CN104592539B - Acid anhydride copolymer finishing coat for film block copolymer tropism control - Google Patents
Acid anhydride copolymer finishing coat for film block copolymer tropism control Download PDFInfo
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- CN104592539B CN104592539B CN201410409101.4A CN201410409101A CN104592539B CN 104592539 B CN104592539 B CN 104592539B CN 201410409101 A CN201410409101 A CN 201410409101A CN 104592539 B CN104592539 B CN 104592539B
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- 229920001400 block copolymer Polymers 0.000 title claims abstract description 86
- 229920001577 copolymer Polymers 0.000 title claims description 14
- 230000010415 tropism Effects 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 74
- 238000000137 annealing Methods 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 230000007935 neutral effect Effects 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000012528 membrane Substances 0.000 claims abstract description 9
- 239000010410 layer Substances 0.000 claims description 53
- 239000000758 substrate Substances 0.000 claims description 35
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 20
- 239000003513 alkali Substances 0.000 claims description 19
- 150000003839 salts Chemical group 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 9
- 238000004528 spin coating Methods 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 7
- -1 hydroxide radical anion Chemical class 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 239000011877 solvent mixture Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 229920006037 cross link polymer Polymers 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 150000003973 alkyl amines Chemical class 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 238000001338 self-assembly Methods 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 238000007385 chemical modification Methods 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 125000002524 organometallic group Chemical group 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 230000008961 swelling Effects 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 125000000524 functional group Chemical group 0.000 claims 1
- 238000013007 heat curing Methods 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- 239000002356 single layer Substances 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 38
- 238000010438 heat treatment Methods 0.000 abstract description 12
- 239000010409 thin film Substances 0.000 abstract description 9
- 238000005266 casting Methods 0.000 abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000002086 nanomaterial Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000000572 ellipsometry Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000012661 block copolymerization Methods 0.000 description 2
- 229920000359 diblock copolymer Polymers 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002094 self assembled monolayer Substances 0.000 description 2
- 239000013545 self-assembled monolayer Substances 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OXHSYXPNALRSME-UHFFFAOYSA-N (4-ethenylphenyl)-trimethylsilane Chemical compound C[Si](C)(C)C1=CC=C(C=C)C=C1 OXHSYXPNALRSME-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- ZMYGBKXROOQLMY-UHFFFAOYSA-N N=NC=NN.N=NC=NN.C1=CC=CC2=CC=CC=C12 Chemical compound N=NC=NN.N=NC=NN.C1=CC=CC2=CC=CC=C12 ZMYGBKXROOQLMY-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005400 gorilla glass Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 210000001258 synovial membrane Anatomy 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
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Abstract
Advanced Lithographic pattern is prepared using self-assembled block copolymers structure to depend on controlling the orientation of these structures in the film.Particularly, the orientation of the cylindrical body perpendicular to block copolymer membrane plane and sheet is needed in most applications.The preferred method for realizing orientation is to pass through heating.The present invention includes controlling Block Copolymer Thin Film by heating using dipole inversion (polarity-switching) finishing coat to be orientated.Finishing coat can be spin-coated on Block Copolymer Thin Film from polarity casting solvent, and it changes composition in thermal annealing and becomes " neutral ".Finishing coat can aid in the tropism control of block copolymer, and in addition to this only by heating, the tropism control is impossible.
Description
Cross reference to related applications
The part continuation application requires U. S. application the 13/761,918th preferential proposed on February 07th, 2013
Power, U.S. Provisional Application No. 61/597,327 priority which proposed on February 10th, 2012, it
Content be incorporated herein by reference.
Invention field
Advanced Lithographic pattern, which is prepared, using self-assembled block copolymers depends on its tropism control in the film.
Block copolymer can be made to be orientated by thermal annealing finishing coat, otherwise the orientation of block copolymer can be extremely difficult.Packet of the present invention
It includes using copolymer finishing coat, can be spin-coated on Block Copolymer Thin Film, and for by heating to control the block
The orientation of copolymer microcell, is then removed.The finishing coat can make existing in Block Copolymer Thin Film in no finishing coat
Under only by heat its will not be orientated microcell orientation.
Background of invention
It is well known [1] that diblock copolymer, which is self-assembled into the clear structure with 5-100nm grades of sizes,.In order to make these
Structure can be used for a variety of applications, needs to use it with film and takes block copolymer structure (such as sheet and cylinder)
To make them perpendicular to the substrate coated by them.A kind of method is needed to generate with the required structure that can be etched
The feature of arrangement.
Brief summary of the invention
The present invention includes polymer topcoat, the block copolymer in film can be made to be orientated by heating, so that
Only by heating the phase separation structure that will not be orientated perpendicular to the planar orientation of film.Moreover, from insoluble or essentially insoluble swollen
The solvent of any component of the block copolymer is by the top coat.Topcoat polymer of the present invention occurs when heated
Performance change, this makes them effective in orientation process.Moreover, by using insoluble or essentially insoluble swollen block copolymerization
The solvent of any component of object can remove topcoat polymer of the invention from the surface of the block copolymer.
In one embodiment, the present invention relates to a kind of is applied to block copolymer film for finishing coat to generate stratiform knot
The method of structure, the layer structure include substrate, surface energy neutral layer, block copolymer and can be total to not destroying or being modified the block
The topcoating composition coated under polymers.The insoluble surface neutral layer generates by methods known in the art, and
It can be made of self-assembled monolayer, " molecular brush (brushes) " or cross-linked polymer.Usually pass through spin coating for the block copolymer
It is applied on insoluble neutral layer.In one embodiment, which is made of various ingredients, one of them is acid
Acid anhydride.In one embodiment, which is derived from maleic anhydride monomer part.It can change component ratio in finishing coat to come most
Optimize the performance of specific block copolymer.In one embodiment, which is dissolved in insoluble or substantially
In the solvent of the non-swelling block copolymer film.In one embodiment, which can be water, alcohol or water and alcohols
Mixture.The solvent can be alkali.In one embodiment, the alkali is aqueous ammonium hydroxide or aqueous alkylaryl hydroxide
Change the like derivatives of ammonium or alkyl ammonium hydroxide.In one embodiment, which is dissolved in alkali, by gained
Salt separate and be re-dissolved in new casting solvent (casting solvent).In one embodiment, the salt casting film
Solvent (salt casting solvent) is the mixture of water, organic solvent or water and organic solvent.In another embodiment party
In case, which is the mixture of alcohol or pure and mild organic solvent.
In one embodiment, the present invention relates to a kind of methods, comprising: a) providing has the substrate on surface, in surface
With layer, block copolymer and finishing coat, b) under conditions of generating first layer, the substrate table is handled with the surface neutral layer
Face；C) under conditions of generating the second layer comprising block copolymer film on said surface, the table is coated with block copolymer
Face neutral layer；D) block copolymer described in top coat, so that third layer is generated on said surface, wherein the third
Layer only can be such that block copolymer microcell is orientated perpendicular to membrane plane by thermal annealing.In numerous applications, preferably only lead to
It crosses heating or so-called thermal annealing realizes orientation.In one embodiment, thermal annealing in the presence of no finishing coat is not
Vertical features can be generated.In one embodiment, the finishing coat of step d) is not damage, dissolving or essentially insoluble swollen
In the solvent or solvent mixture of the block copolymer.In one embodiment, the finishing coat of step d) is applied with face
In the solvent of layer reaction.In one embodiment, the finishing coat of step d) be in solvent mixture, and the solvent mix
Object includes the ingredient reacted with finishing coat.In one embodiment, which is dissolved in comprising water, pure and mild organic solvent
In the liquid of at least one of (or combinations thereof).In one embodiment, which is dissolved in comprising water, pure and mild had
In solvent it is any two or more mixture liquid in.In one embodiment, which also includes alkali.?
In one embodiment, which is alkali.In one embodiment, which is amine.In one embodiment, the amine choosing
Free alkylamine, aliphatic amine and be connected to any combination of functional groups amine (or combinations thereof) constitute group.In an embodiment party
In case, the amine is salt.In one embodiment, the salt has selected from by ammonium cation, alkyl ammonium cation and fat
The cation in group that race's ammonium cation (or combinations thereof) is constituted.In one embodiment, which includes the combination of cation.
In one embodiment, the salt includes anion.In one embodiment, the anion is hydroxide radical anion.
In one embodiment, the alkali includes ammonium hydroxide.In one embodiment, the alkali includes alkyl ammonium hydroxide.
In one embodiment, the alkali includes trimethylamine.In one embodiment, the alkali includes the mixture of salt and amine.
In one embodiment, the finishing coat of reaction is separated again.In one embodiment, the finishing coat of dissolution is separated again.
In one embodiment, the finishing coat separated again is reused in the above-mentioned methods.In one embodiment, pass through one
Kind or a variety of technologies selected from precipitating, evaporation and distillation (or combinations thereof) separate the finishing coat again.In one embodiment, should
Method further includes the thermal annealing after step d).In one embodiment, this method further includes with not damaging, dissolve or not
The removing solvent for being obviously swollen the block copolymer removes the finishing coat from the block copolymer.In an embodiment
In, the finishing coat includes acid anhydrides.In one embodiment, which is derived from maleic anhydride.In one embodiment,
Substrate is selected from by silicon, silica, glass, surface modified glass, plastics, ceramics, transparent substrates, flexible substrates and is used for roll-to-roll
The group that the substrate (or combinations thereof) of technique is constituted.In one embodiment, the block copolymer is by multiple and different block structures
At.In one embodiment, which includes at least one speed to be different from other (one or more) blocks
The block of rate etching.In one embodiment, which includes silicon at least one block.In an embodiment party
In case, which is poly- (styrene-b -4- trimethyl silyl styrene-b-styrene) (poly
(styrene-block-4-trimethylsilylstyrene-block-styrene)).In one embodiment, this is embedding
Section copolymer is poly- (4- trimethyl silyl styrene-b-D, L- lactide) (poly (4-
Trimethylsilylstyrene-block-D, L-lactide)).In one embodiment, block copolymer is at least one
It include tin in a block.In one embodiment, block copolymer includes inorganic component.In one embodiment, block
Copolymer includes organometallic components.In one embodiment, the thermal annealing generates the block copolymerization perpendicular to membrane plane
Object microcell.In one embodiment, the form of the microcell is selected from by sheet, spherical shape and the cylindrical group constituted.In a reality
It applies in scheme, the nanostructure is selected from by sheet, cylinder, vertical arrangement cylinder, horizontally arranged cylindrical, spherical, spiral shell
Revolve the group that shape, reticular structure and classification nanostructure are constituted.In one embodiment, selected from by air environment, indifferent gas
The thermal annealing is carried out under conditions of the group that body environment, decompression and pressurization are constituted.In one embodiment, the surface neutralizes
Layer is comprising selected from by cross-linked polymer, brush (brushes), self-assembled monolayer, chemical modification surface, physical modification surface and thermosetting
Change the component in the group that surface (or combinations thereof) is constituted.
In one embodiment, the present invention provides a kind of method, comprising: a) providing has the substrate on surface, in surface
With layer, block copolymer and finishing coat, b) under conditions of generating first layer, the substrate table is handled with the surface neutral layer
Face；C) under conditions of generating the second layer comprising block copolymer film on said surface, the table is coated with block copolymer
Face neutral layer；And d) with block copolymer described in top coat, to generate third layer on said surface, e) can make it is embedding
Under conditions of section copolymer characteristic is perpendicular to membrane plane orientation, the third layer is handled.In numerous applications, preferably only lead to
It crosses heating or so-called thermal annealing realizes orientation.In one embodiment, the processing of step e) includes thermal annealing.?
In one embodiment, thermal annealing in the presence of no finishing coat will not generate vertical features.In one embodiment, will
The finishing coat is dissolved in trimethylamine.In one embodiment, the coating includes spin coating.
In one embodiment, the polymer salt is and dissolution anhydride polymer and then evaporation solvent in liquefied ammonia
Preparation.In another embodiment, which is dissolved in the solution of ammonia or alkylamine, and by precipitate or evaporate solvent come
Separate the salt.In one embodiment, the alkali is trimethylamine.In numerous applications, preferably only by heating or
So-called thermal annealing realizes orientation.In one embodiment, the invention also includes: heat under conditions of forming nanostructure
(thermal annealing) layer structure.In one embodiment, the method for removing finishing coat includes: to be dissolved in insoluble de-embedding substantially not
It is swollen in the solvent or solvent mixture of Block Copolymer Thin Film layer.In one embodiment, the nanostructure includes circle
Column construction, the cylindrical structure is relative to membrane plane substantially vertical orientation.In one embodiment, the nanostructure
Including sheet (line-space, line-space) structure, the cable architecture is relative to surface plane substantially vertical orientation.We
It is not intended to the form based on block copolymer to limit the present invention.
In one embodiment, the present invention relates on the surface including first, second, and third layer of layer structure,
Described in first layer include cross-linked polymer, wherein the second layer includes block copolymer film, and the wherein third layer
Include acid anhydrides.In one embodiment, the surface includes silicon.
In one embodiment, the substrate is silicon wafer.In one embodiment, the substrate is quartz.?
In one embodiment, the substrate is glass.In one embodiment, the substrate is plastics, in an embodiment
In, the substrate is transparent substrates.In one embodiment, the substrate is the substrate of roll-to-roll.In an embodiment
In, the substrate is coated with interface can be in the substrate surface energy neutral layer between the interface energy of two kinds of blocks.We are not intended to base
The present invention is limited in the neutral layer or substrate that use.In one embodiment, block copolymer is diblock copolymer.?
In one embodiment, block copolymer is triblock copolymer.We be not intended to based in block copolymer block number,
The form of the structure of block/bonded or the orientation texture generated due to annealing is limited the scope of the invention, we are also not intended to
The present invention is limited with regard to the chemical component of block copolymer.
In one embodiment, the present invention relates to apply finishing coat to block copolymer film including multiple steps to produce
The method of raw layer structure.For example, (being shown in Fig. 3) in one embodiment: 1) surface treatment is dissolved in toluene, and is revolved
Be applied on substrate (such as silicon wafer) surface, 2) surface treatment be 250 DEG C be crosslinked 5 minutes, 3) washed 2 times with toluene.For
Next layer has step 4): block copolymer is dissolved in toluene simultaneously spin coating.For another layer, there is step 5): face is applied
Layer is dissolved in trimethylamine aqueous solution and spin coating, then 6) at 190 DEG C by Thin-film anneal 1 minute.Annealing, which can be, keeps nanometer special
Collect to thermal annealing；Can be by 7) by with 3000rpm spin coating water, and apply 40 drop trimethylamine aqueous solutions, then apply
10 drop methanol, so that finishing coat is removed, to show these nanofeatures.Then it can be etched, such as in an embodiment party
8) under the following conditions to block copolymer application oxygen plasma etch in case: pressure=20mTorr, RF power=10W,
ICP power=50W, O2Flow velocity=75sccm, argon gas flow velocity=75sccm, temperature=15 DEG C, time=30 second, as shown in Figure 3.
The brief description of accompanying drawing
In order to thoroughly understand the features and advantages of the invention, referring now to the drawings to the detailed description of the invention.
Fig. 1 diagram display introduces a kind of finishing coat polymerization of the anhydride moiety derived from the maleic anhydride reacted with trimethylamine
The typical example of the finishing coat technique of open loop and the ring-closure reaction of object.
Fig. 2 shows the specific examples of the representative film laminated body for the material for being suitable for invention disclosed herein finishing coat.
Fig. 3 illustrates an embodiment of coating, the annealing and stripping technology of the material for specific group.The figure illustrates
The representative experiment flow of processing step relevant to finishing coat of the present invention disclosed herein.
Fig. 4 provides the non-limiting example of finishing coat design to illustrate the opposite of each component of topcoat copolymer
The control of composition.
It is that Fig. 5 provides an embodiment as a result, including the poly- (styrene-b -4- for being handled and being orientated with finishing coat
Trimethyl silyl styrene-b-styrene) (poly (styrene-block-4-trimethylsilylstyrene-
Block-styrene)) the scanning electron microscope microphoto of block copolymer film.The block copolymer is in the presence of no finishing coat
It cannot be only orientated by heating.
Fig. 6 provides representative as a result, including poly- (the 4- trimethyl silyl benzene second for handling orientation with finishing coat
Alkene-block-D, L- lactide) (poly (4-trimethyl s i lyl styrene-block-D, L-lact ide)) block
The scanning electron microscope microphoto of copolymer.
Definition
In order to be conducive to understand the present invention, many terms are defined below.Here the term meaning defined is related to the present invention
The routine of field technical staff understands identical.Term such as "one" and "the" is non-only to refer to single entity, but including for saying
The general classes of bright specific examples.Here term specific embodiment for describing the present invention, but in addition to claim
Except book limits, uses and do not limit the present invention.
In addition, constitute the compounds of this invention atom be intended to include these atoms all isotope forms.Used here as
Isotope include those with same atoms number but with the atom of different quality number.Pass through general example and does not limit
System, the isotope of hydrogen includes tritium, deuterium, and the isotope of carbon includes13C and14C.Similarly, it is contemplated that the one of the compounds of this invention
A or multiple carbon atoms can be replaced by (one or more) silicon atom.Moreover, it is contemplated that the compounds of this invention (one or
It is multiple) oxygen atom can replace by (one or more) sulphur or selenium atom.
" alkali " used herein includes any entity that can be reacted with anhydride moiety.
" surface energy neutral layer " used herein is identical as " substrate surface neutral layer ".
Brush polymer used herein is the quasi polymer [2] for adhering to the surface of solids.Adhere to solid substrate
Polymer must be intensive enough, to have intensive polymer, then forces polymer from surface extension to avoid being overlapped.
[3]
In field of electronic device, roll-to-roll technique (roll-to-roll processing), also referred to as web processes (web
Processing), reel-to-reel technique (reel-to-reel processing) or R2R, are in flexiplast or metal foil
Roller on prepare the technique of electronic equipment.In the other field earlier than the purposes, the production since flexible material roller is referred to
The applied coatings of raw outlet roller, printing carry out any technique of other techniques and batching after the technique again.The film sun
Can battery (TFSC), also referred to as film photovoltaic cell (TFPV) is that one or more layers thin layer is deposited in substrate or surface is (thin
Film) photovoltaic material and the solar battery for preparing.Possible roll-to-roll substrate includes but is not limited to metallized polyimide terephthaldehyde
Sour glycol ester, metal film (steel), glass-film (such as Corning Gorilla Glass), graphene coating film, poly- naphthalene diformazan
Sour glycol ester (Dupont Teonex) and Kapton film, polymer film, metallized polymeric film, glass or silicon, carbonization polymerization
Object film, glass or silicon.Possible polymer film includes polyethylene terephthalate, kapton, mylar etc..
Block copolymer used herein is made of two or more polymer chains (block), they are chemically distinct
And the connection of mutual covalence key.Block copolymer is proposed to be used in a variety of applications, is based primarily upon them and forms nano-scale patterns
Ability.These self assembly patterns are construed to nanolithographic mask, and inorganic or organic structure as further synthesizing
Template.Lead to the comparison of the chemically or physically performance of different etching speeds between each block by utilizing, so that these are applied
It is possibly realized.Such as do not have the new opplication in standby to often rely in block in fuel cell, battery, data storage and photoelectron
In performance.All these purposes all rely on the self assembly and orientation of rule of the block copolymer in naked eyes visibility.
4- trimethyl silyl styrene is the example of styrene derivative.The following representation of monomer:
And it is abbreviated as TMSS TMS-St.Corresponding polymer architecture are as follows:
And it is abbreviated as PTMSS P (TMS-St).
Present invention further contemplates that for example the modified styrene of basic styryl structures " is spread out by the way that substituent group is added into ring
Biology ".Any derivative of compound shown in Fig. 4 can also be used.Derivative can be such as hydroxy derivatives or halogenated
Derivative." hydrogen " expression-H used herein；" hydroxyl " expression-OH；" oxo " indicates=0；" halogenated " independently expression-
F ,-Cl ,-Br, or-I.
" nanostructure " is preferably generated on the surface using block copolymer, or " the physics spy with controlled orientation
Sign ".These physical features have shape and thickness.For example, the component by block copolymer can form different structures, example
Such as vertical sheet, face inner cylinder and vertical cylinder shape, and they can depend on film thickness, surface can neutral layer and embedding
The chemical property of section.In a preferred embodiment, the block copolymer microcell relative to the first film plane substantially
Vertical arrangement.The structural approach that can control in nanoscale domain or region (i.e. " microcell " or " nanometer microcell ") is substantially
It is even, and the space arrangement of these structures can also be controlled.For example, in one embodiment, the microcell interval of nanostructure
It is about 50nm or smaller.Method described herein can produce with required size, shape, orientation and the structure in period.Its
Afterwards, in one embodiment, it can etch or be further processed these structures in other cases.
It should be pointed out that in one embodiment, this method includes annealing and preferred thermal annealing.We are not intended to
The present invention is confined to a seed type or method for annealing.In one embodiment, annealing includes ultrasonic treatment.In a reality
It applies in scheme, annealing uses solvent.Importantly, block copolymer material preferably below annealing effect rearranges.
Detailed description of the invention
The present invention includes using copolymer finishing coat, which can be spin-coated on Block Copolymer Thin Film, and be used for
The orientation of block copolymer microcell (or feature) is controlled by heating, and then removes it.The finishing coat enables to
The microcell in Block Copolymer Thin Film that will not be orientated in the presence of no finishing coat only by heating is orientated.
In one embodiment, finishing coat is made of each same polymers compositions.In one embodiment, acid anhydrides is
Constant component.In one embodiment, finishing coat components be soluble is in alkali.In one embodiment, finishing coat is dissolved
In trimethylamine.It is had the advantage that using trimethylamine, the advantages of including that can cooperate with the compound of numerous species.
In one embodiment, the present invention expects removing finishing coat.In some embodiments, finishing coat can divide again
From and recycle.
Therefore, the specific group of the acid anhydride copolymer finishing coat for the tropism control of film block copolymer has been disclosed
At and method.However it will be appreciated that those skilled in the art, other than those of having been described, without departing substantially from
There are also more deformations in the case where the present inventive concept of this paper.Therefore subject of the present invention is not limited other than disclosed objective
System.Moreover, all terms are all solved in the mode that most probable is wide in range and context is unified when explaining these contents
It releases.Especially, term " includes " and "comprising" should be construed as non-excluded mode and refer to element, component or step, indicate to refer to
Element, component or the step presence or use or combine that element, component or step can be not expressly mentioned with other.
All publications mentioned in text by it is open or describe relevant method cited in these publications and/or
Material and with herein in conjunction with.Publication described herein is used only for the disclosure of which before the application applying date.This
Do not have any content in text for showing: the present invention invents known to be utilized due to the publication by as discloses in advance.And
The publication date of offer may be different from the practical publication date, need individually confirmation.
Embodiment 1
Acid anhydride copolymer finishing coat for film block copolymer tropism control
With 0.2 micronFilter filters poly- (4- t-butyl styrene -co- methyl methacrylate-
Co- 4- vinyl-benzyl azide) (poly (4-tert-butylstyrene-co-methyl methacrylate-co-4-
Vinyl-benzylazide)) the 0.5wt% solution in toluene, and with 3000rpm spin coating 30 seconds to prepare the flat of about 15nm
Synovial membrane.The film is heated 5 minutes at 250 DEG C with crosslinking on hot plate, and then cleans 3 times with toluene with 3000rpm to remove
Uncrosslinked chain.The most telolemma measured after cleaning with ellipsometry with a thickness of about 14nm.With 0.2 micron
Filter filters the poly- (styrene-b -4- trimethyl silyl styrene-b-benzene of various concentration (1-2.5wt%)
Ethylene) (poly (styrene-block-4-trimethylsilylstyrene-block-styrene)) molten in toluene
Liquid, and (cast) is cast to crosslinking substrate surface under different rotation speeds to generate thickness~30-60nm (1-2*L0)
The film of relative smooth.Then by finishing coat (see Fig. 5) in MeOH:30wt%NH4OH aqueous solution is the molten of 3: 1 (by quality ratio)
1wt% solution in liquid is spun on BCP film with 3000rpm.Discovery MeOH:30wt%NH is measured with ellipsometry4OH water
Solution is that 3: 1 solution does not make block copolymer film thickness change by quality ratio.By sample in Thermolyne
It anneals 1 minute on HP-11515B hot plate at 190 DEG C.Then it is rapidly removed, and is cooled to room temperature on solid metal block.
With 3: 1 MeOH:30wt%NH4OH aqueous solution removes the finishing coat.The sample of removing includes the face of a small amount of (<=5nm) remnants
Coating.Etch the block copolymer film with oxygen plasma etch block copolymer under the following conditions: pressure=
20mTorr, RF power=10W, IcP power=50W, O2Flow velocity=75sccm, argon gas flow velocity=75sccm, temperature=15 DEG C,
Fig. 5 is seen in time=30 second.
Embodiment 2
By the toluene solution of poly- (4- methoxy styrene -co- 4- vinyl benzyl nitrine) (XST-OMe) of 0.5wt%
With 3000rpm spin coating 30 seconds on the chip for cleaned respectively with acetone and isopropanol 3 times.The chip is opened in air
It anneals 5 minutes at 250 DEG C so that film is crosslinked on hot plate.Once chip to be removed to from hot plate and is cooled to room temperature, then just will
It is submerged into toluene 2 minutes, and dries up twice to remove uncrosslinked polymer.The typical film measured by elliptical polarizer
Thickness is 13-15nm grades.Thin slice is formed with poly- (4- trimethyl silyl styrene-b-D, L- lactide) (poly (4-
Trimethylsilylstyrene-block-D, L-lactide)) 1wt% toluene solution is administered to the XST-OMe film of crosslinking.
Then the NH of 30wt% is used4Finishing coat 60nm (TC-PS) shown in OH aqueous solution spin coating Fig. 6.Make together with the application of TC-PS
Topcoat film more evenly is prepared with methanol.It was found that the NH of 30wt%4OH aqueous solution by ellipsometry for being measured
Block copolymer film thickness does not influence.Then by trilamellar membrane stacked body at 170 DEG C (for PTMSS-PLA, in vacuum drying oven
In) annealing 20 hours.When annealing is completed, by the PTMSS-PLA sample annealed in vacuum drying oven under vacuum through about 5 hours
Process is cooled to room temperature.Then by rotating chip with 3000rpm and applying 20 drop strippers with pipette, 30wt% is used
NH4OH aqueous solution removes finishing coat.In general, the film of removing includes considerably less (even if having as surveyed by elliptical polarizer
Words) measurable remaining finishing coat (< 4nm).The sample of removing is without etching direct imaging.See Fig. 6.
Bibliography
1.Bates, F.S.and Fredr ickson, G.H. (1990) " Block Copolymer
Thermodynamics:Theory and Exper iment, " Annu.ReV.Phys.Chem.41,525-557.
2.Milner, S.T. (1991) " Polymer brushes, " Science 251 (4996), 905-914.
3.Zhao, B.and Brittain, W.J. (2000) " Polymer brushes:surface-imobilized
Macromolecules, " Prog.Polym.Sci.25 (5), 677-710.
Claims (45)
1. a kind of method, comprising:
A., substrate, surface neutral layer, block copolymer and the finishing coat for having surface are provided,
B. under conditions of generating first layer, the substrate surface is handled with the surface neutral layer；
C. under conditions of generating the second layer including block copolymer film on said surface, the table is coated with block copolymer
Face neutral layer, and
D. the block copolymer described in top coat, to generate third layer on said surface, wherein only pass through thermal annealing
The third layer can be such that block copolymer microcell is orientated perpendicular to membrane plane, wherein finishing coat is dissolved in liquid, the liquid
Body includes water, two or more any mixture in pure and mild organic solvent.
2. the method according to claim 1, wherein thermal annealing in the presence of no finishing coat does not generate vertical features.
3. the method according to claim 1, wherein the finishing coat of step d) is will not to damage, dissolve or essentially insoluble swollen embedding
In the solvent or solvent mixture of section copolymer.
4. the method according to claim 1, wherein the finishing coat of step d) is in the solvent reacted with finishing coat.
5. the method according to claim 1, wherein the finishing coat of step d) is in solvent mixture, which includes
The component reacted with finishing coat.
6. the method according to claim 1, wherein being dissolved in finishing coat comprising at least one of water, pure and mild organic solvent
In liquid.
7. the method according to claim 1, wherein the liquid also includes alkali.
8. the method according to claim 1, wherein the liquid is alkali.
9. method according to claim 7, wherein the alkali is amine.
10. method according to claim 9, wherein the amine is selected from by alkylamine, aliphatic amine and is connected to any functional group
The group that combined amine is constituted.
11. method according to claim 9, wherein the amine is salt.
12. method according to claim 11, wherein the salt has selected from by ammonium cation, alkyl ammonium cation and aliphatic
The cation in group that ammonium cation is constituted.
13. method according to claim 11, wherein the salt contains the combination of cation.
14. method according to claim 11, wherein the salt contains anion.
15. method according to claim 14, wherein the anion is hydroxide radical anion.
16. method according to claim 7, wherein the alkali includes ammonium hydroxide.
17. method according to claim 7, wherein the alkali includes alkyl ammonium hydroxide.
18. method according to claim 7, wherein the alkali includes trimethylamine.
19. method according to claim 7, wherein the alkali includes the mixture of salt and amine.
20. method according to claim 4, wherein the finishing coat of reaction is separated again.
21. method according to claim 6, wherein the finishing coat of dissolution is separated again.
22. method according to claim 21, wherein the finishing coat that this is separated again is again used in the method according to claim 1
In.
23. method according to claim 21, wherein being separated again by one or more technologies selected from precipitating, evaporation and distillation
The finishing coat.
24. the method according to claim 1 further includes the thermal annealing after step d).
25. method according to claim 24 further includes removing the finishing coat from the block copolymer using removing solvent,
The removing solvent will not damage, dissolve or unobvious swelling block copolymer.
26. according to the method in claim 3, wherein the finishing coat includes acid anhydrides.
27. method according to claim 26, wherein the acid anhydrides is derived from maleic anhydride.
28. the method according to claim 1, wherein the substrate be selected from by silicon, silica, glass, surface modified glass, plastics,
In the group that ceramics, transparent substrates, flexible substrates and the substrate applied to roll-to-roll technique are constituted.
29. the method according to claim 1, wherein the block copolymer includes multiple and different block.
30. method according to claim 29, wherein the block copolymer include it is at least one be different from it is one or more its
The block of the rate etching of its block.
31. method according to claim 29, wherein the block copolymer contains silicon at least one block.
32. method according to claim 29, wherein the block copolymer is poly- (styrene-b -4- trimethyl first silicon
Ring-alkylated styrenes-block-styrene).
33. method according to claim 29, wherein the block copolymer is poly- (4- trimethyl silyl styrene-embedding
Section-D, L- lactide).
34. method according to claim 29, wherein the block copolymer contains tin at least one block.
35. method according to claim 29, wherein the block copolymer includes inorganic component.
36. method according to claim 29, wherein the block copolymer includes organometallic components.
37. method according to claim 24, wherein the thermal annealing generates the block copolymer microcell perpendicular to membrane plane.
38. wherein the form of the microcell is selected from sheet, spherical shape and the cylindrical group constituted according to the method for claim 37.
39. method according to claim 24, wherein the thermal annealing selected from air environment, inert gas environment, decompression and
It is carried out under conditions of the group that pressurization is constituted.
40. method according to claim 2, wherein the surface neutral layer includes selected from by cross-linked polymer, brush
(brushes), the component for the group that the single layer of self assembly, chemical modification surface, physical modification surface and heat cure surface are constituted.
41. a kind of method, comprising:
A) substrate, surface neutral layer, block copolymer and the finishing coat for having surface are provided,
B) under conditions of generating first layer, the substrate surface is handled with the surface neutral layer；
C) under conditions of generating the second layer including block copolymer film on said surface, the table is coated with block copolymer
Face neutral layer；And
D) block copolymer described in top coat, so that third layer is generated on said surface, wherein finishing coat is dissolved
In liquid, which includes water, two or more any mixture in pure and mild organic solvent；
E) under conditions of being orientated block copolymer feature perpendicular to membrane plane, the third layer is handled.
42. wherein the processing of step e) includes thermal annealing according to the method for claim 41.
43. according to the method for claim 42, wherein thermal annealing in the presence of no finishing coat does not generate vertical features.
44. according to the method for claim 41, wherein the finishing coat is dissolved in trimethylamine.
45. according to the method for claim 41, wherein the coating includes spin coating.
Applications Claiming Priority (2)
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| US13/922,011 | 2013-06-19 | ||
| US13/922,011 US9314819B2 (en) | 2012-02-10 | 2013-06-19 | Anhydride copolymer top coats for orientation control of thin film block copolymers |
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| JP6325320B2 (en) * | 2014-04-09 | 2018-05-16 | 東京応化工業株式会社 | Method for manufacturing structure including phase separation structure and method for forming topcoat film |
| JP6413888B2 (en) * | 2015-03-30 | 2018-10-31 | Jsr株式会社 | Pattern forming composition, pattern forming method, and block copolymer |
| WO2017147185A1 (en) * | 2016-02-23 | 2017-08-31 | Board Of Regents The University Of Texas System | Block copolymers for sub-10 nm patterning |
| WO2018051907A1 (en) * | 2016-09-13 | 2018-03-22 | 日産化学工業株式会社 | Overlay film-forming composition and method for producing phase separation pattern |
| WO2018135456A1 (en) * | 2017-01-19 | 2018-07-26 | 日産化学工業株式会社 | Self-assembled film forming composition for forming fine phase separation pattern |
| KR102523359B1 (en) * | 2017-01-19 | 2023-04-19 | 닛산 가가쿠 가부시키가이샤 | Composition for Forming Underlayer Film for Microphase Separation Pattern Formation |
| KR20210032378A (en) * | 2018-07-17 | 2021-03-24 | 닛산 가가쿠 가부시키가이샤 | Composition for forming a block copolymer layer for forming a fine phase separation pattern |
| TW202212508A (en) | 2020-06-08 | 2022-04-01 | 日商日產化學股份有限公司 | Upper layer film-forming composition and method for producing phase separated pattern |
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| CN101971093A (en) * | 2008-02-05 | 2011-02-09 | 美光科技公司 | Method to produce nanometer-sized features with directed assembly of block copolymers |
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| KR20140147718A (en) | 2014-12-30 |
| TW201513222A (en) | 2015-04-01 |
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