CN108329443A - High Florey He Jinsi parameters block polymer and atactic polymer for orienting self assembly and preparation method thereof and self-assembling method - Google Patents
High Florey He Jinsi parameters block polymer and atactic polymer for orienting self assembly and preparation method thereof and self-assembling method Download PDFInfo
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- CN108329443A CN108329443A CN201711375700.9A CN201711375700A CN108329443A CN 108329443 A CN108329443 A CN 108329443A CN 201711375700 A CN201711375700 A CN 201711375700A CN 108329443 A CN108329443 A CN 108329443A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0035—Multiple processes, e.g. applying a further resist layer on an already in a previously step, processed pattern or textured surface
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Abstract
High-molecular compound of the present invention synthesis and application, in particular it relates to can be used for orienting block polymer with high Florey He Jinsi parameters χ and atactic polymer of self assembly and preparation method thereof and self-assembling method.Block polymer is obtained by anionic polymerisation, and greatly, and compatibility is extremely low for Florey He Jinsi parameters (Flory Huggins) between block；Atactic polymer is obtained by the monomer and epoxy methacrylate monomer of the block polymer by free radical polymerization, such atactic polymer is in neutrality the block of above-mentioned block polymer.The block polymer of the present invention, the phase separation structure perpendicular to substrate can be formed after being coated on the atactic polymer neutral line after crosslinking by annealing heat-treats, and production efficiency improves；And the pattern of 20nm or less size ranges can be formed；Meanwhile block polymer provided by the invention and atactic polymer are applied to turn or more of field of microelectronics pattern, reduce its technological requirement and production cost.
Description
Technical field
The invention belongs to high-molecular compound synthesis and applications, in particular it relates to can be used to form 20nm or less
Pattern orient block polymer with high Florey He Jinsi parameters and atactic polymer of self assembly and preparation method thereof with
Self-assembling method.
Background technology
In modern semiconductors industry, the component cost and performance of integrated circuit with its achieved by critical dimension it is close
Cut phase is closed.The pattern of the critical dimension of Nano grade in order to obtain, traditional use means of photolithography are widely used.In traditional light
In carving technology, ultraviolet light (UV) is coated with by being exposed to after mask plate on the substrate of photoresist so that is occurred inside photoresist
Chemical reaction causes its exposure area, and solubility changes in developer solution with unexposed area, to obtain corresponding pattern,
Then it is transferred a pattern on substrate by modes such as etching, deposited metal or ion implantings, is finally completed the transfer of figure.
However, the critical dimension for further reducing pattern in a lithographic process is greatly limited by the cost of equipment and technique to 50nm or less
And in difficulty.In order to overcome these difficulties, orientation self assembly (DSA) block polymer (BCP) material of difference and photoetching technique
It comes into being and is widely studied.
Block polymer can be used since it can spontaneously form the periodical stratiform of 5~50nm, spherical or column structure
It has obtained researcher in orientation self assembly and has widely paid close attention to.Two blocks of BCP used in DSA should have apparent etching
Rate is distinguished, so that being formed by pattern can be transferred on substrate after over etching.The obtained patterns of DSA it is critical
Size is then determined by the molecular weight of BCP, and the size of the formed repetitive structures of BCP is observed after can annealing by film.
In particular, there are many difficulties for the application of 20nm or less pattern processing technologies at present, and if equipment is extremely expensive, technique pole
It is complicated.
Invention content
In order to overcome the application difficulty of 20nm or less patterns processing technology in the prior art, the present invention is provided to orient certainly
The block polymer with high Florey He Jinsi parameters χ of assembling.The Microphase Structure ruler formed after block copolymer phase separation
It is very little to be determined by block polymer degree of polymerization N and Florey He Jinsi parameters (Flory-Huggins parameters) χ.In order to improve
Locomitivity of block polymer segment during annealing heat-treats, it would be desirable to which there is the smaller degree of polymerization and bigger Flory-
The block polymer of Huggins parameters χ, to obtain having smaller phase separation structure size.The present invention passes through total in block
Hydroxyl is introduced in the highly polar block section of polymers, increases the difference of itself and low polar block, so that its parameter χ is increased, but hydroxyl meeting
Termination of anionic polymerization reacts, so being used as hydroxy-protective group by introducing tert-butyldimethyl silyl ether (tBDMS), is polymerizeing
It sloughs after the completion, it is required with high χ block copolymers to obtain.Phase can occur after high-temperature heat treatment for the block polymer
Separation, to improve production efficiency.
On the other hand, the present invention also provides the atactic polymer obtained using the block polymer same monomer, the polymerizations
Object has crosslink unit, and does not dissolve in solvent, two block units of the surface tension between above-mentioned block polymer after cross-linking
Between, the phase separation structure perpendicular to substrate can be obtained after its surface coating BCP and annealing heat-treats.Meanwhile the present invention
The preparation method and purposes of the block polymer and atactic polymer are additionally provided, purposes includes by the atactic polymer
The formation for being orientated Line/Space structures is combined with photoresist with block polymer.
As the first aspect of the present invention, the block with high Florey He Jinsi parameters for orienting self assembly is provided
Polymer (BCP, block co-polymer), the structure with A-b-B are specific as follows
Wherein, R1For C1-C7 alkyl, C4-C7 naphthenic base, C1-C7 alkoxies, C4-C7 cycloalkyloxies；
R2ForOrWherein x is that 2~6, y is 2~5；
M accounts for total monomer structural unit 25%-75%, n and accounts for total monomer structural unit 75%-25%.
Any of the above-described scheme is preferably, the R1For tertiary butyl, cyclohexyl, tert-butoxy, in hexamethylene alkoxy
It is any.
Any of the above-described scheme is preferably, R2For ethoxy, hydroxypropyl, any in methacrylic acid binaryglycol ester
Kind.
Any of the above-described scheme is preferably, the R1It is tert-butoxy, R2It is methacrylic acid binaryglycol ester.
Any of the above-described scheme is preferably, the R1It is tertiary butyl, R2It is ethoxy.
Any of the above-described scheme is preferably, and m accounts for total monomer structural unit 30%-60%, n and accounts for total monomer structural unit
70%-40%.
Any of the above-described scheme is preferably, and m accounts for total monomer structural unit 40-50%, n and accounts for total monomer structural unit 60-
50%.
Any of the above-described scheme is preferably, and m accounts for total monomer structural unit 50%, and n accounts for total monomer structural unit 50%.
Any of the above-described scheme is preferably, and the molecular weight distribution of the block polymer is 1.0-1.2, such as 1.0-1.08.
Any of the above-described scheme is preferably, and the molecular weight of the block polymer is 4-20kg/mol, such as 5-10kg/
mol。
The present invention also provides the preparation method of above-mentioned block polymer, synthetic route is as shown below：
According to implementation sequence, include the following steps：
(1) under the conditions of anhydrous and oxygen-free, solvent, Frozen-thawed cycled, if Frozen-thawed cycled is three times afterwards by reaction bulb are added to reaction bulb
Temperature is down to -78 DEG C；
(2) anionic initiator is added into solvent；And a certain amount of styrene derivative is added, initiator causes poly-
It closes, after reacting one hour, forms polystyrene derivative segments A；
(3) diphenylethlene is added and reacts half an hour, wait for the upper diphenyl of all active reactions termination of styrene derivative
Ethylene；
(4) methacrylate monomers with hydroxy-protective group (tert-butyldimethyl silyl ether, tBDMS) are added, after
Continuous reaction one hour, forms block polymer backbone；
(5) methanol being added into reaction bulb terminates reaction；
(6) reaction product is added drop-wise in methanol solution, filters and wash precipitation, be dried in vacuo, obtain protecting with hydroxyl
Protect the block polymer of group；
(7) tetrahydrofuran solution for configuring tetrabutyl ammonium fluoride, above-mentioned block polymer is dissolved in wherein, is stirred at room temperature 24
Hour, the hydroxy-protective group on demethylating arylate blocks；
(8) reaction product is added drop-wise in methanol solution, filters and wash precipitation, be dried in vacuo, it is required embedding to obtain
Section polymer；
Step (2)-(4) carry out under dry helium gas protection.
Preferably, in step (1), the solvent is tetrahydrofuran.
Any of the above-described scheme is preferably, and the tetrahydrofuran is by water removal deoxygenation.
Any of the above-described scheme is preferably, and in step (2), the initiator is isobutyl group lithium or n-BuLi.
Any of the above-described scheme is preferably, and in step (5), the methanol passes through Frozen-thawed cycled, such as Frozen-thawed cycled, such as freeze thawing
Cycle is three times.
Any of the above-described scheme is preferably, and in step (6), washing precipitation is carried out with methanol.
Any of the above-described scheme is preferably, and in step (6), vacuum drying carries out at room temperature.
The present invention also provides atactic polymers, by the styrenic derivatives monomer for forming block polymer, non-band
The methacrylate-based monomer and epoxy methacrylate monomer of hydroxy-protective group are obtained by free radical polymerization, should
Class atactic polymer is in neutrality two blocks of above-mentioned block polymer.
Preferably, the atactic polymer has the structure of A-r-B-r-C, specific as follows
Wherein, R1For C1-C7 alkyl, C4-C7 naphthenic base, C1-C7 alkoxies, C4-C7 cycloalkyloxies, C4-C7 part or
Whole fluorine naphthenic base；
R2ForOrWherein x is that 2~6, y is 2~5；
R3For epoxy ethylOr epoxycyclohexyl
Any of the above-described scheme is preferably, the R1For tertiary butyl, cyclohexyl, tert-butoxy, in hexamethylene alkoxy
It is any.
Any of the above-described scheme is preferably, R2For ethoxy, hydroxypropyl, any in methacrylic acid binaryglycol ester
Kind.
Any of the above-described scheme is preferably, R3For epoxycyclohexyl.
Any of the above-described scheme is preferably, and p accounts for total monomer structural unit 30%~60%, and q accounts for total monomer structural unit
6l%~30%, s account for total monomer structural unit 5%-10%.
Any of the above-described scheme is preferably, and p accounts for total monomer structural unit 40%~50%, and q accounts for total monomer structural unit
55%~40%, s account for total monomer structural unit 5%-10%.
Any of the above-described scheme is preferably, and p accounts for total monomer structural unit 45%, and q accounts for total monomer structural unit 45%, and s is accounted for
Total monomer structural unit 10%.
Any of the above-described scheme is preferably, and the molecular weight of the atactic polymer is in 5-50kg/mol.
Any of the above-described scheme is preferably, and the molecular weight distribution of the atactic polymer is in 1.4-2.5.
The present invention also provides the preparation methods of the atactic polymer to include the following steps according to implementation sequence：
1) by solvent, styrene derivative monomer, methacrylic acid lipid monomer and ring not with hydroxy-protective group
Reaction vessel is added in oxygen methacrylate-based monomer, initiator；
2) after being completely dissolved and excluding air, reaction bulb is placed in oil bath and starts to react；
3) reaction is terminated after reacting 20h, reaction product is added drop-wise in methanol solution, filters and washs and precipitate for several times (such as
Three times), vacuum drying obtains neutral line atactic polymer.
Preferably, in step 1), the solvent is toluene.
Any of the above-described scheme is preferably, and the initiator is azodiisobutyronitrile (AIBN) or benzoyl peroxide
(BPO)。
Any of the above-described scheme is preferably, and step 1) carries out under nitrogen atmosphere.
Any of the above-described scheme is preferably, implementation steps 1) when, it with stirring, is such as vigorously stirred, the speed of stirring can be certainly
Row setting.
Any of the above-described scheme is preferably, and in step 2), the temperature of oil bath is 65~90 DEG C.
Any of the above-described scheme is preferably, and in step 2), the temperature of oil bath is 70-75 DEG C.
Any of the above-described scheme is preferably, and in step 2), the temperature of oil bath is 75 DEG C.
Any of the above-described scheme is preferably, and in step 3), washing precipitation is carried out with methanol.
Any of the above-described scheme is preferably, and in step 3), vacuum drying carries out at room temperature.
The present invention also provides the above-mentioned block polymers of application and atactic polymer to be self-assembly of Line/Space patterns
Method, in sequence include step：
1) atactic polymer is configured to the solution of 0.5wt%~5wt%, after 0.22 μm of membrane filtration；Rotation
Turn to be coated on substrate surface, then 90 DEG C of baking 2min on hot plate, remove most solvents；Then hot plate temperature is improved extremely
250 DEG C, 15min is toasted, the epoxy group in atactic polymer crosslinks, and forms one layer of solvent resistant and is in neutrality layer to BCP；
2) silicon chip surface that neutral line is prepared in step 1) is coated with one layer of negative photoresist, then uses wide range,
After the exposure of 436nm, 365nm, 248nm or 193nm exposure machine, it is the grid of 100nm~1 μm that being obtained after development, which has size,
Lattice structure plan is orientated for BCP；
3) block polymer is configured to the solution of 0.5wt%~5wt%, after 0.22 μm of membrane filtration, rotation
Turn to be coated on the above-mentioned substrate surface with neutral line and orientation pattern, then 90 DEG C of baking 2min, removal are big absolutely on hot plate
Partial solvent forms one layer of BCP film in grid；
4) substrate obtained in step 3) is placed in vacuum drying oven, is toasted under the conditions of 100~250 DEG C, phase point occurs for BCP
From the layer structure formed perpendicular to neutral line, and 20nm~100nm sizes are formed under the limitation of photoresist orientation pattern
Line/Space structures.
The block polymer collocation neutral line atactic polymer of the present invention, can control its formation figure by molecular weight
The size of case can form the phase separation knot perpendicular to substrate by annealing heat-treats after being coated on the neutral line after crosslinking
The problem of structure, production efficiency improves, overcomes annealing efficiency in existing orientation self-assembling technique；And 7~20nm can be formed
The pattern of size range, the size range for forming pattern expand；Meanwhile block polymer provided by the invention and atactic polymer
Applied to turn or more of field of microelectronics pattern, its technological requirement and production cost are reduced.
Specific implementation mode
In order to it is clearer, correctly understand present disclosure, be further illustrated with reference to specific embodiment,
It illustrates.
Label "-r- " in the present invention indicates atactic polymer；"-b- " indicates block polymer.In the present invention, except special
Illustrate, molecular chain conformation is measured using gel permeation chromatography (GPC) method.
Embodiment 1
Under the conditions of anhydrous and oxygen-free, tetrahydrofuran (THF) 250mL by water removal deoxygenation is added to reaction bulb, freeze thawing follows
Reaction bulb temperature is down to -78 DEG C by ring afterwards three times.Under dry helium gas protection, the 2.5M n-BuLi hexamethylenes that 0.1mL is added are molten
After liquid, be added 1.97g to t-butoxystyrene (tBOS), after reaction one hour, 0.1mL diphenylethlenes (DPE) are added
Half an hour is reacted, the metering system of 2.12g tertiary butyl dimethyl Si ethers protection is added after all active reactions terminate upper DPE
Sour hydroxyl ethyl ester (HEMAtBDMS)The reaction was continued one hour.After reaction to reaction bulb
Middle be added terminates reaction by the methanol 4mL of Frozen-thawed cycled three times.Reaction product is added drop-wise in methanol solution, filter and is washed
For several times, such as three times, then room temperature in vacuo is dried to obtain block polymer PtBOS-b-PHEMAtBDMS to precipitation.Configure 10wt% tetra-
The 100mL tetrahydrofuran solutions of butyl ammonium fluoride, above-mentioned block polymer is dissolved in wherein, is stirred at room temperature 24 hours, is sloughed first
Hydroxy-protective group on base arylate blocks, reaction product is added drop-wise in methanol solution, is filtered and is washed precipitation for several times,
As three times, then room temperature in vacuo is dried to obtain block polymer PtBOS-b-PHEMA.Block polymer PtBOS-b-PHEMA
Weight average molecular weight be 13kg/mol, molecular weight distribution 1.02.55%, the n that m accounts for total monomer structural unit accounts for total monomer structure
The 45% of unit.
In the case where nitrogen atmosphere is vigorously stirred, by solvent toluene 250mL, 17.71gtBOS, 10.55g hydroxyethyl methacrylate second
Ester (HEMA) and 1.96g 3,4- epoxycyclohexyl-methyl acrylate, 0.42g initiator azodiisobutyronitriles (AIBN) are added
Reaction vessel.After being completely dissolved and excluding air, reaction bulb is placed in 75 DEG C of oil baths and starts to react.It is terminated after reaction 20h
Reaction, reaction product is added drop-wise in methanol solution, is filtered and is washed precipitation three times, it is random that room temperature in vacuo is dried to obtain neutral line
Polymer, molecular weight 19kg/mol, molecular weight distribution 1.64.54%, the q that p accounts for total monomer structural unit accounts for total monomer knot
41%, s of structure unit accounts for the 5% of total monomer structural unit.
By above-mentioned polymer using toluene be configured to 3% solution and use 0.22 μm of polytetrafluoroethylene (PTFE) miillpore filter mistake
Filter.
By above-described embodiment gained neutral line polymer solution rotary coating on 8 inches of monocrystalline silicon pieces, at 250 DEG C of hot plate
5min is toasted, measurement film thickness is 20nm；It is coated with negative photoresist in neutral layer surface, 90 DEG C of front baking toasts 60s, film thickness 45nm,
248nm exposure wavelengths expose, and rear at 110 DEG C to dry 60s, development 60s is obtained in 2.38% tetramethylammonium hydroxide (TMAH) developer solution
To induction figure.It is coated with BCP solution, thickness 45nm, 90 DEG C of baking 2min form the Line/Space patterns of 16nm.
Embodiment 2
Under the conditions of anhydrous and oxygen-free, tetrahydrofuran (THF) 250mL by water removal deoxygenation is added to reaction bulb, freeze thawing follows
Reaction bulb temperature is down to -78 DEG C by ring afterwards three times.Under dry helium gas protection, the 2.5M n-BuLi hexamethylenes that 0.6mL is added are molten
After liquid, the t-butyl styrene (tBS) of 4.80g is added, after reacting one hour, 1.8mL diphenylethlenes (DPE) is added and react half
Hour, the methacrylic acid hydroxypropyl of 7.74g tertiary butyl dimethyl Si ethers protection is added after all active reactions terminate upper DPE
Ester (HPMAtBDMS)The reaction was continued one hour.Add after reaction into reaction bulb
Enter and terminates reaction by the methanol 4mL of Frozen-thawed cycled three times.Reaction product is added drop-wise in methanol solution, filter and washs precipitation
For several times, as three times, room temperature in vacuo is dried to obtain block polymer PtBS-b-PHPMAtBDMS.Configure the fluorination of the 10wt% tetrabutyls
The 100mL tetrahydrofuran solutions of ammonium, above-mentioned block polymer is dissolved in wherein, is stirred at room temperature 24 hours, demethylating acrylic acid
Hydroxy-protective group on ester block, reaction product is added drop-wise in methanol solution, is filtered and is washed precipitation for several times, such as three times,
Then room temperature in vacuo is dried to obtain block polymer PtBS-b-PHPMA, molecular weight 5.8kg/mol, and molecular weight distribution is
1.03.50%, the n that m accounts for total monomer structural unit accounts for the 50% of total monomer structural unit.
In the case where nitrogen atmosphere is vigorously stirred, by solvent toluene 250mL, 14.4gtBS, 12.96g hydroxy propyl methacrylate
(HPMA) and reaction is added in 2.84g methyl propenoic acid glycidyl ethers (GMA), 0.16g initiator azodiisobutyronitriles (AIBN)
Container.After being completely dissolved and excluding air, reaction bulb is placed in 75 DEG C of oil baths and starts to react.Reaction is terminated after reacting 20h,
Reaction product is added drop-wise in methanol solution, filter and washs precipitation for several times, such as three times, vacuum drying obtains neutral line and randomly gathers
Close object, molecular weight 30kg/mol, molecular weight distribution 1.87；45%, the q that p accounts for total monomer structural unit accounts for total monomer structure
45%, s of unit accounts for the 10% of total monomer structural unit.
By above-mentioned polymer using propylene glycol methyl ether acetate be configured to 3% solution and use 0.22 μm of polytetrafluoroethylene (PTFE)
Filtering with microporous membrane.
By above-described embodiment gained neutral line polymer solution rotary coating on 8 inches of monocrystalline silicon pieces, at 200 DEG C of hot plate
5min is toasted, measurement film thickness is 20nm；It is coated with negative photoresist in neutral layer surface, 90 DEG C of front baking toasts 60s, film thickness 30nm,
365nm exposure wavelengths expose, and rear at 110 DEG C to dry 60s, development 60s obtains induction figure in 2.38%TMAH developer solutions.Coating
BCP solution, thickness 15nm, 90 DEG C of baking 2min form the Line/Space patterns of 9.6nm.
Embodiment 3
Under the conditions of anhydrous and oxygen-free, tetrahydrofuran (THF) 250mL by water removal deoxygenation is added to reaction bulb, freeze thawing follows
Reaction bulb temperature is down to -78 DEG C by ring afterwards three times.Under dry helium gas protection, the 2.5M n-BuLi hexamethylenes of 0.429mL are added
After solution, the t-butoxystyrene (tBOS) of 3.52g is added, after reacting one hour, 0.3mL diphenylethlenes (DPE) are added
Half an hour is reacted, the metering system of 4.81g tertiary butyl dimethyl Si ethers protection is added after all active reactions terminate upper DPE
Acid diethylene glycol ester (DEGMEAtBDMS)The reaction was continued one hour.Reaction
It is added into reaction bulb after end and terminates reaction by the methanol 4mL of Frozen-thawed cycled three times.It is molten that reaction product is added drop-wise to methanol
In liquid, filters and wash precipitation for several times, such as three times, room temperature in vacuo is dried to obtain block polymer PtBOS-b-PDEGMAtBDMS.
The 100mL tetrahydrofuran solutions for configuring 10wt% tetrabutyl ammonium fluorides, above-mentioned block polymer is dissolved in wherein, is stirred at room temperature 24
Hour, reaction product is added drop-wise in methanol solution, filters and wash by the hydroxy-protective group on demethylating arylate blocks
Wash precipitation for several times, such as three times, then room temperature in vacuo is dried to obtain block polymer PtBOS-b-PDEGMA, molecular weight 8kg/
Mol, molecular weight distribution 1.1；50%, the n that m accounts for total monomer structural unit accounts for the 50% of total monomer structural unit.
In the case where nitrogen atmosphere is vigorously stirred, by solvent toluene 250mL, 14.7gtBOS, 14.5g methacrylic acid diethyl two
Alcohol ester (DEGMA) and 1.28g methyl propenoic acid glycidyl ethers, reaction, which is added, in 5.37g initiators benzoyl peroxide (BPO) holds
Device.After being completely dissolved and excluding air, reaction bulb is placed in 75 DEG C of oil baths and starts to react.Reaction is terminated after reacting 20h, it will
Reaction product is added drop-wise in methanol solution, is filtered and is washed precipitation for several times, such as three times, it is random that room temperature in vacuo is dried to obtain neutral line
Polymer, molecular weight 20kg/mol, molecular weight distribution 2.02；48%, the q that p accounts for total monomer structural unit accounts for total monomer knot
48%, s of structure unit accounts for the 4% of total monomer structural unit.
By above-mentioned polymer using propylene glycol monomethyl ether be configured to 2.5% solution and use 0.22 μm of polytetrafluoroethylene (PTFE) micropore
Membrane filtration.
By above-described embodiment gained neutral line polymer solution rotary coating on 8 inches of monocrystalline silicon pieces, at 250 DEG C of hot plate
5min is toasted, measurement film thickness is 25nm；It is coated with negative photoresist in neutral layer surface, 90 DEG C of front baking toasts 60s, film thickness 50nm,
248nm exposure wavelengths expose, and rear at 110 DEG C to dry 60s, development 60s obtains induction figure in 2.38%TMAH developer solutions.Coating
BCP solution, thickness 50nm, 90 DEG C of baking 2min form the Line/Space patterns of 13.5nm.
Embodiment 4
Under the conditions of anhydrous and oxygen-free, tetrahydrofuran (THF) 250mL by water removal deoxygenation is added to reaction bulb, freeze thawing follows
Reaction bulb temperature is down to -78 DEG C by ring afterwards three times.Under dry helium gas protection, the 2.5M n-BuLi hexamethylenes that 0.15mL is added are molten
After liquid, the cyclohexyl styrene (CHBS) of 1.86g is added, after reacting one hour, it is anti-that 0.1mL diphenylethlenes (DPE) are added
Half an hour is answered, the metering system of 2.034g tertiary butyl dimethyl Si ethers protection is added after all active reactions terminate upper DPE
Sour hydroxyl ethyl ester (HEMAtBDMS), the reaction was continued one hour.It is added after reaction into reaction bulb by Frozen-thawed cycled three times
Methanol 4mL terminates reaction.Reaction product is added drop-wise in methanol solution, filter and washs precipitation for several times, such as three times, room temperature in vacuo
It is dried to obtain block polymer PCHBS-b-PHEMAtBDMS.The 100mL tetrahydrofurans for configuring 10wt% tetrabutyl ammonium fluorides are molten
Above-mentioned block polymer is dissolved in wherein by liquid, is stirred at room temperature 24 hours, the hydroxyl protection base on demethylating arylate blocks
Group, reaction product is added drop-wise in methanol solution, is filtered and is washed precipitation for several times, such as three times, then room temperature in vacuo is dried to obtain
Block polymer PCHBS-b-PHEMA, molecular weight 12kg/mol, molecular weight distribution 1.05.M accounts for total monomer structural unit
50%, n account for the 50% of total monomer structural unit.
In the case where nitrogen atmosphere is vigorously stirred, by solvent toluene 250mL, 16.9gCHBS, 13.2gHEMA and 1.14g methyl-prop
Reaction vessel is added in olefin(e) acid glycidol ether, 0.255g initiators benzoyl peroxide (BPO).It waits being completely dissolved and excludes air
Afterwards, reaction bulb is placed in 75 DEG C of oil baths and starts to react.Reaction is terminated after reacting 20h, reaction product is added drop-wise to methanol solution
In, it filters and washs precipitation for several times, such as three times, room temperature in vacuo is dried to obtain neutral line atactic polymer, molecular weight 29.6kg/
Mol, molecular weight distribution 1.72.45%, the q that p accounts for total monomer structural unit accounts for 51%, s of total monomer structural unit and accounts for total list
The 4% of body structural unit.
By above-mentioned polymer using propylene glycol monomethyl ether be configured to 2.5% solution and use 0.22 μm of polytetrafluoroethylene (PTFE) micropore
Membrane filtration.
By above-described embodiment gained neutral line polymer solution rotary coating on 8 inches of monocrystalline silicon pieces, at 250 DEG C of hot plate
5min is toasted, measurement film thickness is 25nm；It is coated with negative photoresist in neutral layer surface, 90 DEG C of front baking toasts 60s, film thickness 40nm,
248nm exposure wavelengths expose, and rear at 110 DEG C to dry 60s, development 60s obtains induction figure in 2.38%TMAH developer solutions.Coating
BCP solution, thickness 65nm, 90 DEG C of baking 2min form the Line/Space patterns of 20nm.
In the present invention, vacuum drying temperature is not limited to room temperature, and the speed of stirring does not also limit, art technology
Personnel can be voluntarily arranged.
It should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, it will be understood by those of ordinary skill in the art that：It is still
Either which part or all technical features can be carried out so that technical scheme described in the above embodiments is modified
Equivalent replacement；And these modifications or replacements, it does not separate the essence of the corresponding technical solution various embodiments of the present invention technical side
The range of case.
Claims (10)
1. the block polymer with high Florey He Jinsi parameters, the structure with A-b-B is specific as follows
Wherein, R1For C1-C7 alkyl, C4-C7 naphthenic base, C1-C7 alkoxies, C4-C7 cycloalkyloxies；
R2ForWherein x is that 2~6, y is 2~5；
M accounts for total monomer structural unit 25%-75%, n and accounts for total monomer structural unit 75%-25%.
2. block polymer as described in claim 1, it is characterised in that：The R1For tertiary butyl, cyclohexyl, tert-butoxy,
Any one of hexamethylene alkoxy.
3. block polymer as claimed in claim 1 or 2, it is characterised in that：R2For ethoxy, hydroxypropyl, methacrylic acid two
Any one of glycol ester.
4. block polymer as claimed in claim 1 or 2, it is characterised in that：The R1It is tert-butoxy, R2It is metering system
Acid diethylene glycol ester.
5. block polymer as claimed in claim 1 or 2, it is characterised in that：The R1It is tertiary butyl, R2It is ethoxy.
6. the preparation method of block polymer as described in any one of claim 1-5, according to implementation sequence, including following step
Suddenly：
(1) under the conditions of anhydrous and oxygen-free, solvent is added to reaction bulb, the air dissolved in solvent is removed after Frozen-thawed cycled, will react
Bottle temperature is down to -78 DEG C；
(2) anionic initiator and styrene derivative are added into solvent, initiator causes polymerization, after reacting one hour, shape
At polystyrene derivative segments A；
(3) diphenylethlene is added and reacts half an hour, wait for the upper diphenylethlene of all active reactions termination of styrene derivative；
(4) methacrylate-based monomer with hydroxy-protective group is added, the reaction was continued one hour, forms block polymer
Backbone；
(5) methanol being added into reaction bulb terminates reaction；
(6) reaction product is added drop-wise in methanol solution, filters and wash precipitation, be dried in vacuo, obtain carrying hydroxyl protection base
The block polymer of group；
(7) dichloromethane and tetrahydrofuran mixed solvent of configuration tetrabutyl ammonium fluoride, above-mentioned block polymer is dissolved in wherein,
It is stirred at room temperature 24 hours, the blocking group on demethylating arylate blocks；
(8) reaction product is added drop-wise in methanol solution, filters and wash precipitation, be dried in vacuo, to obtain block polymer；
Step (2)-(4) are carried out under helium protection.
7. atactic polymer, by any one of the claim 1-5 styrenic derivatives monomers for forming block polymer,
The methacrylate-based monomer and epoxy methacrylate monomer of not hydroxyl blocking group are obtained by free radical polymerization
It arrives, such atactic polymer is in neutrality two blocks of above-mentioned block polymer.
8. the preparation method of atactic polymer as claimed in claim 7 includes the following steps according to implementation sequence：
1) by solvent, styrene derivative monomer, the methacrylic acid lipid monomer of not hydroxyl blocking group and epoxy methyl
Reaction vessel is added in acrylic ester monomer, initiator；
2) after being completely dissolved and excluding air, reaction bulb is placed in oil bath and starts to react；
3) reaction is terminated after reacting 20h, reaction product is added drop-wise in methanol solution, filters and washs precipitation, be dried in vacuo
To neutral line atactic polymer.
9. preparation method as claimed in claim 8, it is characterised in that：Step 1) -3) it is carried out under dry nitrogen atmosphere.
10. block polymer and atactic polymer as claimed in claim 7 of the application as described in any one of claim 1-5
It is self-assembly of the method for being orientated Line/Space patterns, includes step in sequence：
1) atactic polymer is configured to the solution of 0.5wt%~5wt%, after 0.22 μm of membrane filtration；Rotation applies
Cloth is in substrate surface, and then 90 DEG C of baking 2min on hot plate, remove most solvents；Then hot plate temperature is improved to 250
DEG C, 15min is toasted, the epoxy group in atactic polymer crosslinks, and forms one layer of 10nm~100nm solvent resistant and to block
Polymer is in neutrality layer；
2) silicon chip surface that neutral line is prepared in step 1) is coated with one layer of 10nm~80nm negative photoresist, then uses width
Spectrum, 436nm, 365nm after the exposure of 248nm 193nm exposure machines, obtain after development with size being 100nm~1 μm
Lattice structure pattern for block polymer be orientated；
3) block polymer is configured to the solution of 0.5wt%~5wt%, after 0.22 μm of membrane filtration, rotation applies
Cloth is in the above-mentioned substrate surface with neutral line and orientation pattern, and then 90 DEG C of baking 2min, removal are most on hot plate
Solvent forms one layer of 10nm~100nm block polymer film in grid；
4) pass through long-time high-temperature heat treatment, layer structure of the phase separation formation perpendicular to neutral line occurs for block polymer, and
The Line/Space structures of 20nm or less sizes are formed under the limitation of photoresist orientation pattern.
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| US20160186004A1 (en) * | 2014-12-30 | 2016-06-30 | Rohm And Haas Electronic Materials Llc | Copolymer formulation for directed self assembly, methods of manufacture thereof and articles comprising the same |
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