CN113818010A - Method for modifying organic polymer material and modified organic polymer material - Google Patents
Method for modifying organic polymer material and modified organic polymer material Download PDFInfo
- Publication number
- CN113818010A CN113818010A CN202111250641.9A CN202111250641A CN113818010A CN 113818010 A CN113818010 A CN 113818010A CN 202111250641 A CN202111250641 A CN 202111250641A CN 113818010 A CN113818010 A CN 113818010A
- Authority
- CN
- China
- Prior art keywords
- organic polymer
- polymer material
- precursor
- reaction chamber
- layer deposition
- 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.)
- Pending
Links
- 229920000620 organic polymer Polymers 0.000 title claims abstract description 109
- 239000002861 polymer material Substances 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 62
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 107
- 239000002243 precursor Substances 0.000 claims abstract description 107
- 238000006243 chemical reaction Methods 0.000 claims abstract description 97
- 239000012159 carrier gas Substances 0.000 claims abstract description 29
- 238000007789 sealing Methods 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000010926 purge Methods 0.000 claims abstract description 21
- 239000011261 inert gas Substances 0.000 claims abstract description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims description 26
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 22
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 22
- -1 polyethylene Polymers 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 12
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 10
- 239000004793 Polystyrene Substances 0.000 claims description 8
- GIRKRMUMWJFNRI-UHFFFAOYSA-N tris(dimethylamino)silicon Chemical compound CN(C)[Si](N(C)C)N(C)C GIRKRMUMWJFNRI-UHFFFAOYSA-N 0.000 claims description 8
- 229920002223 polystyrene Polymers 0.000 claims description 6
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 5
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims description 5
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 238000002715 modification method Methods 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 229920002530 polyetherether ketone Polymers 0.000 claims description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 5
- 229920006324 polyoxymethylene Polymers 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 5
- QYKABQMBXCBINA-UHFFFAOYSA-N 4-(oxan-2-yloxy)benzaldehyde Chemical compound C1=CC(C=O)=CC=C1OC1OCCCC1 QYKABQMBXCBINA-UHFFFAOYSA-N 0.000 claims description 4
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- OWKFQWAGPHVFRF-UHFFFAOYSA-N n-(diethylaminosilyl)-n-ethylethanamine Chemical compound CCN(CC)[SiH2]N(CC)CC OWKFQWAGPHVFRF-UHFFFAOYSA-N 0.000 claims description 4
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 4
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 4
- 239000005049 silicon tetrachloride Substances 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 2
- 229920001230 polyarylate Polymers 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 abstract description 25
- 238000005516 engineering process Methods 0.000 abstract description 15
- 239000000126 substance Substances 0.000 abstract description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 31
- 239000007789 gas Substances 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- 238000000151 deposition Methods 0.000 description 12
- 230000001276 controlling effect Effects 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 229920006254 polymer film Polymers 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 238000005121 nitriding Methods 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 235000012431 wafers Nutrition 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000012466 permeate Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000000861 blow drying Methods 0.000 description 4
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000005468 ion implantation Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000004584 weight gain Effects 0.000 description 4
- 235000019786 weight gain Nutrition 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005255 carburizing Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012994 photoredox catalyst Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003380 quartz crystal microbalance Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000012705 liquid precursor Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920006290 polyethylene naphthalate film Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/301—AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
- C23C16/303—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
- C23C16/345—Silicon nitride
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45555—Atomic layer deposition [ALD] applied in non-semiconductor technology
-
- 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
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The present invention relates to a method for modifying an organic polymer material and a modified organic polymer material. The method for modifying the organic polymer material comprises the following steps: 1) placing the organic polymer material in an atomic layer deposition reaction chamber; 2) introducing a carrier gas into the precursor 1, sealing the atomic layer deposition reaction chamber for the first time, wherein the first sealing time is 180-600 s, and introducing an inert gas for purging; 3) then introducing the precursor 2, and sealing the atomic layer deposition reaction chamber for the second time, wherein the sealing time for the second time is 180-600 s; the precursor 2 is selected from ammonia plasma or mixed plasma of nitrogen and hydrogen. The invention uses ALD technology, uses nitrogen-containing precursor as main raw material, makes nitride be filled into organic polymer material with proper filling depth and filling density, and forms film on its surface, so as to obtain modified organic polymer material with good chemical and mechanical properties.
Description
Technical Field
The invention relates to the technical field of material modification, in particular to a modification method of an organic polymer material and the modified organic polymer material.
Background
The modification method of the organic polymer material mainly comprises an ion implantation technology, a plastic filling modification technology, a surface carburization and nitridation technology, a chemical vapor deposition technology and an atomic layer deposition technology (ALD).
Ion implantation refers to the process of irradiating a solid material with a beam of ion beams in vacuum, wherein after the ions are irradiated into the material, the ions and atoms or molecules in the material undergo a series of physical and chemical actions so as to gradually lose energy and slowly decelerate, and finally stay in the solid, and finally cause the surface composition, structure and performance of the material to change. Because high energy is needed for generating ions, when the high-energy ions are contacted with the surface of an organic inert material, the chemical bonds of organic matters are broken to cause structural damage or ablation, the expected surface performance is damaged, lattice defects are generated, and black spots or surface roughness is increased; in addition, the ion implantation mostly uses impurity ions, which can cause that the ion species can not be regulated and controlled, and unwanted impurities are introduced into the organic polymer material, thereby affecting the performance of the organic polymer material.
The plastic filling modification technology is characterized in that in the process of polymerizing a plastic matrix into organic macromolecules, materials such as glass fibers, carbon fibers, metal fibers, mica and the like are filled, and the mechanics and heat resistance of the filled plastic are remarkably improved. However, this method is not suitable for organic polymer materials that have already been formed and, after the polymer is formed, the organic polymer materials are difficult to degrade back into small molecules for re-doping.
Surface carburizing and nitriding techniques are used in the treatment of metals, particularly low carbon and low alloy steels. The workpiece is placed in a high-carbon atmosphere with high activity, the single-phase austenite region with the temperature of 900-. However, the carburizing process requires relatively high temperature, and many common organic polymer materials are difficult to resist high temperature. The other nitriding process, especially the gas nitriding process, has the same characteristics. However, ion nitriding (glow nitriding) belongs to both nitriding technology and ion implantation technology, impurities such as hydrogen and ammonia are introduced in the nitriding process, and high-energy ions damage the surface of an organic matter due to the generation of glow plasma.
Chemical vapor deposition is an expanded atomic layer deposition technology, and is different from atomic layer deposition in that two precursor reactants are introduced into a reaction chamber together by the chemical vapor deposition, so that a thin film is formed by reaction. Since the two components are introduced together, the bulk phase reaction is followed by adhesion to the surface of the substrate to form a film, and thus the kinetic energy is not sufficient to enter the organic polymer material for adhesion, and it is difficult for the product adhered to the substrate to permeate into the organic polymer substrate.
Atomic Layer Deposition (ALD), a new technology for preparing nano-scale thin films, is based on the technical principle that precursors are alternately introduced into a cavity to generate single-layer saturated adsorption reaction, so that self-limiting layer-by-layer deposition is realized. Therefore, the film prepared based on ALD has the characteristics of excellent three-dimensional conformality, surface uniformity and the like, and meanwhile, the accurate sub-monolayer film thickness control can be guaranteed. Due to the unique growth mode and deposition characteristics, the method can directly form a compact film on the surface of a complex substrate, has conformality on an uneven sample and three-dimensional surface packaging, is easy to extend, and is an ideal means for depositing the film on an organic inert material.
Based on the ALD technique, it is expected that the organic polymer material is modified to improve the chemical and mechanical properties of the organic polymer material. At present, a means of modifying an oxide and an organic polymer material by compounding the oxide and the organic polymer material by using an oxygen source as a precursor through an ALD technique has been reported. However, the difficulty of depositing or filling nitrides on organic polymer materials by ALD techniques is relatively greater than that of oxides, and is not easy to achieve, which also limits the development of ALD techniques to a wider field.
Disclosure of Invention
The invention provides a method for modifying an organic polymer material, which is characterized in that an ALD (atomic layer deposition) technology is utilized, a nitrogen-containing precursor is used as a main raw material, nitride is filled into the organic polymer material at a proper filling depth and filling density, and a thin film is formed on the surface of the organic polymer material, so that the modified organic polymer material with better chemical and mechanical properties is obtained.
The method for modifying the organic polymer material comprises the following steps:
1) placing the organic polymer material in an atomic layer deposition reaction chamber;
2) introducing a carrier gas into the precursor 1, sealing the atomic layer deposition reaction chamber for the first time, wherein the first sealing time is 180-600 s, and introducing an inert gas for purging; the precursor 1 is selected from trimethylaluminum, diethylzinc, titanium tetrachloride, silicon tetrahydride, magnesium dicyclopentadienyl, aluminum trichloride, bis (diethylamino) silane, tris (dimethylamino) silane, silicon tetrachloride, Mn (EtCp)2Or Mn (thd)3；
3) Then introducing the precursor 2, and sealing the atomic layer deposition reaction chamber for the second time, wherein the sealing time for the second time is 180-600 s; the precursor 2 is selected from ammonia plasma or mixed plasma of nitrogen and hydrogen.
In one embodiment, when the precursor 1 is introduced, the temperature of the atomic layer deposition reaction chamber is 25-200 ℃, the pulse time of introducing the precursor 1 is 0.1-60 s, and the flow rate of the carrier gas is 50-150 sccm.
In one embodiment, after the precursor 1 is introduced, the vacuum degree of the atomic layer deposition reaction chamber is 100Pa to 150 Pa.
In one embodiment, when the precursor 2 is introduced, the temperature of the atomic layer deposition reaction chamber is 25 ℃ to 200 ℃, and the pulse time for introducing the precursor 2 is 0.1s to 60 s.
In one embodiment, after the precursor 2 is introduced, the vacuum degree of the atomic layer deposition reaction chamber is 200Pa to 500 Pa.
In one embodiment, the organic polymer material is selected from the group consisting of PVC polyvinyl chloride film, PE polyethylene film, PP polypropylene film, PS polystyrene film, ABS modified polystyrene film, PC polycarbonate, PA polyamide, PMMA polymethylmethacrylate film, POM polyoxymethylene film, PET polyethylene terephthalate film, PBT polybutylene terephthalate film, PDMS polydimethylsiloxane film, PEN polyethylene naphthalate film, PPs polyphenylene sulfide film, PEEK polyether ether ketone film, PSF polysulfone film, PI polyimide film, PAR polyester film, LCP liquid crystal polymer film
In one embodiment, the method further comprises the step of cleaning the organic polymer material before placing the organic polymer material in the atomic layer deposition reaction chamber.
In one embodiment, after the second sealing time is over, the method further comprises the steps of introducing inert gas for purging, and repeating the step 2) and the step 3).
In one embodiment, the carrier gas is selected from He, Ne, Ar or Kr.
In one embodiment, the inert gas is selected from He, Ne, Ar or Kr.
The invention also provides a modified organic polymer material prepared by the modification method.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the ALD technology is utilized to fill the nitride into the organic polymer material with proper filling depth and filling density, and a thin film is formed on the surface of the nitride, so that the modified organic polymer material with good chemical and mechanical properties is obtained. Compared with the traditional step of alternately introducing precursors into an atomic layer deposition reaction chamber, the method disclosed by the invention has the advantages that the reaction chamber is closed after the precursors 1 and 2 are introduced, in the closed reaction chamber, the precursors 1 fully permeate into the organic polymer material, a layer of substance is left in the organic polymer material and on the surface of the organic polymer material, then the precursors 2 are introduced to react with the surface of the organic polymer material and the precursors 1 in the organic polymer material to generate nitride, the problem that the nitride is difficult to deposit or fill on the organic polymer material by the ALD technology is solved by controlling the closing time of the reaction chamber, the filling of the nitride in the organic polymer material is successfully realized, and a nitride film is formed on the surface of the organic polymer. The method does not use high-energy particle bombardment and can not cause damage to organic matters; the byproducts are all gaseous and can be removed by purging without introducing additional impurities, and the ALD reaction windows of the precursors 1 and 2 are below the glass transition temperature and the decomposition temperature of the organic polymer material and do not cause the organic matter to denature and decompose. Meanwhile, the nitride is successfully filled in the organic polymer material and covered on the surface, so that the Young modulus of the organic polymer is favorably changed, the adhesive force of the film and the organic polymer substrate is improved, and the desorption probability is reduced.
Drawings
FIG. 1 is a graph showing the weight gain of each cyclic film in example 1;
FIG. 2 is a schematic diagram of the distribution of aluminum elements in a cross section of the polymer of example 1;
fig. 3 is a graphical representation of the weight gain of each recycled film of comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
ALD: atomic Layer Deposition (ALD) layer deposition.
Precursor: reactant precursor used in atomic layer deposition.
Carrier gas: an inert gas used in atomic layer deposition to carry reactants into the reaction chamber that does not react with any of the materials in the reaction chamber.
A flow meter: a gas flowmeter MFC is a device capable of accurately controlling the mass flow rate of a gas.
Sccm: standard pressure, flow of gas per minute (cc or mL) at standard temperature.
Temperature window: in atomic layer deposition, the ALD reaction has the highest temperature interval of the most stable growth rate.
A source bottle: the container for storing the precursor reactant is made of stainless steel.
Pulse: the precursor has certain vapor pressure, and the amount of the precursor required by ALD reaction is small, so that the purpose of introducing a proper amount of the precursor is achieved by opening and closing the precursor control valve instantly in a pulse mode.
At present, a means of modifying an oxide and an organic polymer material by compounding the oxide and the organic polymer material by using an oxygen source as a precursor through an ALD technique has been reported. However, the difficulty of depositing or filling nitrides on organic polymer materials by ALD techniques is relatively greater than that of oxides, and is not easy to achieve, which also limits the development of ALD techniques to a wider field. Specifically, the method comprises the following steps: the difficulties of depositing or filling nitrides on organic polymeric materials by ALD techniques are mainly: 1) the nitrogen source is of limited variety. 2) The energy required by the nitrogen source to participate in the reaction is higher than that of the oxygen source.
The present invention overcomes the above-mentioned difficulties and provides a method for modifying an organic polymeric material.
The technical scheme is as follows:
a method of modifying an organic polymeric material, comprising the steps of:
1) placing the organic polymer material in an atomic layer deposition reaction chamber;
2) introducing a carrier gas into the precursor 1, sealing the atomic layer deposition reaction chamber for the first time, wherein the first sealing time is 180-600 s, and introducing an inert gas for purging; the precursor 1 is selected from trimethylaluminum, diethylzinc, titanium tetrachloride, silicon tetrahydride, magnesium dicyclopentadienyl, aluminum trichloride, bis (diethylamino) silane, tris (dimethylamino) silane, silicon tetrachloride, Mn (EtCp)2Or Mn (thd)3；
3) Then introducing the precursor 2, and sealing the atomic layer deposition reaction chamber for the second time, wherein the sealing time for the second time is 180-600 s; the precursor 2 is selected from ammonia plasma or mixed plasma of nitrogen and hydrogen.
Specifically, in one embodiment, the organic polymer material is selected from one or more of PVC polyvinyl chloride, PE polyethylene, PP polypropylene, PS polystyrene, ABS modified polystyrene, PC polycarbonate, PA polyamide, PMMA polymethylmethacrylate, POM polyoxymethylene, PET polyethylene terephthalate, PBT polybutylene terephthalate, PDMS polydimethylsiloxane, PEN polyethylene naphthalate, PPs polyphenylene sulfide, PEEK polyether ether ketone, PSF polysulfone, PI polyimide, PAR polyarylate, and LCP liquid crystal polymer.
It is understood that the organic polymer material may be an organic polymer thin film or an organic polymer substrate.
In one embodiment, the method further comprises the step of cleaning the organic polymer material before placing the organic polymer material in the atomic layer deposition reaction chamber. Specifically, the cleaning is as follows:
respectively ultrasonically cleaning an organic polymer material (smaller than the size of an atomic layer deposition reaction chamber) for 15min by using acetone, absolute ethyl alcohol and deionized water, blow-drying by using nitrogen after cleaning, placing in an inert gas environment, and cleaning the surface of the organic polymer material by using low-power inert gas plasma (such as Ar and He plasma) when necessary. Through the measures, a large number of possibly uneven nucleation sites on the surface of the organic polymer material can be eliminated, so that the process of penetrating the precursor 1 and the precursor 2 into the organic polymer material is smoother, and the precursors cannot be captured by the surface sites in a large number. The degree of cleaning is controlled, and the penetration depth and filling depth of the precursors 1 and 2 can also be indirectly controlled.
In one embodiment, before the carrier gas is introduced into the precursor 1, the method further comprises vacuumizing the atomic layer deposition reaction chamber by using a vacuum pump, so that the vacuum degree is below 250 Pa.
In one embodiment, before the carrier gas is introduced into the precursor 1, a carrier gas of 20sccm to 1000sccm is introduced through a carrier gas control valve, so that the temperature and the pressure of the atomic layer deposition reaction chamber are stable.
In one embodiment, the source bottle is connected to the gas carrier line at a central location by a precursor control valve. The precursor 1 is placed in a source bottle of the atomic layer deposition equipment, and the precursor 1 has enough vapor pressure and can be brought into an atomic deposition reaction chamber by carrier gas along a pipeline by heating the source bottle.
It can be understood that for the precursor 1 with high activity and high vapor pressure, the temperature for heating the source bottle can be kept at the normal temperature of 25 ℃ +/-10 ℃. For low activity liquid precursor 1, the heating temperature to the source bottle was maintained between 40 ℃ and 150 ℃. For the solid precursor 1, the heating temperature of the source bottle also needs to be controlled between 50 ℃ and 150 ℃.
The temperature of the pipeline is regulated so that the precursor 1 in the source bottle can not be condensed on the inner wall of the pipeline, and the temperature of the pipeline is generally set to be more than 100 ℃ and below the degradation or decomposition temperature of the precursor.
It will be appreciated that the line temperature and source bottle temperature required for different precursors 1 will be different.
In one embodiment, an ALD reaction to form nitrides, such as trimethylaluminum and ammonia, is used to grow aluminum nitride films in a temperature window of 150 ℃ and 600 ℃, the temperature for heating the source bottle of precursor 1 is below 80 ℃, and the temperature for keeping the piping of precursor 1 below 150 ℃.
In one embodiment, when the precursor 1 is introduced, the temperature of the atomic layer deposition reaction chamber is 25-200 ℃, the pulse time of introducing the precursor 1 is 0.1-60 s, and the flow rate of the carrier gas is 50-150 sccm.
It is understood that for higher activity trimethylaluminum, diethylzinc, titanium tetrachloride, silicon tetrahydride, and magnesium metallocene, the temperature of the ald reaction chamber needs to be controlled below the decomposition temperature of precursor 1 and the decomposition temperature of organic materials when the precursor 1 is introduced. Less reactive aluminum trichloride, bis (diethylamino) silane, tris (dimethylamino) silane, silicon tetrachloride, Mn (EtCp)2Or Mn (thd)3When the precursor 1 is introduced, the temperature of the atomic layer deposition reaction chamber needs to be controlled to be above the ALD window and below the decomposition temperature of the precursor 1 and the decomposition temperature of the organic matter.
In one embodiment, after the precursor 1 is introduced, the vacuum degree of the atomic layer deposition reaction chamber is 100Pa to 150 Pa.
And after the precursor 1 is introduced, the atomic layer deposition reaction chamber is closed for the first time. Specifically, the vacuum pump, the gas carrying control valve and the precursor control valve are closed, so that the reaction chamber is in a completely closed state, and a closed space is formed. In this process, since the molecular free path of the precursor 1 is large, the precursor 1 rapidly diffuses in the reaction chamber and contacts with the organic polymer material, and the organic polymer material is inert according to the theory of permeation, and the pores are larger than the molecules of the precursor 1, the precursor 1 diffuses and permeates into the organic polymer material, is partially adsorbed on the surface of the organic polymer material, and partially permeates into the organic polymer material with the large pores.
Optionally, the first closure time is from 180s to 600 s. Preferably, the first sealing time is 180s-240 s. Further preferably, the first blocking time is 180s to 200 s. The first closing time is controlled, and the filling depth of the subsequent nitride can be controlled.
And after the first sealing time is finished, introducing inert gas, purging and cleaning the atomic layer deposition reaction chamber, purging and cleaning redundant precursor 1 in the reaction chamber, and avoiding subsequent bulk phase reaction.
Optionally, the purging and cleaning time is 5 s-30 min, and the flow rate of the inert gas is 50sccm-1000 sccm.
And after the purging and cleaning are finished, the precursor 2 is pulsed.
It is understood that the precursor 2 is a gas that can be directly introduced into the ald reaction chamber.
In one embodiment, the volume fraction of nitrogen is 85% to 95% and the volume fraction of hydrogen is 5% to 15% in the mixed plasma of nitrogen and hydrogen.
In one embodiment, when the precursor 2 is introduced, the temperature of the atomic layer deposition reaction chamber is 25 ℃ to 200 ℃, and the pulse time for introducing the precursor 2 is 0.1s to 60 s.
In one embodiment, after the precursor 2 is introduced, the vacuum degree of the atomic layer deposition reaction chamber is 200Pa to 500 Pa.
And after the precursor 2 is introduced, closing the atomic layer deposition reaction chamber for the second time. Specifically, the vacuum pump and the precursor control valve are closed, so that the reaction chamber is in a completely closed state, and a closed space is formed. In the process, the precursor 2 reacts with the precursor 1 adsorbed on the surface of the organic polymer material and in the organic matter to generate nitride, so that the nitride can be successfully filled in the organic polymer material, and a nitride film is formed on the surface of the organic polymer.
It is understood that depending on the ALD reaction, heat is evolved or absorbed concomitantly. The precursor 2 can be promoted to continuously diffuse into the organic matter no matter in exothermic reaction or endothermic reaction, and the effect of deep filling is achieved on the basis of completely reacting the precursor 1 in the organic polymer material. Among these, the exothermic ALD reaction is more favorable for diffusion.
Optionally, the second sealing time is 180s-600 s. Preferably, the second sealing time is from 180s to 240 s. Further preferably, the second sealing time is 180s to 200 s. The second closing time is controlled, and the filling depth of the subsequent nitride can be controlled.
In one embodiment, after the second sealing time is finished, the method further comprises the steps of introducing inert gas for purging, and repeating the step 2) and the step 3).
As can be understood, inert gas is introduced to purge and clean the atomic layer deposition reaction chamber, and the redundant precursor 2 in the reaction chamber is purged and removed, so that the subsequent bulk phase reaction is avoided.
Optionally, the purging and cleaning time is 5 s-30 min, and the flow rate of the inert gas is 50sccm-1000 sccm.
By repeating the step 2) and the step 3), the filling depth and the filling density of the nitride in the organic polymer material can be controlled, and the chemical and mechanical properties of the modified organic polymer material can be controlled.
According to the invention, the ALD technology is utilized to fill the nitride into the organic polymer material with proper filling depth and filling density, and a thin film is formed on the surface of the nitride, so that the modified organic polymer material with good chemical and mechanical properties is obtained. Compared with the traditional step of alternately introducing precursors into an atomic layer deposition reaction chamber, the method disclosed by the invention has the advantages that after the precursors 1 and 2 are introduced, the reaction chamber is closed, in the closed reaction chamber, the precursors 1 fully permeate into the organic polymer material, a layer of substance is left in the organic polymer material and on the surface of the organic polymer material, then the precursors 2 are introduced to react with the surface of the organic polymer material and the precursors 1 in the organic polymer material to generate nitrides, the filling of the nitrides in the organic polymer material is successfully realized by controlling the closing time of the reaction chamber, and a nitride film is formed on the surface of the organic polymer. The method does not use high-energy particle bombardment and can not cause damage to organic matters; the byproducts are all gaseous and can be removed by purging without introducing additional impurities, and the ALD reaction windows of the precursors 1 and 2 are below the glass transition temperature and the decomposition temperature of the organic polymer material and do not cause the organic matter to denature and decompose.
The invention also provides a modified organic polymer material prepared by the modification method. The nitride is successfully filled in the organic polymer material and covered on the surface, so that the Young modulus of the organic polymer is favorably changed, the adhesion of the film and the organic polymer substrate is improved, and the desorption probability is reduced.
It is understood that the atomic layer deposition reaction chamber refers to a reaction chamber capable of implementing atomic layer deposition techniques including, but not limited to, time-isolated atomic layer deposition or spatially isolated atomic layer deposition, thermal atomic layer deposition, or plasma enhanced atomic layer deposition techniques.
The following examples and comparative examples are further described below, and the starting materials used in the following examples can be commercially available, unless otherwise specified, and the equipment used therein can be commercially available, unless otherwise specified.
Example 1
The embodiment provides a method for modifying an organic polymer material and a modified organic polymer material, and the method comprises the following specific steps:
step 1: ultrasonic cleaning PDMS (polydimethylsiloxane) polymer film with acetone, anhydrous ethanol and deionized water for 15min, blow-drying with nitrogen, placing in inert gas environment, and cleaning surface with He plasma.
Step 2: the method comprises the steps of using self-built plasma enhanced atomic layer deposition equipment, placing a PDMS (polydimethylsiloxane) film with the thickness of 1 micrometer after cleaning in an atomic layer deposition reaction chamber of the equipment, vacuumizing the atomic layer deposition reaction chamber by using a vacuum pump, opening a carrier gas control valve, introducing carrier gas He of 100sccm into the atomic layer deposition reaction chamber, placing trimethylaluminum in a source bottle of the atomic layer deposition equipment, and heating to 28 ℃.
And step 3: controlling the temperature of the atomic layer deposition reaction chamber to be 95 ℃, opening a precursor control valve, introducing trimethylaluminum along with carrier gas pulse, wherein the pulse time is 2s, the carrier gas flow is 100sccm, the vacuum degree in the reaction chamber is 100-150Pa, closing a vacuum pump, the carrier gas control valve and the precursor control valve, and sealing the atomic layer deposition reaction chamber for the first time, wherein the first sealing time is 120 s.
And 4, step 4: and opening the vacuum pump and the gas carrying control valve, introducing He, and purging and cleaning for 1min at the flow rate of 100 sccm.
And 5: controlling the temperature of the atomic layer deposition reaction chamber to be 95 ℃, opening a precursor control valve, and introducing H with the volume fraction of 10%2And 90% (volume fraction) N2The pulse time of the formed mixed plasma is 20s, the vacuum degree in the reaction chamber is 200-250Pa, the vacuum pump, the gas-carrying control valve and the precursor control valve are closed, the atomic layer deposition reaction chamber is closed for the second time, and the second closing time is 60 s.
Step 6: and opening the vacuum pump and the gas carrying control valve, introducing He, and purging and cleaning for 1min at the flow rate of 100 sccm. And (5) repeating the steps 3-6, recording the steps 3-6 as one cycle, and performing the cycle for 100 times in total to obtain the modified organic polymer material.
And 7: detection of
And placing the inorganic silicon wafer substrate with the natural oxide layer on the surface in the plasma enhanced atomic layer deposition equipment, and depositing reactants on the silicon wafer substrate as a contrast while depositing the reactants in the PDMS by adopting the same reaction conditions as the steps. The characterization of the mass gain of the PDMS polymer film and the inorganic silicon wafer in each cycle was performed by using a quartz crystal microbalance, and the results are shown in fig. 1, in this example, the mass gain curve of the PDMS polymer film was fast first and slow later, which indicates that the trimethylaluminum precursor penetrated into the organic polymer substrate and finally reacted to form aluminum nitride, so that the mass gain did not meet the self-limiting characteristic of atomic layer deposition, until nearly 30 cycles, the substrate surface had formed a planar film from islands, and the weight gain was gradually the same as the weight gain of the inorganic silicon wafer substrate.
The cross section of the deposited polymer was probed for Al using EDS elemental spectroscopy module of SEM, and as a result, as shown in fig. 2, it was found that Al element, in addition to being concentrated at the surface, also penetrated into the underlying PDMS polymer substrate.
Example 2
This example provides a method of modifying an organic polymer material and a modified organic polymer material, which are different from those of example 1 in that: the precursors 1 are different, and the process parameters are different. The method comprises the following specific steps:
step 1: and ultrasonically cleaning the PDMS polymer film for 15min by using acetone, absolute ethyl alcohol and deionized water respectively, blow-drying by using nitrogen, placing the PDMS polymer film in an inert gas environment, and cleaning the surface by using He plasma.
Step 2: the method comprises the steps of using self-built plasma enhanced atomic layer deposition equipment, placing a cleaned PDMS film in an atomic layer deposition reaction chamber of the equipment, vacuumizing the atomic layer deposition reaction chamber by using a vacuum pump, opening a carrier gas control valve, introducing carrier gas He of 100sccm into the atomic layer deposition reaction chamber, placing tris (dimethylamino) silane TDMAS in a source bottle of the atomic layer deposition equipment, and heating to 30 ℃.
And step 3: controlling the temperature of the atomic layer deposition reaction chamber to be 120 ℃, opening a precursor control valve, introducing tris (dimethylamino) silane TDMAS along with carrier gas pulse, wherein the pulse time is 0.2s, the carrier gas flow is 100sccm, the vacuum degree in the reaction chamber is 100-150Pa, closing a vacuum pump, the carrier gas control valve and the precursor control valve, sealing the atomic layer deposition reaction chamber for the first time, and sealing for the first time for 180 s.
And 4, step 4: and opening the vacuum pump and the gas carrying control valve, introducing He, and purging and cleaning for 1min at the flow rate of 100 sccm.
And 5: controlling the temperature of the atomic layer deposition reaction chamber to be 120 ℃, opening a precursor control valve, and introducing H with the volume fraction of 10%2And 90% (volume fraction) N2The pulse time of the formed mixed plasma is 20s, the vacuum degree in the reaction chamber is 200-500Pa, the vacuum pump, the gas-carrying control valve and the precursor control valve are closed, the atomic layer deposition reaction chamber is closed for the second time, and the second closing time is 60 s.
Step 6: and opening a vacuum pump and a gas carrying control valve, introducing, purging and cleaning for 1min, wherein the flow rate is 100 sccm. And (5) repeating the steps 3-6, recording the steps 3-6 as one cycle, and performing the cycle for 100 times in total to obtain the modified organic polymer material.
Comparative example 1
This comparative example provides a method of modifying an organic polymer material and a modified organic polymer material, which are different from example 1 in that: the process parameters are different. The method comprises the following specific steps:
step 1: and ultrasonically cleaning the PDMS polymer film for 15min by using acetone, absolute ethyl alcohol and deionized water respectively, blow-drying by using nitrogen, placing the PDMS polymer film in an inert gas environment, and cleaning the surface by using He plasma.
Step 2: the self-built plasma enhanced atomic layer deposition equipment is used, a PDMS film with the thickness of 1 micrometer after cleaning is placed in an atomic layer deposition reaction chamber of the equipment, the atomic layer deposition reaction chamber is vacuumized by a vacuum pump, a carrier gas control valve is opened, carrier gas He of 100sccm is introduced into the atomic layer deposition reaction chamber, trimethylaluminum is placed in a source bottle of the atomic layer deposition equipment, and the heating is carried out to 28 ℃.
And step 3: controlling the temperature of the atomic layer deposition reaction chamber to be 95 ℃, opening a precursor control valve, introducing trimethylaluminum along with carrier gas pulse, wherein the pulse time is 2s, the carrier gas flow is 100sccm, the vacuum degree is 100-.
And 4, step 4: and opening the vacuum pump and the gas carrying control valve, introducing He, and purging and cleaning for 1min at the flow rate of 100 sccm.
And 5: controlling the temperature of the atomic layer deposition reaction chamber to be 95 ℃, opening a precursor control valve, and introducing N2And (3) plasma, wherein the pulse time is 20s, the vacuum degree is 200-250Pa, the vacuum pump, the gas carrying control valve and the precursor control valve are closed, the atomic layer deposition reaction chamber is closed for the second time, and the second closing time is 60 s.
Step 6: and opening the vacuum pump and the gas carrying control valve, introducing He, and purging and cleaning for 1min at the flow rate of 100 sccm. And (5) repeating the steps 3-6, recording the steps 3-6 as circulation once, and circulating for 100 times in total to obtain the modified organic polymer material.
And 7: detection of
And placing the inorganic silicon wafer substrate with the natural oxide layer on the surface in the plasma enhanced atomic layer deposition equipment, and depositing reactants on the silicon wafer substrate as a contrast while depositing the reactants in the PDMS by adopting the same reaction conditions as the steps.
The fitting of the thickness measurement of PDMS and inorganic silicon wafers using an AlN model in an elliptical polarization spectrometer model M2000 of J Wollam, the thickness of the fitting is substantially 0, which indicates that aluminum nitride cannot be grown and penetration cannot be generated by the process.
The comparative example was characterized for mass gain of the PDMS polymer film per cycle using a quartz crystal microbalance, and the results are shown in figure 3. Also, this process does not allow the growth of aluminum nitride and does not allow for penetration.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A method of modifying an organic polymeric material, comprising the steps of:
1) placing the organic polymer material in an atomic layer deposition reaction chamber;
2) introducing a carrier gas into the precursor 1, sealing the atomic layer deposition reaction chamber for the first time, wherein the first sealing time is 180-600 s, and introducing an inert gas for purging; the precursor 1 is selected from trimethylaluminum, diethylzinc, titanium tetrachloride, silicon tetrahydride, magnesium dicyclopentadienyl, aluminum trichloride, bis (diethylamino) silane, tris (dimethylamino) silane, silicon tetrachloride, Mn (EtCp)2Or Mn (thd)3；
3) Then introducing the precursor 2, and sealing the atomic layer deposition reaction chamber for the second time, wherein the sealing time for the second time is 180-600 s; the precursor 2 is selected from ammonia plasma or mixed plasma of nitrogen and hydrogen.
2. The method according to claim 1, wherein the atomic layer deposition reaction chamber is at a temperature of 25 ℃ to 200 ℃ when the precursor 1 is introduced, the pulse time for introducing the precursor 1 is 0.1s to 60s, and the flow rate of the carrier gas is 50sccm to 150 sccm.
3. The method for modifying an organic polymer material according to claim 2, wherein the degree of vacuum of the atomic layer deposition reaction chamber after the precursor 1 is introduced is 100Pa to 150 Pa.
4. The method according to claim 1, wherein the temperature of the ald reaction chamber is 25-200 ℃ and the pulse time for introducing the precursor 2 is 0.1-60 s when introducing the precursor 2.
5. The method for modifying an organic polymer material according to claim 4, wherein a vacuum degree of the atomic layer deposition reaction chamber after the precursor 2 is introduced is 200Pa to 500 Pa.
6. The method for modifying an organic polymer material according to any one of claims 1 to 5, wherein the organic polymer material is selected from one or more of polyvinyl chloride, polyethylene, polypropylene, polystyrene, ABS-modified polystyrene, polycarbonate, polyamide, polymethylmethacrylate, polyoxymethylene, polyethylene terephthalate, polybutylene terephthalate, polydimethylsiloxane, polyethylene naphthalate, polyphenylene sulfide, polyetheretherketone, polysulfone, polyimide, polyarylate and liquid crystal polymer.
7. The method for modifying an organic polymer material according to any one of claims 1 to 5, further comprising a step of cleaning the organic polymer material before placing the organic polymer material in the atomic layer deposition reaction chamber.
8. The method for modifying an organic polymer material according to any one of claims 1 to 5, wherein after the second sealing time is over, the method further comprises the steps of introducing inert gas for purging, and repeating the steps 2) and 3).
9. The method of modifying an organic polymer material according to any one of claims 1 to 5, wherein the carrier gas is selected from He, Ne, Ar or Kr; and/or
The inert gas is selected from He, Ne, Ar or Kr.
10. A modified organic polymer material, characterized by being produced by the modification method according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111250641.9A CN113818010A (en) | 2021-10-26 | 2021-10-26 | Method for modifying organic polymer material and modified organic polymer material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111250641.9A CN113818010A (en) | 2021-10-26 | 2021-10-26 | Method for modifying organic polymer material and modified organic polymer material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113818010A true CN113818010A (en) | 2021-12-21 |
Family
ID=78917369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111250641.9A Pending CN113818010A (en) | 2021-10-26 | 2021-10-26 | Method for modifying organic polymer material and modified organic polymer material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113818010A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114318292A (en) * | 2021-12-31 | 2022-04-12 | 中储粮成都储藏研究院有限公司 | Method for coating flame-retardant film layer by chemical vapor deposition method |
| CN116271213A (en) * | 2023-03-13 | 2023-06-23 | 浙江广慈医疗器械有限公司 | Polyether-ether-ketone-based high-activity biological fusion device, preparation method and application thereof |
| CN118389997A (en) * | 2024-06-26 | 2024-07-26 | 深圳市汉嵙新材料技术有限公司 | Two-dimensional polymer film material and preparation method thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295657A (en) * | 2010-06-02 | 2011-12-28 | 气体产品与化学公司 | Organoaminosilane precursors and methods for depositing films comprising the same |
| CN103219434A (en) * | 2012-01-18 | 2013-07-24 | 陈敏璋 | Composite substrate, manufacturing method thereof and light emitting component |
| CN109478497A (en) * | 2016-07-22 | 2019-03-15 | Dnf 有限公司 | Utilize the preparation method of the silicon nitride film of Plasma-Atomic layer sedimentation |
| US20190086807A1 (en) * | 2017-09-21 | 2019-03-21 | Asm Ip Holding B.V. | Method of sequential infiltration synthesis treatment of infiltrateable material and structures and devices formed using same |
| CN110050086A (en) * | 2016-12-15 | 2019-07-23 | Asm Ip控股有限公司 | Sequence infiltration synthesis device |
| CN110177899A (en) * | 2016-12-15 | 2019-08-27 | Asm Ip控股有限公司 | Sequence infiltration synthesis device |
| KR20200059748A (en) * | 2018-11-21 | 2020-05-29 | 한양대학교 산학협력단 | Method of modifying the surface of polymer pattern |
| CN111218665A (en) * | 2020-01-17 | 2020-06-02 | 上海新微技术研发中心有限公司 | Method for low-temperature deposition of silicon nitride with adjustable optical performance on flexible substrate |
| KR102129316B1 (en) * | 2018-02-12 | 2020-07-02 | 한국기계연구원 | Organic-inorganic hybrid composite and method of manufacturing the same |
| CN111364017A (en) * | 2020-04-20 | 2020-07-03 | 国家纳米科学中心 | Aluminum nitride film and preparation method and application thereof |
| CN111378960A (en) * | 2020-04-27 | 2020-07-07 | 复旦大学 | Microwave-assisted atomic layer deposition method and reactor |
| US20210017649A1 (en) * | 2019-07-18 | 2021-01-21 | Uchicago Argonne, Llc | Sequential infiltration synthesis of group 13 oxide electronic materials |
-
2021
- 2021-10-26 CN CN202111250641.9A patent/CN113818010A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295657A (en) * | 2010-06-02 | 2011-12-28 | 气体产品与化学公司 | Organoaminosilane precursors and methods for depositing films comprising the same |
| CN103219434A (en) * | 2012-01-18 | 2013-07-24 | 陈敏璋 | Composite substrate, manufacturing method thereof and light emitting component |
| CN109478497A (en) * | 2016-07-22 | 2019-03-15 | Dnf 有限公司 | Utilize the preparation method of the silicon nitride film of Plasma-Atomic layer sedimentation |
| CN110050086A (en) * | 2016-12-15 | 2019-07-23 | Asm Ip控股有限公司 | Sequence infiltration synthesis device |
| CN110177899A (en) * | 2016-12-15 | 2019-08-27 | Asm Ip控股有限公司 | Sequence infiltration synthesis device |
| US20190086807A1 (en) * | 2017-09-21 | 2019-03-21 | Asm Ip Holding B.V. | Method of sequential infiltration synthesis treatment of infiltrateable material and structures and devices formed using same |
| KR102129316B1 (en) * | 2018-02-12 | 2020-07-02 | 한국기계연구원 | Organic-inorganic hybrid composite and method of manufacturing the same |
| CN111819305A (en) * | 2018-02-12 | 2020-10-23 | 韩国机械研究院 | Organic-inorganic composite and preparation method thereof |
| KR20200059748A (en) * | 2018-11-21 | 2020-05-29 | 한양대학교 산학협력단 | Method of modifying the surface of polymer pattern |
| US20210017649A1 (en) * | 2019-07-18 | 2021-01-21 | Uchicago Argonne, Llc | Sequential infiltration synthesis of group 13 oxide electronic materials |
| CN111218665A (en) * | 2020-01-17 | 2020-06-02 | 上海新微技术研发中心有限公司 | Method for low-temperature deposition of silicon nitride with adjustable optical performance on flexible substrate |
| CN111364017A (en) * | 2020-04-20 | 2020-07-03 | 国家纳米科学中心 | Aluminum nitride film and preparation method and application thereof |
| CN111378960A (en) * | 2020-04-27 | 2020-07-07 | 复旦大学 | Microwave-assisted atomic layer deposition method and reactor |
Non-Patent Citations (1)
| Title |
|---|
| 冯丽萍等: "《薄膜技术与应用》", 29 February 2016, 西北工业大学出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114318292A (en) * | 2021-12-31 | 2022-04-12 | 中储粮成都储藏研究院有限公司 | Method for coating flame-retardant film layer by chemical vapor deposition method |
| CN114318292B (en) * | 2021-12-31 | 2024-03-29 | 中储粮成都储藏研究院有限公司 | Method for coating flame-retardant film layer by chemical vapor deposition method |
| CN116271213A (en) * | 2023-03-13 | 2023-06-23 | 浙江广慈医疗器械有限公司 | Polyether-ether-ketone-based high-activity biological fusion device, preparation method and application thereof |
| CN116271213B (en) * | 2023-03-13 | 2023-10-20 | 浙江广慈医疗器械有限公司 | Polyether-ether-ketone-based high-activity biological fusion device, preparation method and application thereof |
| CN118389997A (en) * | 2024-06-26 | 2024-07-26 | 深圳市汉嵙新材料技术有限公司 | Two-dimensional polymer film material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113818010A (en) | Method for modifying organic polymer material and modified organic polymer material | |
| TWI585857B (en) | Method of manufacturing semiconductor device, method of processing substrate and computer readable recording medium | |
| Elam et al. | Surface chemistry and film growth during TiN atomic layer deposition using TDMAT and NH3 | |
| US9330904B2 (en) | Method of manufacturing semiconductor device and substrate processing apparatus | |
| CA2690978C (en) | Method in depositing metal oxide materials | |
| TWI564963B (en) | Method of manufacturing semiconductor device and method of processing substrate | |
| US8956984B2 (en) | Method of manufacturing semiconductor device, method of processing substrate, substrate processing apparatus, and non-transitory computer-readable recording medium | |
| JP4258518B2 (en) | Film forming method, film forming apparatus, and storage medium | |
| Kim et al. | Remote plasma enhanced atomic layer deposition of TiN thin films using metalorganic precursor | |
| JP5651451B2 (en) | Semiconductor device manufacturing method, substrate processing method, and substrate processing apparatus | |
| US20080038486A1 (en) | Radical Assisted Batch Film Deposition | |
| TW201214561A (en) | Method of manufacturing semiconductor device and substrate processing apparatus | |
| JP2007051327A (en) | Film deposition method | |
| Jain et al. | About the importance of purge time in molecular layer deposition of alucone films | |
| Aghaee et al. | On the role of micro-porosity in affecting the environmental stability of atomic/molecular layer deposited (ZnO) a (Zn–O–C 6 H 4–O) b films | |
| CN106068335A (en) | Germanium or the ald of germanium oxide | |
| KR20170045138A (en) | Multi-step atomic layer deposition process for silicon nitride film formation | |
| CN114250453A (en) | Substrate processing apparatus and method for manufacturing semiconductor device | |
| CN113661269A (en) | Pulsed thin film deposition method | |
| JP2003236976A (en) | Silicon oxide coating film with excellent gas barrier property and packaging body using it | |
| JP5841222B2 (en) | Semiconductor device manufacturing method, substrate processing method, and substrate processing apparatus | |
| Johansson | Surface Modification of Plastics: Atomic Layer Deposition | |
| KR20010036268A (en) | Method for forming a metallic oxide layer by an atomic layer deposition | |
| JP2017150068A (en) | Diffusion rate-limiting thermochemical vapor deposition coating | |
| Fearn et al. | A kinetic Monte Carlo Model of Silicon CVD Growth from a Mixed H2/siH4 Gas Source |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211221 |