is 15 mm/min, and the thickness of the TAPP-COFs film is regulated to be within 200 nm. The organic mixed solvent is a mixture of ethanol, 1, 2-dichlorobenzene and acetic acid, the volume ratio of the ethanol to the mixture is 8,1,2-dichlorobenzene, the volume ratio of the ethanol to the mixture is 4, and the volume ratio of the acetic acid to the mixture is 2. Wherein acetic acid is a reaction catalyst. And vacuumizing the closed solution, filling protective gas, heating to 140 ℃, and inducing condensation reaction, wherein the reaction is 4 h. The sensing device is cleaned by adopting an organic solution prepared from isopropanol, acetone and trichloroethylene, and then is vacuumized and dried.
(4) Porphyrin-loaded COFs/nitrogen-doped graphene quantum dots/In 2 O 3 Immersing the flexible sensing device of the composite film In a rare earth metal salt mixed solution, carrying out metallization treatment, carrying out organic solvent heat steaming treatment and glow treatment after the metallization treatment is finished, and obtaining the rare earth metal doped porphyrin COFs/nitrogen doped graphene quantum dots/In based on the rare earth metal doped porphyrin COFs/nitrogen doped graphene quantum dots/In after the termination treatment 2 O 3 The composite film sensor specifically comprises: the preparation method of the rare earth metal salt mixed solution comprises the following steps: 80 mg praseodymium chloride was added to 10 ml propylene glycol methyl ether and stirred for 8 h to form a homogeneous mixture. Immersing the sensing device into the mixture 40 s, carrying out pulling coating at the speed of 20 mm/min by using a pulling coating machine, wherein the average thickness of each layer of rare earth metal doped porphyrin COFs formed after the pulling coating is 10-50 nm, and regulating the total thickness of the rare earth metal doped porphyrin COFs to be within 200 nm after 6-8 times of coating. The sensing device is cleaned by propylene glycol methyl ether, and then vacuumized and dried. Sensing deviceUnder the protection of helium, the mixture is exposed to propylene glycol methyl ether vapor at the temperature of 140 ℃ and the pressure of 50 KPa, and is kept at 24 h. The organic solution prepared from isopropyl alcohol, acetone and trichloroethylene was used for washing, followed by vacuum drying 30 to h. And cleaning the sensing device by adopting argon plasma. The frequency of the plasma cleaning machine is 13.56MHz, the power is 100W, and the plasma cleaning time is 5 min, thus obtaining the sensor.
The sensors prepared in examples 1 to 2 were subjected to 2-butanone detection, and the results are shown in FIGS. 1 to 5.
As shown in fig. 1, the left view in fig. 1 is a partial view of the interdigital electrode, and Jin Cha refers to a pitch of about 2 um. The right graph in fig. 1 is a partial graph of the composite film, and the nanopores on the surface of the film are uniformly distributed.
As shown in fig. 2, the sensitivity of the sensor to butanone at different concentrations was 198, 164, 126, 96, 75, 43, 25, 19, 16,8, respectively. The sensor pair Ding Tongbiao exhibits an n-type sensing response characteristic.
As shown in FIG. 3, the sensitivity to 200 ppb butanone was changed at different humidity conditions of 20%,40%,60%,70%,80%,90%, etc., and it was found that the sensitivity was decreased when the humidity was increased from 20% to 60%. As the ambient humidity continues to increase, the sensitivity tends to stabilize.
As shown in fig. 4, the sensitivity response value to butanone is the largest among the sensitivities to different VOCs, and is 5 times or more the sensitivity response value to other VOCs. The sensor exhibits excellent selectivity.
As shown in fig. 5, the sensor pair Ding Tongbiao fabricated in example 2 exhibited p-type sensing response characteristics.
Claims (6)
1. Based on rare earth metal doped porphyrin COFs/carbon-based quantum dot/In 2 O 3 The composite film sensor is characterized by comprising a flexible substrate, a flexible interdigital electrode and a rare earth metal doped porphyrin COFs/carbon-based quantum dots/In which are sequentially laminated 2 O 3 A composite film; in the composite film 2 O 3 Indium element in, carbon element in carbon-based quantum dot, porphyrin in porphyrin COFs and thin filmThe molar ratio of the earth to the metal is 40-55%, 8-18%, 10-20% and 4-9%; the average particle size of the carbon-based quantum dots is 3-5 nm; the carbon-based quantum dots are nitrogen-doped graphene quantum dots or sulfur-doped graphene quantum dots; the rare earth metal salt is neodymium chloride or praseodymium chloride; the rare earth metal doped porphyrin COFs/carbon-based quantum dot/In-based porphyrin-doped rare earth metal doped porphyrin COFs/carbon-based quantum dot/In-based porphyrin-doped copper-based 2 O 3 The manufacturing method of the composite film sensor comprises the following steps:
(1) Preparing a flexible interdigital electrode with a flexible substrate;
(2) Immersing the flexible interdigital electrode with the flexible substrate In a colloidal solution containing carbon-based quantum dots and indium compounds for spin coating and coating, taking out and drying after finishing, and then carrying out steam-assisted crystallization treatment and glow treatment to obtain the loaded carbon-based quantum dots/In 2 O 3 A flexible sensing device of the composite film;
(3) Will load carbon-based quantum dot/In 2 O 3 Immersing the flexible sensing device of the composite film In a porphyrin COFs precursor solution for lifting and coating, taking out and drying after finishing, and then carrying out mixed organic solvent steam assisted crystallization treatment to obtain the supported porphyrin COFs/carbon-based quantum dots/In 2 O 3 A flexible sensing device of the composite film;
(4) Porphyrin-loaded COFs/carbon-based quantum dot/In 2 O 3 Immersing the flexible sensing device of the composite film In a rare earth metal salt mixed solution, carrying out metallization treatment, carrying out organic solvent heat steaming treatment and glow treatment after the metallization treatment is finished, and obtaining the rare earth metal doped porphyrin COFs/carbon-based quantum dots/In based on the rare earth metal doped porphyrin COFs/carbon-based quantum dots/In after the termination treatment 2 O 3 A sensor of the composite film;
in the step (2), the preparation method of the colloidal solution containing the carbon-based quantum dots and the indium compound comprises the following steps: dissolving an indium-containing compound and a carbon-based quantum dot in a solvent, sequentially adding a surfactant and hydrochloric acid, and mixing to obtain a colloidal solution of the carbon-based quantum dot and the indium-containing compound; the mass ratio of the carbon-based quantum dots to the indium-containing compound is 1.2-2.4:0.24-0.8;
in the step (3), the step of lifting and coating is as follows: depositing thiophenic aldehyde derivatives on the carbon-based quantum dots/In by using a lifting film plating machine 2 O 3 Depositing 5, 10, 15, 20-tetra (4-aminophenyl) porphyrin on the surface of the composite film to form a porphyrin COFs film layer; the ratio of the thiophene aldehyde derivative to the bridging unit of 5, 10, 15, 20-tetra (4-aminophenyl) porphyrin is 1:3-1:9; the lifting speed of the lifting coating machine is 15-25 mm/min, the lifting times are 5-10 times, and the soaking time is 45-60 s;
in the step (4), the preparation method of the rare earth metal salt mixed solution comprises the following steps: adding 50-100-mg rare earth metal salt into 6-10 ml organic solvent, stirring 4-8 h to form a uniform mixture.
2. The sensor of claim 1, wherein in step (1), the method for preparing the flexible interdigital electrode with the flexible substrate comprises the following steps: spin-coating an adhesive on the surface of a flexible substrate with silicon dioxide on the surface, then baking for the first time, spin-coating photoresist on the surface of the adhesive, baking for the second time, and performing photoetching treatment and third baking to form a substrate; the substrate is sprayed and developed by a developer, a metal layer is deposited by adopting a vacuum coating technology, an interdigital electrode consisting of a titanizing adhesive layer, a platinized diffusion barrier layer and a gold-plated conductive layer is constructed, and residual photoresist is removed by stripping treatment, so that the flexible interdigital electrode with the flexible substrate is obtained; the thicknesses of the titanizing adhesive layer, the platinizing diffusion barrier layer and the gold plating conductive layer are respectively 30-60 nm, 50-150 nm and 40-120 nm.
3. The sensor of claim 1, wherein in step (2), the spin-on coating parameters are: under the condition of room temperature, the humidity is regulated to be 50-80%, the spin coating speed is 4000-6000 rpm, and the spin coating time is 40-80 s; the steam assisted crystallization treatment process comprises the following steps: introducing oxygen carrying water vapor into a furnace tube, wherein the temperature of the furnace tube is 180-200 ℃, and the partial pressure of the water vapor is 0.4-0.6; the glow treatment process comprises the following steps: oxygen glow treatment is adopted, the power is 5-100W, and the time is 5-15 min.
4. The sensor of claim 1, wherein in step (3), the mixed organic solvent consists of ethanol, 1, 2-dichlorobenzene, and acetic acid; the volume ratio of the ethanol to the 1, 2-dichlorobenzene to the acetic acid is 8-20:4-10:1-5; the process of the mixed organic solvent steam assisted crystallization treatment comprises the following steps: acetic acid in a mixed organic solvent is used as a reaction catalyst, and heated to 100-140 ℃ in protective gas to induce thiophene aldehyde derivatives and 5, 10, 15, 20-tetra (4-aminophenyl) porphyrin to carry out condensation reaction for 3-12 h.
5. The sensor of claim 1, wherein in step (4), the metallization is performed by: porphyrin-loaded COFs/carbon-based quantum dot/In 2 O 3 Immersing the flexible sensor of the composite film in the mixed solution of rare earth metal salt for 25-40 s, and then carrying out lifting coating at a speed of 10-20 mm/min by adopting a lifting coating machine for 5-10 times; the organic solvent heat steaming treatment comprises the following steps: exposing to organic solvent vapor with temperature of 120-150deg.C and pressure of 50-200 KPa under helium protection, and maintaining 24-48 h; the glow treatment comprises the following steps: argon plasma is adopted, the power is 20-100W, and the time is 5-20 min.
6. A rare earth metal doped porphyrin COFs/carbon based quantum dot/In based porphyrin according to claim 1 2 O 3 The application of the composite film sensor in detecting ppb level 2-butanone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310699713.0A CN116429850B (en) | 2023-06-14 | 2023-06-14 | Based on rare earth metal doped porphyrin COFs/carbon-based quantum dot/In 2 O 3 Composite film sensor and its making method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310699713.0A CN116429850B (en) | 2023-06-14 | 2023-06-14 | Based on rare earth metal doped porphyrin COFs/carbon-based quantum dot/In 2 O 3 Composite film sensor and its making method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116429850A CN116429850A (en) | 2023-07-14 |
| CN116429850B true CN116429850B (en) | 2023-09-22 |
Family
ID=87091153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310699713.0A Active CN116429850B (en) | 2023-06-14 | 2023-06-14 | Based on rare earth metal doped porphyrin COFs/carbon-based quantum dot/In 2 O 3 Composite film sensor and its making method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116429850B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104833707A (en) * | 2015-05-29 | 2015-08-12 | 南京信息工程大学 | Planar gas-sensitive sensing element and manufacturing method thereof |
| CN108535336A (en) * | 2018-04-24 | 2018-09-14 | 南京信息工程大学 | A kind of preparation method of graphene/molybdenum disulfide/cadmium sulfide composite sensing material |
| CN110975918A (en) * | 2019-12-18 | 2020-04-10 | 武汉理工大学 | Indium zinc sulfide-nitrogen doped graphene foam composite photocatalytic material and preparation method and application thereof |
| CN112014445A (en) * | 2020-09-04 | 2020-12-01 | 南京信息工程大学 | Ternary composite material and application thereof |
| CN113075266A (en) * | 2021-03-25 | 2021-07-06 | 南京信息工程大学 | NGQD/Fe2O3Graphene foam composite film and preparation method and application thereof |
| CN114076783A (en) * | 2021-11-17 | 2022-02-22 | 吉林大学 | 2-butanone sensor based on ZnO nano sensitive material and preparation method thereof |
-
2023
- 2023-06-14 CN CN202310699713.0A patent/CN116429850B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104833707A (en) * | 2015-05-29 | 2015-08-12 | 南京信息工程大学 | Planar gas-sensitive sensing element and manufacturing method thereof |
| CN108535336A (en) * | 2018-04-24 | 2018-09-14 | 南京信息工程大学 | A kind of preparation method of graphene/molybdenum disulfide/cadmium sulfide composite sensing material |
| CN110975918A (en) * | 2019-12-18 | 2020-04-10 | 武汉理工大学 | Indium zinc sulfide-nitrogen doped graphene foam composite photocatalytic material and preparation method and application thereof |
| CN112014445A (en) * | 2020-09-04 | 2020-12-01 | 南京信息工程大学 | Ternary composite material and application thereof |
| CN113075266A (en) * | 2021-03-25 | 2021-07-06 | 南京信息工程大学 | NGQD/Fe2O3Graphene foam composite film and preparation method and application thereof |
| CN114076783A (en) * | 2021-11-17 | 2022-02-22 | 吉林大学 | 2-butanone sensor based on ZnO nano sensitive material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Three-Dimensional van der Waals Heterostructure-Based Nanocages as Supersensitive 3‑Hydroxy-2-butanone Gas Sensors at Room Temperature;Shaofeng Shao 等;《ACS Sens.》;第8卷;228-242 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116429850A (en) | 2023-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Qian et al. | Planar perovskite solar cells with 15.75% power conversion efficiency by cathode and anode interfacial modification | |
| CN105469996B (en) | A kind of perovskite solar cell based on metal nanoparticle modifying interface and preparation method thereof | |
| JP6063039B2 (en) | Fuel cell electrode and manufacturing method thereof | |
| JP4093532B2 (en) | Method for producing amorphous metal oxide thin film material | |
| CN108205008B (en) | Toxin sensor based on organic photoelectric chemical transistor and preparation method thereof | |
| CN105239054B (en) | A kind of preparation facilities and method of micron grain size organic inorganic hybridization perovskite thin film | |
| KR101816800B1 (en) | Method of preparing metal nano wire and 3D metal nano catalyst | |
| JP2012114424A (en) | Solar cell and method of manufacturing the same | |
| Luck et al. | Improved uniformity in high-performance organic photovoltaics enabled by (3-aminopropyl) triethoxysilane cathode functionalization | |
| CN106496913A (en) | The preparation method of a kind of silicon chip/graphene oxide/poly-4 vinylpyridine brush/polypyrrole gold nano composites | |
| JP5194893B2 (en) | Dye-sensitized photoelectric conversion element and solar cell | |
| CN116429850B (en) | Based on rare earth metal doped porphyrin COFs/carbon-based quantum dot/In 2 O 3 Composite film sensor and its making method and application | |
| CN106409935B (en) | A kind of MoO3/MoS2/ LiF flexibility heterojunction solar batteries and preparation method thereof | |
| CN107271488A (en) | A kind of preparation method of nano composite structure gas sensitive | |
| Zhou et al. | Solution-processable ZnO/3-aminopropyltriethoxysilane hybrid cathode interlayer for non-fullerene organic solar cells | |
| Li et al. | Chemiresistive Polymer Percolation Network Gas Sensor Created with a Nanosphere Template | |
| CN110429032A (en) | One kind being based on Ni3(HITP)2The preparation method of the field effect transistor of conductive MOF film | |
| CN105789453A (en) | Self-assembly micromolecule with chlorine substituent and method for improving work content of electrode | |
| CN116539676B (en) | Sensor based on metal phthalocyanine MOFs nano-sphere array with multistage mesoporous structure, and preparation method and application thereof | |
| CN110455875B (en) | Gas sensitive material, gas sensor and preparation method thereof | |
| CN114361339A (en) | Perovskite solar cell and preparation method thereof | |
| TWI509103B (en) | Manufacturing method of platinum nanoparticles solution and self-assembled platinum counter electrode | |
| Smirnov et al. | Vertically aligned carbon nanotubes for microelectrode arrays applications | |
| CN111234304A (en) | Polyaniline @ silver nanowire/polyimide porous gradient composite film, preparation method and application | |
| Bhardwaj et al. | Attribution of H+ Transportation of Nafion-Film on Different Substrates Using Planar Inter-Digitated Electrodes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |