CN104592539A - Anhydride copolymer top coats for orientation control of thin film block copolymers - Google Patents
Anhydride copolymer top coats for orientation control of thin film block copolymers Download PDFInfo
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Abstract
For producing a high-quality lithography pattern, to use self-assembled block copolymer structures, it is required to regulate orientation of the structures in a thin film. Particularly, most of applications need cylinder- and plate-shaped orientations which are perpendicular to a surface of the block copolymer film. A preferred method of achieving the orientation is provided by heating. The present invention includes a use of a top coat for polarity-switching to regulate orientation of the block copolymer thin film by heating. The top coat may be spin-coated on the block copolymer thin film from a polar casting solvent and allow a composition to be changed and ''neutralized'' during thermal annealing. The top coat, otherwise, facilitates regulation of orientation of the block copolymer which would not be possible only by heating.
Description
The cross reference of related application
This part continuation application requires the U. S. application the 13/761st proposed on 02 07th, 2013, the right of priority of No. 918, the U.S. Provisional Application the 61/597th that this U.S. Application claims proposed on 02 10th, 2012, the right of priority of No. 327, their content is incorporated to herein by reference.
Invention field
The advanced Lithographic pattern of self-assembled block copolymers preparation is used to depend on its tropism control in the film.Can make segmented copolymer orientation by thermal annealing finishing coat, otherwise the orientation of segmented copolymer can be very difficult.The present invention includes and use multipolymer finishing coat, it can be spin-coated on Block Copolymer Thin Film, and for by heating with the orientation controlling this segmented copolymer microcell, is then removed.This finishing coat can make in Block Copolymer Thin Film do not have under finishing coat by means of only heating its can not the microcell orientation of orientation.
Background of invention
It is known [1] that Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock is self-assembled into the clear structure with 5-100nm level size.In order to make these structures can be used for multiple application, need it is used with film and makes block copolymer structure (such as sheet and cylindrical) orientation, thus make them perpendicular to the substrate coated by them.Need a kind of method to produce the feature with the etched structural arrangement of required energy.
Brief summary of the invention
The present invention comprises polymer topcoat, its segmented copolymer orientation making in film by heating, thus make only by heat can not the phase separation structure of orientation perpendicular to the planar orientation of film.And, never dissolve or the solvent of any component of this segmented copolymer not swelling substantially by this top coat.There is performance variation when heating in topcoat polymer of the present invention, this makes them effective in orientation process.And, not dissolve or the surface of topcoat polymer of the present invention from this segmented copolymer can remove by the solvent of any component of not swelling segmented copolymer substantially by using.
In one embodiment, the present invention relates to a kind of block copolymer film that is applied to by finishing coat to produce the method for laminate structure, this laminate structure comprises in substrate, surface energy and layer, segmented copolymer and can at the topcoating composition do not destroyed or apply under this segmented copolymer of modification.This insoluble surface neutralization layer produces by means commonly known in the art, and can be made up of self-assembled monolayer, " molecular brush (brushes) " or cross-linked polymer.Usually by spin coating, this segmented copolymer is applied on insoluble neutralization layer.In one embodiment, this topcoat polymer is made up of various ingredients, and one of them is acid anhydrides.In one embodiment, this acid anhydrides is derived from maleic anhydride monomer part.Component ratio in finishing coat can be changed and carry out the performance of the specific segmented copolymer of optimization.In one embodiment, this topcoating composition is dissolved in do not dissolve or this block copolymer film not swelling substantially solvent in.In one embodiment, this solvent can be the mixture of water, alcohol or water and alcohols.This solvent can be alkali.In one embodiment, described alkali is the like derivatives of the ammonium hydroxide of water-based or the alkyl ammonium hydroxide of water-based or alkyl ammonium hydroxide.In one embodiment, this acid anhydride copolymer is dissolved in alkali, the salt of gained is separated and is dissolved in again in new casting solvent (casting solvent).In one embodiment, this salt casting solvent (salt castingsolvent) is the mixture of water, organic solvent or water and organic solvent.In another embodiment, this solvent is the mixture of alcohol or alcohol and organic solvent.
In one embodiment, the present invention relates to a kind of method, comprise: the substrate with surface, surperficial neutralization layer, segmented copolymer and finishing coat a) are provided, b) under the condition producing the first layer, process described substrate surface with described surface neutralization layer; C) under generation comprises the condition of the second layer of block copolymer film on said surface, with segmented copolymer coating described surface neutralization layer; D) with segmented copolymer described in top coat, thus produce third layer on said surface, wherein said third layer only can make segmented copolymer microcell perpendicular to membrane plane orientation by thermal annealing.In numerous applications, preferably orientation is realized only by heating or so-called thermal annealing.In one embodiment, the thermal annealing under finishing coat is not being had to produce vertical features.In one embodiment, steps d) finishing coat be not damaging, dissolve or substantially in the solvent of this segmented copolymer not swelling or solvent mixture.In one embodiment, steps d) finishing coat be in the solvent reacted with finishing coat.In one embodiment, steps d) finishing coat be in solvent mixture, and this solvent mixture comprises the composition reacted with finishing coat.In one embodiment, this finishing coat is dissolved in the liquid of at least one comprised in water, alcohol and organic solvent (or its combination).In one embodiment, this finishing coat is dissolved in comprise in water, alcohol and organic solvent any two or more mixture liquid in.In one embodiment, this liquid also comprises alkali.In one embodiment, this liquid is alkali.In one embodiment, this alkali is amine.In one embodiment, described amine is selected from the group be made up of alkylamine, fatty amine and the amine (or its combination) that is connected to any combination of functional groups.In one embodiment, described amine is salt.In one embodiment, described salt has the positively charged ion in the group being selected from and being made up of ammonium cation, alkyl ammonium cation and aliphatics ammonium cation (or its combination).In one embodiment, this salt comprises cationic combination.In one embodiment, described salt comprises negatively charged ion.In one embodiment, described negatively charged ion is hydroxide radical anion.In one embodiment, described alkali comprises ammonium hydroxide.In one embodiment, described alkali comprises alkyl ammonium hydroxide.In one embodiment, described alkali comprises Trimethylamine 99.In one embodiment, described alkali comprises the mixture of salt and amine.In one embodiment, the finishing coat of reaction is separated again.In one embodiment, the finishing coat of dissolving is separated again.In one embodiment, this finishing coat be separated again is reused in the above-mentioned methods.In one embodiment, be selected from precipitation by one or more, evaporation is separated this finishing coat again with the technology of distillation (or its combination).In one embodiment, the method also comprises steps d) after thermal annealing.In one embodiment, the method also comprises with not damaging, to dissolve or the stripping solvent of not obvious this segmented copolymer swelling removes described finishing coat from described segmented copolymer.In one embodiment, described finishing coat comprises acid anhydrides.In one embodiment, this acid anhydrides is derived from maleic anhydride.In one embodiment, substrate is selected from by silicon, silicon oxide, glass, surface modified glass, plastics, pottery, transparent substrates, flexible substrates and the group that forms to the substrate (or its combination) of roller technique for roller.In one embodiment, described segmented copolymer is made up of multiple different block.In one embodiment, this segmented copolymer comprises at least one to be different from the block of the speed etching of other (one or more) block.In one embodiment, this segmented copolymer comprises silicon at least one block.In one embodiment, this segmented copolymer is poly-(styrene-b-4-trimethyl silyl styrene-b-vinylbenzene) (poly (styrene-block-4-trimethylsilylstyrene-block-styrene)).In one embodiment, this segmented copolymer is poly-(4-trimethyl silyl styrene-b-D, L-rac-Lactide) (poly (4-trimethylsilylstyrene-block-D, L-lactide)).In one embodiment, segmented copolymer comprises tin at least one block.In one embodiment, segmented copolymer comprises inorganic component.In one embodiment, segmented copolymer comprises organometallic components.In one embodiment, described thermal annealing produces the segmented copolymer microcell perpendicular to membrane plane.In one embodiment, the form of this microcell is selected from by sheet, the spherical and cylindrical group formed.In one embodiment, described nanostructure is selected from by sheet, cylindrical, the horizontal group that forms of cylindrical, spherical, volution, reticulated structure and classification nanostructure cylindrical, arranged vertically.In one embodiment, under the condition being selected from the group be made up of air ambient, inert gas environment, decompression and supercharging, described thermal annealing is carried out.In one embodiment, described surface neutralization layer comprises the component be selected from by cross-linked polymer, brush (brushes), self-assembled monolayer, chemical modification surface, group that physically modified is surperficial and thermofixation is surperficial (or its combination) is formed.
In one embodiment, the invention provides a kind of method, comprise: the substrate with surface, surperficial neutralization layer, segmented copolymer and finishing coat a) are provided, b) under the condition producing the first layer, process described substrate surface with described surface neutralization layer; C) under generation comprises the condition of the second layer of block copolymer film on said surface, with segmented copolymer coating described surface neutralization layer; And d) with segmented copolymer described in top coat, thus produce third layer on said surface, e) under the condition that segmented copolymer feature can be made perpendicular to membrane plane orientation, process described third layer.In numerous applications, preferably orientation is realized only by heating or so-called thermal annealing.In one embodiment, step e) described process comprise thermal annealing.In one embodiment, the thermal annealing under finishing coat is not being had to produce vertical features.In one embodiment, described finishing coat is dissolved in Trimethylamine 99.In one embodiment, described coating comprises spin coating.
In one embodiment, this polymer salt is by dissolving acid anhydride polymer in liquefied ammonia and then evaporating solvent and preparing.In another embodiment, this salt is dissolved in the solution of ammonia or alkylamine, and is separated this salt by precipitation or evaporating solvent.In one embodiment, described alkali is Trimethylamine 99.In numerous applications, preferably orientation is realized only by heating or so-called thermal annealing.In one embodiment, the present invention also comprises: heating (thermal annealing) laminate structure under the condition forming nanostructure.In one embodiment, remove the method for finishing coat to comprise: be dissolved in insoluble de-embedding substantially in the solvent of not swelling Block Copolymer Thin Film layer or solvent mixture.In one embodiment, described nanostructure comprises cylindrical structural, and this cylindrical structural is relative to membrane plane perpendicular orientation.In one embodiment, described nanostructure comprises sheet (line-space, line-space) structure, and described line structure is relative to surface plane perpendicular orientation.We do not wish to limit the present invention based on the form of segmented copolymer.
In one embodiment, the present invention relates to the laminate structure comprising first, second, and third layer from the teeth outwards, wherein said the first layer comprises cross-linked polymer, and the wherein said second layer comprises block copolymer film, and wherein said third layer comprises acid anhydrides.In one embodiment, described surface comprises silicon.
In one embodiment, described substrate is silicon wafer.In one embodiment, described substrate is quartz.In one embodiment, described substrate is glass.In one embodiment, described substrate is plastics, and in one embodiment, described substrate is transparent substrates.In one embodiment, described substrate is the substrate of roller to roller.In one embodiment, described substrate is coated with in the substrate surface energy of interfacial energy between the interfacial energy of two kinds of blocks and layer.We do not wish to limit the present invention based on the neutralization layer used or substrate.In one embodiment, segmented copolymer is Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock.In one embodiment, segmented copolymer is triblock copolymer.We do not wish to limit the scope of the invention based on the structure/keyed jointing of the block number in segmented copolymer, block or the form of oriented structure that produces due to annealing, and we do not wish that chemical component with regard to segmented copolymer is to limit the present invention yet.
In one embodiment, the present invention relates to comprise multiple step use finishing coat to produce the method for laminate structure to block copolymer film.Such as, (be shown in Fig. 3) in one embodiment: 1) surface treatment is dissolved in toluene, and be spun on substrate (such as silicon wafer) on the surface, 2) surface treatment is crosslinked 5 minutes at 250 DEG C, 3) by toluene wash 2 times.For lower one deck, there is step 4): segmented copolymer is dissolved in also spin coating in toluene.For one deck again, there is step 5): finishing coat to be dissolved in trimethylamine aqueous solution and spin coating, then 6) at 190 DEG C by Thin-film anneal 1 minute.Annealing can be the thermal annealing making nanofeature orientation; Can 7 be passed through) pass through with 3000rpm spin coating water, and apply 40 trimethylamine aqueous solutions, then apply 10 methyl alcohol, thus release surface coating, manifest these nanofeature.Then can etch, such as in one embodiment 8) apply oxygen plasma etch to segmented copolymer under the following conditions: pressure=20mTorr, RF power=10W, ICP power=50W, O
2flow velocity=75sccm, argon gas flow velocity=75sccm, temperature=15 DEG C, time=30 seconds, as shown in Figure 3.
Brief description of drawings
In order to more thoroughly understand the features and advantages of the invention, with reference now to accompanying drawing to the detailed description of the invention.
Fig. 1 illustrates the typical example of the finishing coat technique that Open loop and closed loop that display introduces a kind of topcoat polymer of the anhydride moiety derived from the maleic anhydride reacted with Trimethylamine 99 reacts.
Fig. 2 illustrates the specific examples of the representative film laminated body of the material being suitable for finishing coat of the present invention disclosed herein.
Fig. 3 diagram is for an embodiment of the coating of the material of particular group, annealing and stripping technology.The figure illustrate the representative experiment flow of the treatment step relevant to finishing coat of the present invention disclosed herein.
Fig. 4 provides the control of the non-limiting example of finishing coat design thus the relative composition of each component of illustration topcoat multipolymer.
Fig. 5 provides the result of an embodiment, comprises the scanning electron microscope Photomicrograph of poly-(styrene-b-4-trimethyl silyl styrene-b-vinylbenzene) (poly (styrene-block-4-trimethylsilylstyrene-block-styrene)) block copolymer film of the orientation with finishing coat process.This segmented copolymer is do not have under finishing coat only can not orientation by heating.
Fig. 6 provides representational result, comprise poly-(the 4-trimethyl silyl styrene-b-D by finishing coat process orientation, L-rac-Lactide) the scanning electron microscope Photomicrograph of (poly (4-trimethyl s i lyl styrene-block-D, L-lact ide)) segmented copolymer.
Definition
In order to be conducive to understanding the present invention, define many terms below.The routine of the term implication those skilled in the art related to the present invention defined here is understood identical.Term such as " one " and " being somebody's turn to do " is non-only refers to single entity, but comprise for illustration of the general classes of specific examples.Here term is for describing particular of the present invention, but except claims limit, its use does not limit the present invention.
In addition, the atom forming the compounds of this invention is intended to all isotope form comprising these atoms.Isotropic substance used herein comprises those and has same atoms number but the atom with different mass number.By general example and not restriction, the isotropic substance of hydrogen comprises tritium, deuterium, and the isotropic substance of carbon comprises
13c and
14c.Similarly, the one or more carbon atoms that it is expected to the compounds of this invention can be replaced by (one or more) Siliciumatom.And (one or more) Sauerstoffatom that it is expected to the compounds of this invention can be replaced by (one or more) sulphur or selenium atom.
" alkali " used herein comprises any entity that can react with anhydride moiety.
" with layer in surface energy " used herein is identical with " with layer in substrate surface ".
Brush polymkeric substance used herein is the base polymer [2] adhering to solid surface.The polymkeric substance adhering to solid substrate is sufficiently intensive, thus has intensive polymkeric substance, then forces polymkeric substance from surface extension to avoid overlap.[3]
In electronic device field, roller is to roller technique (roll-to-roll processing), also referred to as web processes (web processing), reel-to-reel technique (reel-to-reel processing) or R2R are the technique preparing electronics on the roller of flexiplast or tinsel.Early than in the other field of this purposes, batching again after referring to the applied coatings of the generation outlet roller from flexible materials roller, print or carrying out any technique of other techniques and this technique.Thin-film solar cells (TFSC), also referred to as film photovoltaic cell (TFPV), is the solar cell prepared in substrate or one or more layers thin layer of deposited on silicon (film) photovoltaic material.Possible roller to roller substrate including, but not limited to metallized polyimide ethylene glycol terephthalate, metallic membrane (steel), glassy membrane (such as Corning Gorilla Glass), Graphene coat film, PEN (Dupont Teonex) and Kapton film, polymeric film, metallized polymeric film, glass or silicon, carbonized polymers film, glass or silicon.Possible polymeric film comprises polyethylene terephthalate, kapton, mylar etc.
Segmented copolymer used herein is made up of two or more polymer chains (block), and they are chemically different and covalence key connects mutually.Segmented copolymer is proposed to be used in multiple application, mainly forms the ability of nano-scale patterns based on them.These self-assembly patterns are construed to nanolithographic mask, and are used as the template of further synthesizing inorganic or organic structure.Causing the chemistry of different etching speed or the contrast of physicals between each block by utilizing, making these application become possibility.New opplication such as in fuel cell, battery, data storage and photoelectron are not standby depends on the internal performance of block usually.All these purposes all depend on self-assembly and the orientation of the rule of segmented copolymer in naked eyes visual range.
4-trimethyl silyl vinylbenzene is the example of styrene derivatives.The following representation of monomer:
And be abbreviated as TMSS TMS-St.Corresponding polymer architecture is:
And be abbreviated as PTMSS P (TMS-St).
The present invention also expects such as by adding substituting group by the vinylbenzene " derivative " of basic styryl structures modification in ring.Any derivative of compound shown in Fig. 4 can also be used.Derivative can be such as hydroxy derivatives or halo derivatives." hydrogen " used herein expression-H; " hydroxyl " expression-OH; " oxo " represents=0; " halo " be expression-F independently ,-Cl ,-Br, or-I.
Preferably use segmented copolymer to produce from the teeth outwards " nanostructure ", or have " physical features " of controlled orientation.These physical features have shape and thickness.Such as, different structures can be formed by the component of segmented copolymer, such as vertical sheet, cylindrical and vertically cylindrical in face, and they can depend in film thickness, surface energy and the chemical property of layer and block.In a preferred embodiment, this segmented copolymer microcell is substantially vertically arranged relative to the plane of the first film.The structural approach of (i.e. " microcell " or " nanometer microcell ") in nanoscale domain or region can be controlled for roughly even, and the spatial disposition of these structures can be controlled.Such as, in one embodiment, the microcell of nanostructure is spaced apart about 50nm or less.Method described herein can produce has desired size, shape, orientation and the structure in cycle.Thereafter, in one embodiment, can etch or process these structures further in other cases.
It is pointed out that in one embodiment, the method comprises annealing and preferred thermal annealing.We do not wish the type that the present invention is confined to anneal or method.In one embodiment, annealing comprises supersound process.In one embodiment, annealing uses solvent.Importantly, rearranging of the block copolymer material preferably below annealing effect.
Detailed description of the invention
The present invention includes and use multipolymer finishing coat, this finishing coat can be spin-coated on Block Copolymer Thin Film, and for being controlled the orientation of segmented copolymer microcell (or feature) by heating, and then it is removed.This finishing coat can make not to be had under finishing coat only by heating the microcell orientation that can not occur in the Block Copolymer Thin Film of orientation.
In one embodiment, finishing coat is made up of each same polymeric constituent.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 99.Use Trimethylamine 99 to have advantage, comprise the advantage that can cooperate with the compound of numerous species.
In one embodiment, the present invention expects release surface coating.In some embodiments, finishing coat can be separated and recycle.
Therefore, specific composition and the method for the acid anhydride copolymer finishing coat of the tropism control for film segmented copolymer has been disclosed.But should be clear and definite, to those skilled in the art, except described those except, also have more distortion when not deviating from present inventive concept herein.Therefore theme of the present invention is not limited except disclosed aim.And when explaining these contents, all terms all make an explanation in the mode unified with context that most probable is wide in range.Especially, term " comprises " and " comprising " should be interpreted as non-excluded mode and mention key element, component or step, represents that key element, component or the step mentioned can exist with other not specifically mentioned key element, component or step or use or combine.
The all publications mentioned in literary composition by open or describe the relevant method and/or material quoted in these publications and be combined herein.The publication discussed herein is only for its disclosure before the application's applying date.Be used for showing without any content herein: the present invention is open in advance by such publication because make use of known invention.And the date of publication provided may be different from the actual date of publication, it needs to confirm separately.
embodiment 1
For the acid anhydride copolymer finishing coat of film segmented copolymer tropism control
With 0.2 micron
metre filter poly-(4-t-butyl styrene-altogether-methyl methacrylate--4-vinyl-benzyl azide altogether) (poly (4-tert-butylstyrene-co-methylmethacrylate-co-4-vinyl-ben zylazide)) 0.5wt% solution in toluene, and with 3000rpm spin coating 30 seconds to prepare the smooth film of about 15nm.This film is heated 5 minutes with crosslinked at 250 DEG C by hot plate, and cleans 3 times to remove uncrosslinked chain with 3000rpm toluene subsequently.The thickness of the most telolemma recorded by ellipsometry after cleaning is about 14nm.With 0.2 micron
poly-(styrene-b-4-trimethyl silyl styrene-b-vinylbenzene) (poly (styrene-block-4-trimethylsilylstyrene-block-styrene)) solution in toluene of metre filter different concns (1-2.5wt%), and under different speed of rotation curtain coating (cast) to crosslinking group basal surface to produce thickness ~ 30-60nm (1-2*L
0) the film of relative smooth.Then by finishing coat (see Fig. 5) at MeOH:30wt%NH
4the OH aqueous solution is that the 1wt% solution in the solution of 3: 1 (by quality ratio) is spun on BCP film with 3000rpm.Measure by ellipsometry and find MeOH:30wt%NH
4the OH aqueous solution be by quality ratio 3: 1 solution segmented copolymer film thickness is changed.Sample is annealed 1 minute at 190 DEG C on ThermolyneHP-11515B hot plate.Then it is removed rapidly, and on solid metal block cool to room temperature.With the MeOH:30wt%NH of 3: 1
4the OH aqueous solution peels off this finishing coat.The sample peeled off comprises the finishing coat that (<=5nm) is remaining on a small quantity.This block copolymer film is etched under the following conditions: pressure=20mTorr, RF power=10W, IcP power=50W, O with oxygen plasma etch segmented copolymer
2flow velocity=75sccm, argon gas flow velocity=75sccm, temperature=15 DEG C, time=30 seconds, see Fig. 5.
Embodiment 2
By the toluene solution of poly-(4-methoxy styrene--4-vinyl benzyl nitrine altogether) (XST-OMe) of 0.5wt% on the wafer having cleaned 3 times respectively with acetone and Virahol with 3000rpm spin coating 30 seconds.This wafer is opened on hot plate air and within 5 minutes, is cross-linked to make film 250 DEG C of annealing.Once by wafer from hot plate removing and cool to room temperature, be then just submerged in toluene 2 minutes, and be dried up twice to remove uncrosslinked polymkeric substance.The typical thickness recorded by elliptical polarizer is 13-15nm level.Thin slice is formed with poly-(4-trimethyl silyl styrene-b-D, L-rac-Lactide) (poly (4-trimethylsilylstyrene-block-D, L-lactide)) 1wt% toluene solution is administered to crosslinked XST-OMe film.Then the NH of 30wt% is used
4finishing coat 60nm (TC-PS) shown in OH aqueous solution spin coating Fig. 6.Use methyl alcohol to prepare together with the using of TC-PS evenly topcoat film.Find the NH of 30wt%
4the OH aqueous solution does not affect for the segmented copolymer film thickness measured by ellipsometry.Subsequently trilamellar membrane stacked body is annealed 20 hours at 170 DEG C (for PTMSS-PLA, in vacuum drying oven).When having annealed, by the PTMSS-PLA sample of annealing in vacuum drying oven under vacuo through the process cool to room temperature of about 5 hours.Then by rotating wafer with 3000rpm and applying 20 stripping liquids by pipette, 30wt%NH is used
4finishing coat is peeled off by the OH aqueous solution.Usually, as by elliptical polarizer surveyed, the film of stripping comprises the remaining finishing coat (< 4nm) that considerably less (if any) can survey.The sample peeled off is without the need to etching direct imaging.See Fig. 6.
Reference
1.Bates，F.S.and Fredr ickson，G.H.(1990)“Block CopolymerThermodynamics：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)“Polymerbrushes：surface-imobilized macromolecules，”Prog.Polym.Sci.25(5)，677-710.
Claims (46)
1. a method, comprising:
A., the substrate with surface, surperficial neutralization layer, segmented copolymer and finishing coat are provided,
B., under the condition producing the first layer, described substrate surface is processed with described surface neutralization layer;
C. produce under comprising the condition of the second layer of block copolymer film on said surface, with segmented copolymer coating described surface neutralization layer, and
D. use segmented copolymer described in top coat, thus produce third layer on said surface, wherein, segmented copolymer microcell can be made perpendicular to membrane plane orientation by means of only third layer described in thermal annealing.
2. method according to claim 1, is not wherein having the thermal annealing under finishing coat not produce vertical features.
3. method according to claim 1, wherein steps d) finishing coat be can not damage, dissolve or substantially in the solvent of not swelling segmented copolymer or solvent mixture.
4. method according to claim 1, wherein steps d) finishing coat be in the solvent reacted with finishing coat.
5. method according to claim 1, wherein steps d) finishing coat be in solvent mixture, this solvent mixture comprises the component of reacting with finishing coat.
6. method according to claim 1, is wherein dissolved in finishing coat in the liquid of at least one comprised in water, alcohol and organic solvent.
7. method according to claim 1, is wherein dissolved in liquid by finishing coat, and this liquid comprises two or more the mixture any in water, alcohol and organic solvent.
8. method according to claim 7, wherein this liquid also comprises alkali.
9. method according to claim 7, wherein this liquid is alkali.
10. method according to claim 8, wherein said alkali is amine.
11. methods according to claim 10, wherein said amine is selected from the group be made up of alkylamine, fatty amine and the amine that is connected to any combination of functional groups.
12. methods according to claim 10, wherein said amine is salt.
13. methods according to claim 12, wherein said salt has the positively charged ion in the group being selected from and being made up of ammonium cation, alkyl ammonium cation and aliphatics ammonium cation.
14. methods according to claim 12, wherein this salt contains cationic combination.
15. methods according to claim 12, wherein said salt contains negatively charged ion.
16. methods according to claim 15, wherein said negatively charged ion is hydroxide radical anion.
17. methods according to claim 8, wherein said alkali comprises ammonium hydroxide.
18. methods according to claim 8, wherein said alkali comprises alkyl ammonium hydroxide.
19. methods according to claim 8, wherein said alkali comprises Trimethylamine 99.
20. methods according to claim 8, wherein said alkali comprises the mixture of salt and amine.
21. methods according to claim 4, are wherein separated the finishing coat of reaction again.
22. methods according to claim 6, are wherein separated the finishing coat of dissolving again.
23. methods according to claim 22, the finishing coat wherein this be separated again is used in method according to claim 1 again.
24. methods according to claim 22, are wherein selected from precipitation by one or more, evaporation are separated this finishing coat again with the technology of distillation.
25. methods according to claim 1, also comprise steps d) after thermal annealing.
26. methods according to claim 25, also comprise and use stripping solvent to remove described finishing coat from described segmented copolymer, this stripping solvent can not damage, dissolve or not obvious this segmented copolymer swelling.
27. methods according to claim 3, wherein said finishing coat comprises acid anhydrides.
28. methods according to claim 27, wherein this acid anhydrides is derived from maleic anhydride.
29. methods according to claim 1, wherein this substrate is selected from by silicon, silicon oxide, glass, surface modified glass, plastics, pottery, transparent substrates, flexible substrates with in being applied to group that roller forms to the substrate of roller technique.
30. methods according to claim 1, wherein said segmented copolymer comprises multiple different block.
31. methods according to claim 30, wherein this segmented copolymer comprise at least one be different from other block one or more speed etching block.
32. methods according to claim 30, wherein this segmented copolymer contains silicon at least one block.
33. methods according to claim 30, wherein this segmented copolymer is poly-(styrene-b-4-trimethyl silyl styrene-b-vinylbenzene).
34. methods according to claim 30, wherein this segmented copolymer is poly-(4-trimethyl silyl styrene-b-D, L-rac-Lactide).
35. methods according to claim 30, wherein this segmented copolymer contains tin at least one block.
36. methods according to claim 30, wherein this segmented copolymer comprises inorganic component.
37. methods according to claim 30, wherein this segmented copolymer comprises organometallic components.
38. methods according to claim 25, wherein said thermal annealing produces the segmented copolymer microcell perpendicular to membrane plane.
39. according to the method for claim 38, and wherein the form of this microcell is selected from the group of sheet, spherical and cylindrical formation.
40. methods according to claim 25, wherein said thermal annealing carries out under the condition being selected from the group that air ambient, inert gas environment, decompression and supercharging are formed.
41. methods according to claim 2, wherein said surface neutralization layer comprises the segmentation be selected from by the individual layer of cross-linked polymer, brush (brushes), self-assembly, chemical modification surface, the surperficial and surperficial group formed of thermofixation of physically modified.
42. 1 kinds of methods, comprising:
A) substrate with surface, surperficial neutralization layer, segmented copolymer and finishing coat is provided,
B) under the condition producing the first layer, described substrate surface is processed with described surface neutralization layer;
C) under generation comprises the condition of the second layer of block copolymer film on said surface, with segmented copolymer coating described surface neutralization layer; And
D) with segmented copolymer described in top coat, thus third layer is produced on said surface,
E) under the condition making segmented copolymer feature perpendicular to membrane plane orientation, described third layer is processed.
43. according to the method for claim 42, wherein step e) described process comprise thermal annealing.
44. according to the method for claim 43, and the thermal annealing wherein under existing without finishing coat is not producing vertical features.
Described finishing coat, according to the method for claim 42, is wherein dissolved in Trimethylamine 99 by 45..
46. according to the method for claim 42, and wherein said coating comprises spin coating.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13/922,011 US9314819B2 (en) | 2012-02-10 | 2013-06-19 | Anhydride copolymer top coats for orientation control of thin film block copolymers |
| US13/922,011 | 2013-06-19 |
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| Publication Number | Publication Date |
|---|---|
| CN104592539A true CN104592539A (en) | 2015-05-06 |
| CN104592539B CN104592539B (en) | 2019-01-11 |
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| CN201410409101.4A Active CN104592539B (en) | 2013-06-19 | 2014-06-19 | Acid anhydride copolymer finishing coat for film block copolymer tropism control |
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| KR (1) | KR102303669B1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109689779A (en) * | 2016-09-13 | 2019-04-26 | 日产化学株式会社 | Upper layer film formation with composition with mutually separate method of manufacturing pattern |
| CN112771091A (en) * | 2018-07-17 | 2021-05-07 | 日产化学株式会社 | Composition for forming block copolymer layer for forming fine phase separation pattern |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| JP7061799B2 (en) * | 2016-02-23 | 2022-05-02 | ボード オブ リージェンツ，ザ ユニバーシティ オブ テキサス システム | Block copolymers for patterning less than 10 nm |
| WO2018135455A1 (en) * | 2017-01-19 | 2018-07-26 | 日産化学工業株式会社 | Underlayer film-forming composition for forming fine phase separation pattern |
| CN110198995B (en) | 2017-01-19 | 2021-10-08 | 日产化学株式会社 | Composition for forming self-assembled film for forming 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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| US7989026B2 (en) * | 2008-01-12 | 2011-08-02 | International Business Machines Corporation | Method of use of epoxy-containing cycloaliphatic acrylic polymers as orientation control layers for block copolymer thin films |
| US8999492B2 (en) * | 2008-02-05 | 2015-04-07 | Micron Technology, Inc. | Method to produce nanometer-sized features with directed assembly of block copolymers |
| US8426313B2 (en) * | 2008-03-21 | 2013-04-23 | Micron Technology, Inc. | Thermal anneal of block copolymer films with top interface constrained to wet both blocks with equal preference |
| US8114301B2 (en) * | 2008-05-02 | 2012-02-14 | Micron Technology, Inc. | Graphoepitaxial self-assembly of arrays of downward facing half-cylinders |
| JP2010115832A (en) * | 2008-11-12 | 2010-05-27 | Panasonic Corp | Method for promoting self-formation of block copolymer and method for forming self-formation pattern of block copolymer using the method for promoting self-formation |
| KR20110018678A (en) * | 2009-08-18 | 2011-02-24 | 연세대학교 산학협력단 | Control of perpendicular orientations for cylinder-forming nano structure using functional terminated polystyrene |
| CN101734610B (en) * | 2009-12-15 | 2012-05-23 | 江苏大学 | Multilayer film for low load working condition of micro electro mechanical system and preparation method thereof |
| US8623458B2 (en) * | 2009-12-18 | 2014-01-07 | International Business Machines Corporation | Methods of directed self-assembly, and layered structures formed therefrom |
| WO2011116223A1 (en) * | 2010-03-18 | 2011-09-22 | Board Of Regents The University Of Texas System | Silicon-containing block co-polymers, methods for synthesis and use |
| WO2013040483A1 (en) * | 2011-09-15 | 2013-03-21 | Wisconsin Alumni Research Foundation | Directed assembly of block copolymer films between a chemically patterned surface and a second surface |
| WO2013069544A1 (en) * | 2011-11-09 | 2013-05-16 | Jsr株式会社 | Self-organization composition for pattern formation and pattern formation method |
| US9157008B2 (en) * | 2012-02-10 | 2015-10-13 | Board Of Regents, The University Of Texas System | Anhydride copolymer top coats for orientation control of thin film block copolymers |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109689779A (en) * | 2016-09-13 | 2019-04-26 | 日产化学株式会社 | Upper layer film formation with composition with mutually separate method of manufacturing pattern |
| CN112771091A (en) * | 2018-07-17 | 2021-05-07 | 日产化学株式会社 | Composition for forming block copolymer layer for forming fine phase separation pattern |
| CN112771091B (en) * | 2018-07-17 | 2023-09-12 | 日产化学株式会社 | Composition for forming block copolymer layer for forming fine phase separation pattern |
Also Published As
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| KR102303669B1 (en) | 2021-09-16 |
| JP6480674B2 (en) | 2019-03-13 |
| SG10201403252YA (en) | 2015-01-29 |
| CN104592539B (en) | 2019-01-11 |
| KR20140147718A (en) | 2014-12-30 |
| JP2015005750A (en) | 2015-01-08 |
| TW201513222A (en) | 2015-04-01 |
| TWI658055B (en) | 2019-05-01 |
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