CN104119477B - Resist polymer and comprise the anti-corrosion agent composition of this polymer - Google Patents

Resist polymer and comprise the anti-corrosion agent composition of this polymer Download PDF

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CN104119477B
CN104119477B CN201410165789.6A CN201410165789A CN104119477B CN 104119477 B CN104119477 B CN 104119477B CN 201410165789 A CN201410165789 A CN 201410165789A CN 104119477 B CN104119477 B CN 104119477B
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resist
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CN104119477A (en
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朱炫相
金真湖
韩俊熙
柳印泳
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Aiskai New Material High Performance Co Ltd
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Korea Kumho Petrochemical Co Ltd
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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
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/004—Photosensitive materials
    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2037—Exposure with X-ray radiation or corpuscular radiation, through a mask with a pattern opaque to that radiation
    • G03F7/2039—X-ray radiation
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34

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Abstract

The present invention relates to the resist polymer of a kind of formula 1 below and the anti-corrosion agent composition containing this polymer, when utilizing photoetching technique to form pattern, particularly, when forming pattern by NTD mode, by improving the dissolubility to organic developer solution, nargin and resolution are improved, useful for forming the Resist patterns with low LWR, it addition, the improvement excellent effect of contrast.Chemical formula 1In described chemical formula 1, R1To R4, a and b respectively as description define.

Description

Resist polymer and comprise the anti-corrosion agent composition of this polymer
Technical field
The present invention relates to a kind of resist polymer utilizing photoetching technique to use when forming pattern and the anti-corrosion agent composition that comprises this polymer.
Background technology
Recently, photoetching (lithography) technology actively carries out adopting the high-volume manufacture (HVM, highvolumnmanufacturing) of ArF immersion lithography (immersion), is substantially carried out realizing the technological development of below 50nm live width.Additionally, as the method for contact hole (contacthole) pattern for realizing 30nm live width, actively carry out the developmental research of discharged-area development technology (NTD, negative-tonedevelopment).
Discharged-area development technology (NTD, negative-tonedevelopment) is to print critical details in a play not acted out on stage, but told through dialogues layer, is obtained the image inversion technology of the image quality of excellence by photomask (brightfileldmask).NTD resist generally utilizes containing acid labile group and light acid propellant resin.NTD resist irradiates exposure under (actinicradiation) at light width, then light acid propellant forms acid, blocks acid labile group, therefore cause that the polarity of exposure area changes after this acid exposure during bakeing.Its result, between exposure area and the unexposed area of resist, dissolubility there are differences, the unexposed area of resist is eliminated by specific organic developer such as ketone, esters or ethers organic developer, therefore, remains the pattern generated due to insoluble exposure area.
By the foregoing specific mechanism of action, conventional 193nm photoresist is applicable to the situation of NTD resist, specific problem can be caused.As one example, the photoresist pattern after development, compared to resist layer before exposure, its thickness loss is a lot, thus, during follow-up etching, a part for Resist patterns is completely etched away, and causes the defect of pattern.Thickness loss as above, is by conventional use of macromole acid labile group, for instance three grades of large-scale ester groups, caused by losing from resist layer cut-out.For dipole inversion, for having only to the conventional 193nm photoresist of acid labile group amassed as generally noted above, thickness loss is more serious because of the high-load of as above group.In order to solve the problems referred to above, if using thicker resist layer, it is likely that pattern chaps, and the other problems such as focus minimizing, therefore can not provide the solution of practical significance.Additionally, NTD uses the pattern be full of cracks occurred when typical 193nm photoresist, due to the base polymer from (methyl) acrylate, particularly individually carry out the specific acid unstability group of dipole inversion, such as, after cutting off tertiary alkyl ester and acetal disengaging base, larger amount of produced by the exposure area of photoresist (methyl) acrylic acid units, cause that problem more worsens.Additionally, rely solely on the standard resist at the bigger acid labile group of described polarity for dipole inversion for the situation of NTD, there is the reduction that another kind of problem is elching resistant.
Therefore, actively carry out solving the research of described problem.
Patent documentation
Patent documentation 1: Korea S's Patent Publication the 2012-0026991st (2012.03.20 is open)
Patent documentation 2: Korea S's Patent Publication the 2012-0061757th (2012.06.13 is open)
Patent documentation 3: Korea S's Patent Publication the 2012-0078672nd (2012.07.10 is open)
Patent documentation 4: Korea S's Patent Publication the 2012-0098540th (2012.09.05 is open)
Patent documentation 5: Korea S's Patent Publication the 2012-0101618th (2012.09.14 is open)
Patent documentation 6: Korea S's Patent Publication the 2012-0114168th (2012.10.16 is open)
Summary of the invention
It is an object of the invention to provide a kind of resist polymer, photoetching technique is utilized to form pattern, particularly, when forming pattern by NTD mode, by improving dissolubility to organic developer solution, nargin and resolution are improved, and have a Resist patterns forming low line width roughness (LWR, linewidthroughness) and useful, it addition, contrast improves excellent effect.
Another object of the present invention is to provide a kind of anti-corrosion agent composition, it comprises described polymer.
In order to reach described purpose, according to one embodiment of the invention, it is provided that have the resist polymer of formula 1 below.
Chemical formula 1
In described chemical formula 1,
R1It is selected from group: hydrogen atom；Hydroxyl；Acetal radical；Itrile group；It is selected from by halogen, itrile group, hydroxyl, alkoxyl, acetal radical, acyl group, aldehyde radical, the substituted or unsubstituted carbon number of more than one substituent groups in the group that carboxyl and ester group form is the alkyl of 1～20, carbon number is the alkoxyl of 1～20, carbon number is the aryl of 6～30, silylation, carbon number is the thiazolinyl of 2～20, carbon number be 3～30 cycloalkyl and ring in comprise at least one selected from N, P, the heterocyclic radical that heteroatomic carbon number is 2～30 in the group of O and S composition；And their combination；
R2It is the alkoxyl of 1～20 for carbon number；
R3And R4It is each independently the cycloalkyl selecting thiazolinyl that aryl that alkane halogeno-group that alkyl that free hydrogen atom, carbon number are 1～20, carbon number are 1～20, carbon number are 6～30, carbon number are 2～20, carbon number to be 3～30 and by their group formed, or the formation that is bonded to each other comprises the heterocyclic radical of oxygen atom in ring；
A and b when meeting a+b=1,0 < a/ (a+b) < 1,0 <b/ (a+b) < 1.
Preferably, described R1Can select in the group that free hydrogen atom, hydroxyl, acetal radical, itrile group and the functional group represented by following chemical formula 2 form:
Chemical formula 2
In described chemical formula 2, n is the integer of 1～3,
Ra selects in the group that free hydrogen atom, hydroxyl and acetal radical form,
Described RbFor selecting freedomnullAcid-sensitive sensillary base (acidlabilegroup) in the group formed，Now，R’、R " and R " ' be each independently choosing free carbon number be the alkyl of 1～20、Carbon number is the cycloalkyl of 3～30、Hydroxyl、(carbon number is the alkyl of 1～10) cycloalkyl、Hydroxy alkyl、Carbon number is the alkoxyl of 1～20、(carbon number is the alkoxyl of 1～10) alkyl、Acetyl group、Acetyl alkyl、Carboxyl、(carbon number is the alkyl of 1～10) carboxyl、In the group that (carbon number is the cycloalkyl of 3～18) carboxyl and the Heterocyclylalkyl that carbon number is 3～30 form，Or group adjacent one another are connects can form the saturated of carbon number 3～30 or undersaturated hydrocarbon ring or heterocycle，R " " it is the alkyl of 1～10 for carbon number，Z is the integer of 0 to 3，W is the integer of 0 to 10.
Preferably, described resist polymer, it is possible to choosing freely has in the group of compound composition of formula 1 below a to 1x structure:
In described chemical formula 1a to 1x, RbFor selecting freedomnullAcid-sensitive sensillary base in the group formed，Now，R’、R " and R " ' be each independently choosing free carbon number be the alkyl of 1～20、Carbon number is the cycloalkyl of 3～30、(carbon number is the alkyl of 1～10) cycloalkyl、Hydroxy alkyl、Carbon number is the alkoxyl of 1～20、(carbon number is the alkoxyl of 1～10) alkyl、Acetyl group、Acetyl alkyl、Carboxyl、(carbon number is the alkyl of 1～10) carboxyl、In the group that (carbon number is the cycloalkyl of 3～18) carboxyl and the Heterocyclylalkyl that carbon number is 3～30 form，Or group adjacent one another are connects can form the saturated or undersaturated hydrocarbon ring or heterocycle that carbon number is 3～30，R " " it is the alkyl of 1～10 for carbon number，Z is the integer of 0 to 3，W is the integer of 0 to 10，Wherein，A and b is when meeting a+b=1，Meet 0 < a/ (a+b) < 1 and 0 <b/ (a+b) < 1.
Preferably, described resist polymer is 1,000 to 50 according to the weight average molecular weight (hereinafter referred to as " Mw ") of gel permeation chromatography (gelpermeationchromatography:GPC) polystyrene conversion, 000g/mol.
Preferably, the weight average molecular weight of described resist polymer is 1 to 3 with the molecular weight distribution of the ratio (Mw/Mn) of number-average molecular weight.
According to another embodiment of the present invention, it is provided that a kind of anti-corrosion agent composition comprising described resist polymer.
Preferably, relative to the gross weight of anti-corrosion agent composition, the content of described resist polymer is 3 to 20 weight %.
Described anti-corrosion agent composition, it is possible to be discharged-area development anti-corrosion agent composition.
According to another embodiment of the present invention, it is provided that a kind of method forming Resist patterns, it comprises the steps: to be coated on substrate by described anti-corrosion agent composition and is formed the step of resist film；After resist film described in heat treated, with the step that predetermined pattern is exposed；And, the step of the Resist patterns that development is exposed.
Preferably, described exposure technology can utilize the light source in the group selecting free KrF excimer laser, ArF excimer laser, extreme ultraviolet laser, X-ray and electron beam to form to implement.
Preferably, described development can utilize the organic developer solution of counter-rotative type to implement.
The particular content of other specific embodiments of the present invention, has description in the following detailed description.
Invention effect
The polymer that the present invention relates to, when utilizing photoetching technique to form pattern, particularly, when forming pattern by NTD mode, by improving dissolubility to organic developer solution, nargin and resolution are improved, and are formed and have a fine Resist patterns of low LWR and useful.
Detailed description of the invention
Below, embodiments of the invention are described in detail.But this is only used as illustration and proposes, and the present invention is not limited to this, and protection scope of the present invention should be as the criterion with the record of claims.
Unless be otherwise noted in this manual, all compounds or substituent group can be substituted or unsubstituted.At this, it is replaced and refers to that hydrogen is selected from any one in the group being made up of halogen atom, hydroxyl, carboxyl, cyano group, nitro, amino, sulfydryl, methyl mercapto, alkoxyl, itrile group, aldehyde radical, epoxy radicals, ether, ester group, carbonyl, acetal radical, ketone group, alkyl, perfluoroalkyl, cycloalkyl, Heterocyclylalkyl, pi-allyl, benzyl, aryl, heteroaryl and their derivant thereof and their combination and replaces.
Unless be otherwise noted in this manual, " their combination " refers to, plural functional group is by alkylidene (such as methylene (-CH that singly-bound, double bond, three keys, carbon number are 1～102-), ethylidene (-CH2CH2-) etc.), carbon number be 1～10 perfluorinated alkylidene (such as, perfluoromethylene (-CF2-), perfluor ethylidene (-CF2CF2-) etc.), the hetero atom such as N, O, P, S or Si or comprise its functional group (such as, carbonyl (-C=O-), ether (-O-), ester group (-COO-) is comprised in molecule,-S-, the assorted alkylidene of-NH-or-N=N-etc.) etc. linking group combine, or plural functional group through condensation connect.
Along with the wire spoke of semiconductor integrated circuit is more and more less, one of required characteristic is line width roughness.But, polymer as traditional PTD (positivetonedevelopment) type, main use (methyl) acrylic monomers, synthesis bipolymer, terpolymer, quadripolymer use, so alternately (alternative) or random (randomization) between monomer is not easy,, when thus be accordingly used in anti-corrosion agent composition, there is the problem that line edge roughness reduces in easy massing (block).
To this, in the present invention, preparation COMA base polymer uses, maleic anhydride and cyclic hydrocarbon alternating polymerization according to a certain percentage, therefore massing need not be worried, thus preventing the reduction of line edge roughness characteristic, irradiating the ArF light time, in order to reduce the light of absorption, make the generation ring-opening reaction of maleic anhydride, by the carboxylic acid that open loop generates, make organic developer solution of developer solution as NTD photoresist, the dissolubility of such as n-butyl acetate reduces, the carboxyl generated when open loop replaces with acid-unstable group, therefore while can improving the dissolubility to organic developer solution, improve the selection ratio between exposure area and unexposed area, when forming pattern, nargin and the resolution of excellence can be reached, and low line width roughness.
That is, the resist polymer that the one embodiment of the invention prepared by described preparation method is related to, has the structure of following chemical formula 1:
Chemical formula 1
In described chemical formula 1,
R1For being selected from group: hydrogen atom；Hydroxyl；Acetal radical；Itrile group；It is selected from by halogen, itrile group, hydroxyl, alkoxyl, acetal radical, acyl group, aldehyde radical, carbonyl, the substituted or unsubstituted carbon number of more than one substituent groups in the group that carboxyl and ester group form is the alkyl of 1～20, carbon number is the alkoxyl of 1～20, carbon number is the aryl of 6～30, silylation, carbon number is the thiazolinyl of 2～20, carbon number be 3～30 cycloalkyl and ring in comprise at least one selected from N, P, the heterocyclic radical that heteroatomic carbon number is 2～30 in the group that O and S forms；And their combination,
R2It is the alkoxyl of 1～20 for carbon number,
R3And R4Being each independently and selecting thiazolinyl that aryl that haloalkyl that alkyl that free hydrogen atom, carbon number are 1～20, carbon number are 1～20, carbon number are 6～30, carbon number are 2～20, carbon number is the cycloalkyl of 3～30 and by their group formed, or it is bonded to each other and forms the heterocyclic radical comprising oxygen atom in ring
A and b when meeting a+b=1,0 < a/ (a+b) < 1,0 <b/ (a+b) < 1.
Preferably, R1nullFor being selected from group: hydrogen atom，Hydroxyl，Acetal radical，Itrile group，Or，It is selected from by halogen、Itrile group、Hydroxyl、Carbon number is the alkoxyl of 1～10、Carbon number is the acetal radical of 2～10、Carbon number is the acyl group of 2～10、Aldehyde radical、Carboxyl and ester group (-COOR，Here R is carbon number is the alkyl of 1～20) the substituted or unsubstituted carbon number of more than one substituent groups in the group that forms is the alkyl of 1～20、Carbon number is the alkoxyl of 1～20、Carbon number is the aryl of 6～18、Silylation、Carbon number is a ring type cycloalkyl of 3～14、Carbon number is the two ring type cycloalkyl of 8～18、Carbon number is the three-ring type cycloalkyl of 10～30、Carbon number is the four ring type cycloalkyl of 10～30、The free N of at least one choosing is comprised in ring、P、The heterocyclic radical that heteroatomic carbon number is 3～30 in the group that O and S forms，And their combination；It is further preferred that described R1For selecting in the group that the functional group that free hydrogen atom, hydroxyl, itrile group, acetal radical and following chemical formula 2 represent forms.
Chemical formula 2
In described chemical formula 2, n is the integer of 1～3,
RaFor in the group that hydrogen atom, hydroxyl and acetal radical form,
It is preferably the functional group of hydrogen atom, hydroxyl and following chemical formula 3a or 3b,
Described RbFor selecting freedomAcid-sensitive in the group formed
nullBase (acidlabilegroup)，Now，R’、R " and R " ' be each independently choosing free carbon number be the alkyl of 1～20、Carbon number is the cycloalkyl of 3～30、Hydroxyl、(carbon number is the alkyl of 1～10) cycloalkyl、Hydroxy alkyl、Carbon number is the alkoxyl of 1～20、(carbon number is the alkoxyl of 1～10) alkyl、Acetyl group、Acetyl alkyl、Carboxyl、(carbon number is the alkyl of 1～10) carboxyl、In the group that (carbon number is the cycloalkyl of 3～18) carboxyl and the Heterocyclylalkyl that carbon number is 3～30 form，Or group adjacent one another are connects can form the saturated or undersaturated hydrocarbon ring or heterocycle that carbon number is 3～30，R " " it is the alkyl of 1～10 for carbon number，Z is the integer of 0 to 3，W is the integer of 0 to 10.It is further preferred that RbFor selecting in the group that the free tert-butyl group, TMS, hydroxyl-2-ethyl, 1-methoxy-propyl, 1-methoxyl group-1-Methylethyl, 1-ethoxycarbonyl propyl, 1-ethyoxyl-1-Methylethyl, 1-methoxyl group-1-ethyl, 1-ethyoxyl-1-ethyl, t-butoxy-2-ethyl, 1-isobutoxy-1-ethyl and following chemical formula 4a～4j form:
In described chemical formula 4a～4j, R', R " and R " ' is each independently the alkyl that selects free carbon number to be 1～10, carbon number be 3～18 cycloalkyl and the group that forms of hydroxyl in, o and s is the integer of 0～15, and p is the integer of 0～11, q and r is each independently the integer of 0～9, t is the integer of 0～7, and u and v is each independently the integer of 0～6, simultaneously, 0≤q+r≤16,0≤q+t≤14.
It is further preferred that described R1It can be any one functional group in following chemical formula 2a to 2e.
In described chemical formula 2a～2e, RbAs acid sensitive group, as defined above.
Additionally, in described chemical formula 1, R2For functional group after the ring-opening reaction of the maleic anhydride caused by alcohol compound.During described ring-opening reaction, the carbon number of alcohol is more many, or apparatus derivatorius, the open loop degree reduction of maleic anhydride, and therefore, the alcohol compound of use in ring-opening reaction, carbon number is more few more favourable, linear chain structure is more favourable.Therefore, described R2It is preferably the straight chain alcohol radical that carbon number is 1～10, more preferably methoxyl group, ethyoxyl, propoxyl group or butoxy.
In described chemical formula 1, described R3Selecting free carbon number is the alkyl of 1～10, three-ring type cycloalkyl that two ring type cycloalkyl that a ring type cycloalkyl that aryl that carbon number is 6～30, carbon number are 3～14, carbon number are 8～18, carbon number are 10～30, carbon number be 10～30 four ring type cycloalkyl and the group that forms of their combination in；R4It can be the alkyl of carbon number 1～10；Or, described R3And R4Combine, form the THP trtrahydropyranyl in ring with oxygen (O).More specifically, described R3Can be methyl or ethyl, described R4For methyl, or described R3And R4Combine, form the THP trtrahydropyranyl in ring with oxygen (O).
In described chemical formula 1, a and b represents each repetitive content in main chain, means the Replacement rate that polymer dissolves in developer solution simultaneously.The polymer that the present invention relates to, described a and b is when meeting a+b=1, meet 0 < a/ (a+b) < 1 and 0 <b/ (a+b) < 1, preferably meet 0.3≤a/ (a+b)≤0.7 and 0.3≤b/ (a+b)≤0.7 such that it is able to form fine pattern.
Concrete example as described polymer, it is possible to enumerate the compound etc. with following chemical formula 1a to 1x, but be not limited to this.Additionally, in following chemical formula 1a to 1x, the order of each repetitive in structural formula can change.
In described chemical formula 1a～1x, a and b is as defined above identical, additionally, Rb is as acid sensitive group, as defined above identical, it is preferable that can be the tert-butyl group.
It addition, in the polymer, more preferably the compound (here, Rb is the tert-butyl group) of chemical formula 1a or chemical formula 1i.
There is the resist polymer that the present invention of configuration as described above relates to, it is possible to prepare by the following method: make cycloolefin (cycloolefin) and maleic anhydride (maleicanhydride) polymerization step (step 1) to prepare polymer；Described polymer is made to react with alcohol, so that from the step (step 2) of the repetitive generation ring-opening reaction of maleic anhydride in polymer；Hydroxyl in resulting polymers is substituted by the step (step 3) of acetal radical.
Hereinafter, each step being described in detail, step 1 is make cycloolefin (cycloolefin) and maleic anhydride (maleicanhydride) polymerization step to prepare polymer.Following reaction equation 1 is, according to the method for producing polymer of one embodiment of the invention, indicates that the polymerization procedure of cycloolefin and maleic anhydride, but this is the example to the present invention, however it is not limited to this.
Reaction equation 1
(in described reaction equation 1, R1, a and b as defined above identical.)
Described cycloolefin can be, provides the derivant of the norborene of repetitive a in described chemical formula 1, more preferably containing R in chemical formula 11The norbornene derivative of functional group.This cycloolefin can pass through conventional method and prepare, it is also possible to buys commercially available compound and uses.
Being polymerized between described cycloolefin and maleic anhydride, the polymerization that can adopt routine carries out, the polymerization polymerizations such as such as polymerisation in bulk, polymerisation in solution, suspension polymerisation, mass suspension polymerization, emulsion polymerization prepare, it is preferable that can be obtained by radical polymerization.Now, as long as using radical polymerization initiator as conventional in azodiisobutyronitrile (AIBN), benzoyl peroxide (BPO), lauroyl peroxide, azo two dissident's lactams butyronitrile, AMBN or tert-butyl hydroperoxide etc. as radical polymerization initiator, it does not have special restriction.
Additionally, described polymerization can at oxolane, Isosorbide-5-Nitrae-ether compound such as dioxanes, Di Iso Propyl Ether；The ketone such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK)；The esters such as ethyl acetate；The amine equal solvent such as dimethylformamide, dimethyl acetylamide carries out.
In addition, the molecular weight distribution of the polymer of preparation, consider the mol ratio etc. of each repetitive in the polymer of final preparation, suitably can be regulated by make consumption and the response time of change polymerization initiator, polyreaction remains in the unreacted monomer in reactant and by-product after terminating, it is preferable that remove with solvent precipitation.
Then, step 2 is to implement the step of ring-opening reaction, makes the polymer in the preparation of described step 1 react with alcohol, so that from the repetitive generation ring-opening reaction of maleic anhydride in polymer.
Following reaction equation 2 is, method for producing polymer according to one embodiment of the invention, indicate that the polymer that the polyreaction of cycloolefin and maleic anhydride obtains reacts with alcohol, so that the part from maleic anhydride constituting described polymer carries out the stage of ring-opening reaction, but this is the example to the present invention, however it is not limited to this.
Reaction equation 2
(in described reaction equation 2, R1、R2, a and b as defined above identical, R is carbon number is the alkyl of 1～20.) specifically, the alcohol compound that described alcohol compound can use the carbon numbers such as methanol to be 1～20.During described ring-opening reaction, the carbon number of alcohol is more many, or apparatus derivatorius, the open loop degree reduction of maleic anhydride, and therefore, the alcohol compound of use in ring-opening reaction, carbon number is more few more favourable, linear chain structure is more favourable.Therefore, described alcohol compound is preferably the straight chain alcohol compounds that carbon number is 1～10, more preferably carbon number is the lower alcohols compound of the straight chain of 1～4.Additionally, described alcohol compound make consumption, it is possible to the amount according to the repetitive from maleic anhydride comprised in polymer, suitably adjust.
Step 3 is, hydroxyl in the polymer obtained by described step 2 is substituted by the step of acetal radical.Following reaction equation 3 represents substitution reaction, according to the method for producing polymer of one embodiment of the invention, hydroxyl in the polymer obtained by described step 2 is substituted by the step of acetal radical, but this is the example to the present invention, however it is not limited to this.
Reaction equation 3
(in described reaction equation 3, R1～R3, a and b as defined above identical.)
Specifically, described substitution reaction is implemented as follows, makes the polymer obtained in step 2 react with ether compound or anhydride, and the functional group comprised in described ether compound or anhydride can replace the hydroxyl in this polymer.
Described ether compound can be the line style containing thiazolinyl or halogen or ring-like ether compound, can replace the functional group of hydroxyl in described polymer when described thiazolinyl or halogen.Specifically, comprise, with described hydroxyl, the ether compound of functional group or the anhydride of substitution reaction can occur, it is possible to be the compound of formula 5 below a～5g, but be not limited to this, these compounds can be used alone one of which, or mixes two or more use.
Described substitution reaction, it is possible to implement under the existence of the compounds such as trifluoroacetic acid, trifluoromethyl acetic acid, at this point it is possible to use the described compound of catalytic amount.
In described polymer during hydroxyl generation substitution reaction, when comprising hydroxyl in the repetitive of cyclenes hydrocarbon monomer, described hydroxyl can be replaced simultaneously.
By the polymer of COMA (cycloolefinmaleicanhydride) type prepared by described preparation method, maleic anhydride and cycloolefin are often with certain proportion alternating polymerization, therefore, the problem that the line edge roughness caused because of the massing of monomer during without considering to prepare traditional resist polymer reduces, the raw ring-opening reaction of the maleic anhydride environment-development used when forming polymer, it also is able to one of problem solving existing COMA polymer, that is, when irradiating the light of ArF193nm, maleic acid absorbs the problem that the transparency that is big and that cause reduces.
In addition, the carboxyl generated when the raw open loop of described maleic anhydride environment-development, reduce the dissolubility in organic developer solution of NTD photoresist, then, described carboxyl is replaced by acetal radical, thus at unexposed area, dissolubility in organic developer solution increases to proper range, in exposure area, by causing the de-base reaction of described acetal radical from the acid of light acid propellant, it is possible to reduce the dissolubility in organic developer solution.
In addition, carboxyl is made to be replaced by acetal radical, so that the size sloughing group dissolved in developing process after de-base reacts and remove minimizes, thus reducing the thickness loss of resist film, additionally, described al base is sensitive relative to other any three grades of esters or acid sensitive group, therefore, de-base immediately such that it is able to improve the contrast (contrastratio) at the interface of exposure area and unexposed area.
Following reaction equation 4 briefly shows, and utilizes the polymer that the present invention relates to form the reaction mechanism of pattern in NTD photoresist.Following reaction equation 4 is only intended to illustrate an example of the present invention, but is not limited to this.
Reaction equation 4
Utilize the polymer (i) that the present invention relates to when forming Resist patterns; when irradiating ArF light; there is acid in the light acid propellant comprised in resist; the acid so generated is when PEB (postexposurebaking); to resist film internal diffusion; make the de-base of blocking group of polymer (i), be converted to polymer (ii).Then, organic developer solution is utilized to develop, at unexposed area, it is washed off after resist development containing polymer (i), in exposure area, the resist carrying out de-base reaction and containing polymer (ii) dissolubility in organic developer solution reduces, and therefore gives over to pattern.Reaction mechanism as above is illustrated with situation about using in ArF resist, but is not limited to this, can use in all photoetching techniques using the CAR types such as KrF, EUV, X ray.Additionally, to be particularly suitable as NTD pattern material useful above-mentioned.
The polymer that the present invention relates to, can be 1,000 to 50 according to the weight average molecular weight (hereinafter referred to as " Mw ") of gel permeation chromatography (GPC, gelpermeationchromatography) polystyrene conversion, 000g/mol.When the weight average molecular weight of described polymer is too small, it is possible to cause that corrosion resistance is not enough, when the weight average molecular weight of described polymer is excessive, it may be difficult to form suitable film or reduce alkali solubility.Preferably, described weight average molecular weight is 2,000 to 10,000g/mol, demonstrates the dissolubility of excellence at this point for described developer solution.
Furthermore it is preferred that, the molecular weight distribution of the weight average molecular weight of described polymer and the ratio (Mw/Mn) of number-average molecular weight is 1 to 3, more preferably 1 to 2.If additionally, when the molecular weight distribution of described polymer is more than 3, it is possible to line edge roughness is bad.Therefore, using the additive against corrosion belonged in described weight average molecular weight and range of molecular weight distributions as photoetching compositions use time, it is possible in developability, coating and thermostability, show corresponding physical property.
According to another embodiment of the present invention, it is provided that a kind of anti-corrosion agent composition containing described polymer.
Specifically, described anti-corrosion agent composition, as resist base polymer, comprises described polymer and solvent.
Described polymer is such as above-mentioned identical, relative to the gross weight of anti-corrosion agent composition, it is possible to containing the described polymer of 3 to 20 weight %.If the content of described polymer is less than 3 weight %, the viscosity of compositions is too low, thus being difficult to be formed the thin film of desired thickness, and due to relatively large number of light acid propellant, pattern loss (patternloss) is serious, if more than 20 weight %, then film thickness is blocked up and reduce radiation penetration power, it is difficult to obtain longitudinal grin pattern.
Additionally, when being usually formed resist thin film, while comprising described polymer, the base polymer that resin based on also comprising is suitable for.As concrete example, choosing freely (methyl) acrylate polymer can be used, (α-trifluoromethyl) Acrylic Ester-Maleic Anhydride, cyclic-olefin-maleic anhydride copolymer, polynorbornene, the macromolecular compound obtained is reacted by the ring-opening methathesis of cycloolefin, the macromolecular compound adding hydrogen in the polymer obtained and obtain will be reacted by the ring-opening methathesis of cycloolefin, make hydroxy styrenes and (methyl) acrylate derivative, styrene, vinyl naphthalene, vinyl anthracene, vinylpyrene, hydroxyvinyl naphthalene, hydroxyvinyl anthracene, indenes, hydroxyl indenes, acenaphthylene, the macromolecular compound of any one combined polymerization of norbornadiene apoplexy due to endogenous wind, in the group that novolac resin and their mixture form.
In order to obtain uniform and smooth resist coated film, it is preferable that described polymer and acid-producing agent are dissolved in the solvent with suitable evaporation rate and viscosity and use.As the solvent that can use in the present invention, the esters such as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, acetic acid methyl cellosolve, acetic cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl acetas, propylene glycol monopropyl ether acetas can be enumerated, methyl isopropyl Ketone, Ketohexamethylene, methyl-2 hydroxy propanoic acid ethyl ester, ethyl-2 hydroxy propanoic acid ethyl ester, 2-heptanone, the ketone such as ethyl lactate, gamma-butyrolacton etc., wherein, can be used alone one, or mixing uses two or more.
Described solvent can suitably regulate it and make consumption according to solvent physical property, i.e. volatility, viscosity etc., so as to form uniform etchant resist.
Additionally, described anti-corrosion agent composition can also contain acid-producing agent.
Described acid-producing agent is light acid propellant (photoacidgenerator, hereinafter referred to as " PAG "), the iodine salt (iodoniumsalts) of salt, sulfosalt (sulfoniumsalts), salt, diazol, pyridiniujm or acid imide etc. can be used, can be preferably used in the sulfosalt represented by following chemical formula 6a and 6b more than one, perfluoro butyl sulfonic acid triphenyl sulfonium salt (triphenylsulfoniumnonaflate) more can be preferably used.
Chemical formula 6a
Chemical formula 6b
In described chemical formula 6a and 6b,
X1、X2、Y1And Y2Be each independently the alkyl that selects free hydrogen atom, carbon number to be 1～10, pi-allyl, carbon number be 1～10 perfluoroalkyl, benzyl, carbon number be 6～30 aryl and the group that forms of their combination in any one, described X1And X2And Y1And Y2Can be bonded to each other and form the saturated or unsaturated hydrocarbons ring that carbon number is 3 to 30,
X3、X4、X5、Y3、Y4And Y5Be each independently the alkyl that selects free hydrogen atom, carbon number to be 1～30, aryl that alkoxyl that halogen radical, carbon number are 1～30, carbon number are 6～30, sulfo-phenoxy group (thiophenoxy), carbon number be 1～30 thio alkoxy (thioalkoxy), carbon number be 1～20 alkoxy carbonyl methoxyl group (alkoxycarbonylmethoxy) and the group that forms of their combination in any one
The Z of anionicsite is OSO2CF3、OSO2C4F9、OSO2C8F17、N(CF3)2、N(C2F5)2、N(C4F9)2、C(CF3)3、C(C2F5)3、C(C4F9)3Or the functional group represented by following chemical formula 6c.
Chemical formula 6c
In described chemical formula 6c,
V1And V2It is each independently halogen atom,
W1For-(C=O)-or-(SO2)-,
W2It is the alkylidene of 1～10 for carbon number
W3For the cycloalkyl selecting free carbon number to be 3～30, carbon number be 6～30 aryl, carbon number be 7～30 aralkyl, carbon number be 6～30 aryloxy group, carbon number be 6～30 arylthio base and the group that forms of heterocyclic radical that carbon number is 5～30 in any one
W4For the alkyl selecting free hydrogen atom, halogen radical, carbon number to be 1～10, carbon number be 1～10 alkoxyl, carbon number be 1～10 haloalkyl, carbon number be 1～10 alkyl thio-base, carbon number be 6～30 aryl and the group that forms of their combination in any one
O is the integer of 0 to 1,
P is the integer of 0 to 2.
In described acid-producing agent, anion contains cyclic alkyl such that it is able to suitably keeping acid diffusion length in etchant resist shorter, show high osmosis, it is as a result, it is possible to obtain high-resolution resist.
Preferably, described anionicsite Z can select in the group that the functional group that freely following chemical formula 7-1 to 7-36 represents forms.
Additionally, in described chemical formula 6a and 6b, it is preferable that the structure represented by following chemical formula 8-1 to 8-16 can be enumerated as cation portion.
Acid-producing agent as above, it is possible to be used alone or mix two or more use.Additionally, relative to polymer solids content 100 weight portion, the content of described acid-producing agent can be 0.3 to 15 weight portion, it is preferred to 0.5 to 10 weight portion, more preferably 2 to 10 weight portions.When the content of acid-producing agent is more than 15 weight portion, the verticality of pattern is remarkably decreased, if during less than 0.3 weight portion, it is possible to reduce the bendability of pattern.
Additionally, to improve for the purpose of coating etc., the anti-corrosion agent composition that the present invention relates to can also contain additive.
As described additive, as long as be usually applicable to the additive of anti-corrosion agent composition, it does not have any particular restriction, specifically can enumerate Alkaline solubilization inhibitor, acid dispersion inhibitor, surfactant etc., wherein it is possible to containing individually a kind of, or two or more mixing contains.
As long as the Alkaline solubilization inhibitor that described Alkaline solubilization inhibitor is usually applicable to anti-corrosion agent composition all can use, phenol or carboxylic acid derivates etc. can be enumerated as concrete example.
Described acid dispersion inhibitor functions as follows, it is suppressed that diffusion development when being irradiated by light and spread from the acid of acid-producing agent generation to etchant resist, it is suppressed that unexposed portion generation chemical reaction.By using this acid dispersion inhibitor, while the storage stability of radiation-sensitive resin composition can be improved, improve the resolution as resist further, it is possible to suppress the time (PED) till being exposed to development treatment to change the line width change of the corrosion-resisting pattern caused.
nullAlkali compounds can be used as this acid dispersion inhibitor，As its concrete example，Ammonia can be enumerated、Methylamine、2-aminopropane.、N-hexylamine、Aminocyclopentane、Methylene diamine、Ethylenediamine、Dimethylamine、Diisopropylamine、Diethylene triamine、N,N-dimethyl methyl diamidogen、N,N-dimethyl-ethylenediamine、Trimethylamine、Triethylamine、N,N,N',N'-tetramethyl methanediamine、N,N,N',N'-tetramethylethylenediamine、N,N,N',N'-tetramethyl tetren、Diethylamide、Methylethyl propylamine、Benzylamine、Phenethylamine、Benzyl dimethylamine、Tetramethylammonium hydroxide、Aniline、N,Accelerine triphenylamine、Phenylenediamine、Pyrroles、Oxazole、Isoxazole、Thiazole、Isothiazole、Imidazoles、Pyrazoles、Pyrrolin、Pyrrolidine、Imidazolidine derivatives、Imidazolidine derivative、Pyridine derivate、Pyridyl derivatives、Pyrimidine derivatives、Pyrazines derivatives、Pyrazoline derivative、Pyrazolidine derivatives、Piperidine derivative、Bridged piperazine derivatives、The amines such as morpholine，Aminoacid、Indole-carboxylic acid、Amino acid derivativges (such as nicotinic acid、Alanine、Arginine、Aspartic acid etc.)、3-pyridine-sulfonic acid、Para-methylbenzenepyridinsulfonate sulfonate、2 hydroxy pyrimidine、Amino metacresol、2,4-quinoline diol、2-(2-ethoxy) pyridine、The nitrogen compounds such as 1-(2-ethoxy) piperazine，Methanamide、N-METHYLFORMAMIDE、N,Dinethylformamide、Acetamide、N-methylacetamide、N,N-dimethyl acetylamide、Propionic acid、The amide derivatives such as Benzoylamide，Or phthalimide、Butanimide、The imide derivatives etc. such as maleimide.
Relative to polymer solids content 100 weight portion, the content of described acid dispersion inhibitor can be 0.01 to 5 weight portion, it is preferred to 0.1 to 1 weight portion.If the content of acid dispersion inhibitor is less than 0.01 weight portion, then along with impact time delay after exposure is relatively big, it is possible to affect picture shape, if more than 5 weight portions, it is likely that reduce resolution and light sensitivitys.
Described surfactant is used for improving coating and developability etc., can enumerate polyoxyethylene lauryl ether, Steareth, polyoxyethylene, polyethylene glycol dilaurate etc. as concrete example, but be not limited to this.
When utilizing the anti-corrosion agent composition that the present invention with composition as described above relates to form corrosion-resisting pattern, showing the line width roughness (Linewidthroughness) of improvement, C/H pattern and L/S pattern all show outstanding resolution.Additionally, have good process window (processwindow), so be independently obtained in that excellent pattern contour (patternprofile) with substrate type, show the contrast of improvement.Therefore, described anti-corrosion agent composition is useful as the chemically amplified corrosion-resisitng agent composition that the X-rays such as far ultraviolet rays, synchrotron radiation such as KrF excimer laser, ArF excimer laser or F2 excimer laser and the radiation such as charged particles such as EUV are sensed.
According to still another embodiment of the present invention, it is provided that a kind of method utilizing described anti-corrosion agent composition to form pattern.
Specifically, the method forming described pattern comprises the steps: to be coated with described anti-corrosion agent composition on substrate and the step that forms etchant resist；After etchant resist described in heat treated, with the step that predetermined pattern is exposed；And the step of the corrosion-resisting pattern being exposed that develops.
Described substrate can use wafer substrate, and the coating process of substrate can be utilized the methods such as spin coating, flow coat or roller coat.
Specifically, on the substrates such as silicon wafer, coated film thickness is 0.3 to 2.0 μm, by its prebake 1 to 10 minute at 60 to 150 DEG C, it is preferable that prebake 1 to 5 minute at 80 to 130 DEG C.
Then, in order to form fine pattern, part etchant resist is irradiated with lonizing radiation.Now, the lonizing radiation that can use are not particularly limited, but can use as ultraviolet I-ray, far ultraviolet KrF excimer laser, ArF excimer laser, F2 excimer laser, X-ray, charged particle line electron ray etc., according to the kind of acid-producing agent can suitably select use.
Specifically, irradiating lonizing radiation makes light exposure be 1 to 200mJ/cm2Left and right, it is preferred to 10 to 100mJ/cm2Left and right, postexposure bake at 60 to 150 DEG C afterwards (PEB) 1 to 5 minute, it is preferable that postexposure bake 1 to 3 minute at 80 to 130 DEG C.
The corrosion-resisting pattern being exposed after step of exposure, by impregnating the methods such as (dip) method, puddle (puddle) method, spraying (spray) method, utilize developer solution to soak to develop for 0.1 to 3 minute, it is preferably 0.5 to 2 minute, thus forming desired pattern on substrate.
At this moment, as developer solution, as long as the developer solution used usually used as counter-rotative type developer solution, it is possible to use, it does not have be particularly limited to.Specifically, ketones solvent (such as, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), acetylacetone,2,4-pentanedione etc.)；Esters solvent (such as, methyl acetate, n-butyl acetate, propylene glycol methyl ether acetate, methyl formate, ethyl lactate etc.)；Alcohols solvent (methanol, ethylene glycol, glycol monoethyl ether etc.)；Amide solvent (N-methyl-pyrrolidon, N,N-dimethylformamide etc.)；The polar solvent of ether solvent (dioxanes, oxolane etc.) etc. or can use varsol (such as, toluene, dimethylbenzene, pentane, hexane etc.) organic developer solution, described developer solution can mix more than one and use, it is also possible to mix use with water.Wherein, it is preferred to n-butyl acetate.At this moment, described developer solution can also contain surfactant as required.
As it has been described above, according to utilizing the anti-corrosion agent composition that the present invention relates to form patterning method, it is possible to form the fine Resist patterns with excellent light sensitivity and resolution.
Below, embodiments of the invention are described in detail, in order to general technical staff of the technical field of the invention can easily implement.But, the present invention can be realized by various different modes, but is not limited to embodiment described herein.
The synthesis example 1 of polymer
Step 1
In 1L jacket type (jackettype) reactor, 1 is used as polymer solvent, 4-dioxanes (1,4-dioxane) 306g, dissolve norborene (norbornene) (i) 50g and maleic anhydride (maleicanhydride) (ii) 52g, then, dissolve the azodiisobutyronitrile (azobisbutyronitril as initiator, AIBN) 15g, then by the temperature of reactor to 75 DEG C, stir three hours.After the polymeric solution of acquisition is cooled to room temperature, slowly it is added drop-wise to normal hexane (n-hexane) as precipitation solvent and carries out precipitation.Utilize vacuum filter sediment separate out and solution, carry out drying under reduced pressure to separating the precipitate obtained, it is thus achieved that the polymer (iii) of 91g.
Polymer to above-mentioned preparation, uses GPC (Gelpermeationchromatography) and 1HNMR to be analyzed.
Analyzing result, the weight average molecular weight (Mw) of the polystyrene conversion of this polymer is 6,086g/mol, and the ratio (Mw/Mn) of weight average molecular weight and number-average molecular weight is 1.85.
1HNMR(CDCl3, internal standard: tetramethylsilane): 1.2～1.8 (br, 6H), 2.2～3.6 (br, 6H).
Step 2
Polymer (iii) 91g synthesized in described step 1 is dissolved in the 1 of 270g, 4-dioxanes (1, in 4-dioxane), while being stirred, add the methanol (methylalcohol) (iv) of 85g, then, the sulfonic acid 0.1g as catalyst is added.Mixed solution is stirred one in the oil bath of 85 DEG C.Reaction after the reaction solution of acquisition is cooled to room temperature, is slowly added drop-wise to normal hexane (n-hexane) and carries out precipitation after terminating.Utilize vacuum filter sediment separate out, carry out drying under reduced pressure one to separating the precipitate obtained, it is thus achieved that the polymer (v) of 85g.
Polymer to above-mentioned preparation, uses 1HNMR to be analyzed.
1HNMR(CDCl3, internal standard: tetramethylsilane): 1.2～1.8 (br, 6H), 2.2～3.6 (br, 6H), 3.5～3.8 (s, 3H)
Step 3
Polymer (v) 50g at the 2-in-1 one-tenth of described step is dissolved in butanone (methylethylketone) (vi) 350ml, add vinyl ethyl ether (ethylvinylether) 17.4g and trifluoroacetic acid (trifluoroaceticacid) 2.7g, stir one.Utilize1HNMR determines reaction end, and reaction utilizes distilled water wash 3 times after terminating.Collect the organic layer in reactant liquor, using normal hexane (n-hexane) as precipitation solvent so that it is precipitation.Utilize vacuum filter sediment separate out, carry out drying under reduced pressure one to separating the precipitate obtained, it is thus achieved that the polymer (1a) of 52g.
Polymer to described preparation, uses GPC to be analyzed.Analyzing result, the weight average molecular weight (Mw) of the polystyrene conversion of this polymer is 6,580g/mol, and the ratio (Mw/Mn) of weight average molecular weight and number-average molecular weight is 1.70.
Polymer to described preparation, uses 1HNMR to be analyzed.
1HNMR(CDCl3, internal standard: tetramethylsilane): (ppm) 0.8～1.8 (br, 12H), 1.8～3.0 (br, 6H), 3.4～3.8 (s, 5H), 5.7～5.9 (s.1H)
The synthesis example 2 of polymer
In the step 1 of the synthesis example 1 of described polymer, in order to increase molecular weight, initiator as reactant liquor uses 10g azodiisobutyronitrile, reaction temperature is adjusted to 70 DEG C and implements polymerization, in addition, according to the method synthetic polymer (1a) identical with the method for the synthesis example 1 of described polymer.
Polymer to described preparation, uses GPC (Gelpermeationchromatography) to be analyzed.Analyzing result, the weight average molecular weight (Mw) of the polystyrene conversion of this polymer is 10,185g/mol, and the ratio (Mw/Mn) of weight average molecular weight and number-average molecular weight is 1.3.
The synthesis example 3 of polymer
Step 1
nullIn 1L jacket type (jackettype) reactor，1 is used as polymer solvent,4-dioxanes (1,4-dioxane)525g，Dissolve 3-bicyclo-[2,2,1]-5-in the heptan alkene-2-base-3-hydroxy-propionic acid tert-butyl ester (3-bicyclo [2.2.1] hept-5-en-2-yl-3-hydroxy-propionicacidtert-butylester,Hereinafter referred to as BHP) (vii) 123g and maleic anhydride (ii) 52g，Then，Dissolve the azodiisobutyronitrile (azobisbutyronitril as initiator,AIBN)15g，Then by the temperature of reactor to 75 DEG C，Stir three hours.After the polymeric solution of acquisition is cooled to room temperature, slowly it is added drop-wise to normal hexane (n-hexane) and carries out precipitation.Utilize vacuum filter sediment separate out and solution, carry out drying under reduced pressure to separating the precipitate obtained, it is thus achieved that the polymer (viii) of 142g.
Polymer to described preparation, uses GPC and 1HNMR to be analyzed.
Analyzing result, the weight average molecular weight (Mw) of the polystyrene conversion of this polymer is 5,222g/mol, and the ratio (Mw/Mn) of weight average molecular weight and number-average molecular weight is 1.55.
1HNMR (CDCl3, internal standard: tetramethylsilane): (ppm) 0.6～1.6 (br, 13H), 1.6～3.0 (br, 9H), 3.6～3.8 (1H)
Step2
Polymer (viii) 100g synthesized in described step 1 is dissolved in the 1 of 300g, 4-dioxanes (1, in 4-dioxane), while being stirred, add the methanol (methylalcohol) (iv) of 13g, then, the sulfonic acid 0.2g as catalyst is added.Mixed solution is stirred one in the oil bath of 85 DEG C.Reaction after the reaction solution of acquisition is cooled to room temperature, is slowly added drop-wise to normal hexane (n-hexane) and carries out precipitation after terminating.Utilize vacuum filter sediment separate out, carry out drying under reduced pressure one to separating the precipitate obtained, it is thus achieved that the polymer (ix) of 85g.
Polymer to described preparation, uses 1HNMR to be analyzed.
1HNMR (CDCl3, internal standard: tetramethylsilane): (ppm) 0.8～2.0 (br, 13H), 2.0～3.0 (br, 9H), 3.6～4.4 (4H), 8.0～9.0 (br, 1H)
Step 3
Polymer (ix) 50g at the 2-in-1 one-tenth of described step is dissolved in butanone (methylethylketone) (vi) 350ml, adds vinyl ethyl ether (ethylvinyLether) 35g and trifluoroacetic acid (trifluoroaceticacid) 2.7g, stirs one.Utilize1HNMR determines reaction end, and reaction utilizes distilled water wash 3 times after terminating.Collect the organic layer in reactant liquor, using normal hexane (n-hexane) as precipitation solvent so that it is precipitation.Utilize vacuum filter sediment separate out, carry out drying under reduced pressure one to separating the precipitate obtained, it is thus achieved that the polymer (1b) of 48g.
Polymer to described preparation, uses GPC to be analyzed.Analyzing result, the weight average molecular weight (Mw) of the polystyrene conversion of this polymer is 5,450g/mol, and the ratio (Mw/Mn) of weight average molecular weight and number-average molecular weight is 1.45.
Polymer to described preparation, uses 1HNMR to be analyzed.
1HNMR(CDCl3, internal standard: tetramethylsilane): (ppm) 1.0～1.6 (br, 19H), 1.6～2.0 (br, 15H), 3.0～3.8 (br, 4H), 4.6～4.8 (4H), 5.8～6.0 (br, 2H)
The synthesis example 1 of comparative polymers
nullBy methyl adamantane methyl acrylate (methyladamantanemethacylate) 25g of polymerization monomer、Gamma-butyrolacton methacrylate (γ-butyrolactonemethacrylate) 19.2g、The 1 of hydroxyadamantane methyl acrylate (hydroxyladamantanemethacrylate) 26.2g and azo-bis-iso-dimethyl (dimethylazobisisobutylate) 4g and the 200g as polymerization initiator,4-dioxanes (1,4-dioxane) together pour in flask and mix，Then after utilizing nitrogen to be replaced by flask interior nitrogen，By inside reactor heating temperatures to 70 DEG C.Reaction 5 hours at the same temperature.If polymerization terminates, then reaction solution as a result is cooled to room temperature.Will be cooled to the reaction solution of room temperature utilizes excessive normal hexane (n-hexane) to carry out isolated by filtration after precipitation.Carrying out drying under reduced pressure after the filtration article same solvent washing separated, 5 obtain the polymer (9) of 5g.
(in described formula, the mol ratio (l:m:n) of each repetitive is 0.4:0.3:0.3)
Utilizing the GPC polymer measurement to preparing, its result, the weight average molecular weight (Mw) of the polystyrene conversion of this polymer is 7840g/mol, and the ratio (Mw/Mn) of weight average molecular weight and number-average molecular weight is 1.93.
Test example 1
In order to evaluate the effect of the polymer that the present invention relates to, the polymer being used in described synthesis example preparing prepares anti-corrosion agent composition, after utilizing the anti-corrosion agent composition of preparation to form Resist patterns, evaluates its patternability.
In detail, polymer 100 weight portion obtained in step 3 relative to Macroscopic single crystal example 1, at methyl proxitol acetate 1,000 weight portion dissolves the perfluoro butyl sulfonic acid triphenyl sulfonium salt of 5 weight portions and the alkalinity additive triisopropanolamine (Triisopropanolamine) of 2.0 weight portions, utilizes the film filter of 0.2 μm to filter and prepare anti-corrosion agent composition.Utilize capstan to be coated on substrate by prepared anti-corrosion agent composition, and dry 90 seconds at 110 DEG C, form the tunicle that thickness is 0.10 μm.After utilizing ArF excimer laser (eyeglass opening number: 0.93) to be exposed the tunicle formed, heat treatment 90 seconds at 110 DEG C.Then, utilize n-butyl acetate to carry out through 40 seconds developing, wash, dry, form Resist patterns.
Additionally, except each material content shown in table 1 below uses, to be prepared for anti-corrosion agent composition with described identical method, and utilize it to form Resist patterns.
For the Resist patterns formed, determine exposure energy (Dose, mJ), resolution and EL.The results are shown in table 1.
To the L/S pattern of 0.07 μm formed after development, the light exposure formed with the live width of 1:1, for optimum exposure (Eop), is at this moment differentiated the minimum pattern size obtained and is defined as resolution.
Additionally, for assessment process scope, determine El (energylatitudemargin), El indicates that the intensity of variation in CD specification, according to the CD of energy variation.
Table 1
As described in described table 1, comprising the resist of the embodiment 1-1 to 1-11 of the polymer of the present invention, its resolution, EL and light sensitivitys aspect represent the characteristic being balancedly improved.Particularly, except the kind of polymer is different, use embodiment 1-6 prepared by same amount of light acid propellant and alkali compounds, 1-10,1-11 to compare with comparative example 1, embodiment 1-6,1-10,1-11 resist, in resolution, EL and light sensitivitys, improve effect more preferably.
Test example 2
The various polymer that preparation the present invention relates to, evaluate the patternability of these polymer.
Specifically, outside the monomer shown by table 2 below, polymer is prepared according to the method identical with described embodiment 1, and utilize this polymer, according to the method identical with test example 1, prepare anti-corrosion agent composition, and form Resist patterns, then, exposure energy, resolution and EL value are measured respectively.The results are shown in table 2.
Table 2
nullIn described table 2，MA is maleic anhydride (maleicanhydride)，BP is 3-bicyclo-[2,2,1]-5-in heptan alkene-2-base-propanoic acid tert-butyl ester (3-bicyclo [2.2.1] hept-5-en-2-yl-propionicacidtert-butylester)，BHP is 3-bicyclo-[2,2,1]-5-in the heptan alkene-2-base-3-hydroxy-propionic acid tert-butyl ester (3-bicyclo [2.2.1] hept-5-en-2-yl-3-hydroxy-propionicacidtert-butylester)，BHPA is 5-bicyclo-[2,2,1]-5-in the heptan alkene-2-base-5-hydroxy-pentanoic acid tert-butyl ester (5-bicyclo [2.2.1] hept-5-en-2-yl-5-hydroxy-pentanoicacidtert-butylester)，BCN is 5-bicyclo-[2,2,1]-5-in heptan alkene-2-nitrile (bicyclo [2.2.1] hept-5-ene-2-carbonitrile)，Simultaneously，PBH is 5-propyl group bicyclo-[2,2,1]-5-in heptan alkene (5-propylbicyclo [2.2.1] hept-2-ene).
Table 3
Result of the test, comprises the anti-corrosion agent composition of the embodiment 2-1 to 2-15 of the various polymer of the compound being equivalent to chemical formula 1 of the present invention, and its resolution, EL and light sensitivitys aspect represent the characteristic being balancedly improved.
Above the preferred embodiments of the present invention are described in detail, but scope of the presently claimed invention is not limited to this, the various deformation of the basic conception utilizing the present invention defined in appended claims and improvement form fall within the interest field of the present invention.

Claims (11)

1. there is a resist polymer for structure shown in formula 1 below, wherein,
Chemical formula 1
In described chemical formula 1,
R1It is selected from group: hydrogen atom；Hydroxyl；Acetal radical；Itrile group；It is selected from by halogen, itrile group, hydroxyl, alkoxyl, acetal radical, acyl group, aldehyde radical, the substituted or unsubstituted carbon number of more than one substituent groups in the group that carboxyl and ester group form is the alkyl of 1～20, carbon number is the alkoxyl of 1～20, carbon number is the aryl of 6～30, silylation, carbon number is the thiazolinyl of 2～20, carbon number be 3～30 cycloalkyl and ring in comprise and at least one select free N, P, the heterocyclic radical that heteroatomic carbon number is 2～30 in the group that O and S forms；And their combination,
R2It is the alkoxyl of 1～20 for carbon number,
R3And R4It is each independently the cycloalkyl selecting thiazolinyl that aryl that haloalkyl that alkyl that free hydrogen atom, carbon number are 1～20, carbon number are 1～20, carbon number are 6～30, carbon number are 2～20, carbon number to be 3～30 and in group that their combination forms, or it is bonded to each other and forms the heterocyclic radical comprising oxygen atom in ring
A and b when meeting a+b=1,0 < a/ (a+b) < 1,0 <b/ (a+b) < 1.
2. resist polymer according to claim 1, wherein,
Described R1Select in the group that free hydrogen atom, hydroxyl, acetal radical, itrile group and the functional group represented by following chemical formula 2 form:
Chemical formula 2
In described chemical formula 2,
N is the integer of 1～3,
RaSelect in the group that free hydrogen atom, hydroxyl and acetal radical form,
Described RbFor selecting freedomAcid-sensitive sensillary base in the group formed, now, R ', R " and R " ' be each independently choosing free carbon number be the alkyl of 1～20, carbon number is the cycloalkyl of 3～30, hydroxyl, hydroxy alkyl, carbon number is the alkoxyl of 1～20, acetyl group, acetyl alkyl, carboxyl, the alkyl that carbon number is 1～10 that carboxyl replaces, in the cycloalkyl that carbon number is 3～18 that carboxyl replaces and the group that Heterocyclylalkyl that carbon number is 3～30 forms, or group adjacent one another are connects can form the saturated or undersaturated hydrocarbon ring or heterocycle that carbon number is 3～30, R " " it is the alkyl of 1～10 for carbon number, z is the integer of 0 to 3, w is the integer of 0 to 10.
3. resist polymer according to claim 1, wherein,
Described resist polymer is in the group that the compound with formula 1 below a to 1x structure forms:
In described chemical formula 1a to 1x, RbFor selecting freedomnullAcid-sensitive sensillary base in the group formed，Now，R’、R " and R " ' be each independently choosing free carbon number be the alkyl of 1～20、Carbon number is the cycloalkyl of 3～30、Hydroxyl、Hydroxy alkyl、Carbon number is the alkoxyl of 1～20、Acetyl group、Acetyl alkyl、Carboxyl、The alkyl that carbon number is 1～10 that carboxyl replaces、In the cycloalkyl that carbon number is 3～18 that carboxyl replaces and the group that Heterocyclylalkyl that carbon number is 3～30 forms，Or group adjacent one another are connects can form the saturated or undersaturated hydrocarbon ring or heterocycle that carbon number is 3～30，R " " it is the alkyl of 1～10 for carbon number，Z is the integer of 0 to 3，W is the integer of 0 to 10，Wherein，A and b is when meeting a+b=1，0 < a/ (a+b) < 1 and 0 <b/ (a+b) < 1.
4. resist polymer according to claim 1, wherein,
Described resist polymer is 1,000 to 50,000g/mol according to the weight average molecular weight of gel permeation chromatography polystyrene conversion.
5. resist polymer according to claim 1, wherein,
The molecular weight distribution of the weight average molecular weight of described resist polymer and the ratio (Mw/Mn) of number-average molecular weight is 1 to 3.
6. an anti-corrosion agent composition, it contains the resist polymer described in claim 1.
7. anti-corrosion agent composition according to claim 6,
Relative to the gross weight of anti-corrosion agent composition, the content of described resist polymer is 3 to 20 weight %.
8. anti-corrosion agent composition according to claim 6, wherein,
Described anti-corrosion agent composition is discharged-area development anti-corrosion agent composition.
9. a forming method for Resist patterns, it comprises the steps:
It is coated on substrate by the anti-corrosion agent composition described in claim 6 to be formed the step of resist film；
After resist film described in heat treated, with the step that predetermined pattern is exposed；And,
The step of the Resist patterns that development is exposed.
10. the forming method of Resist patterns according to claim 9,
Described exposure technology utilizes the light source in the group selecting free KrF excimer laser, ArF excimer laser, extreme ultraviolet laser, X-ray and electron beam to form to implement.
11. the forming method of Resist patterns according to claim 9,
Described development is to utilize the organic developer solution of counter-rotative type to implement.
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