CN109388021A

CN109388021A - Composition is used in organic film formation

Info

Publication number: CN109388021A
Application number: CN201810863232.8A
Authority: CN
Inventors: 橘诚郎; 橘诚一郎; 长井洋子; 郡大佑; 荻原勤
Original assignee: Shin Etsu Chemical Co Ltd
Current assignee: Shin Etsu Chemical Co Ltd
Priority date: 2017-08-04
Filing date: 2018-08-01
Publication date: 2019-02-26
Anticipated expiration: 2038-08-01
Also published as: TWI653284B; KR20190015060A; KR102051189B1; CN109388021B; TW201910420A

Abstract

The present invention provides a kind of organic film formation composition that can form organic film, the organic film can be by using that will not cause the stripper of damage, the commonly used ammonia spirit containing hydrogen peroxide for being referred to as SC1 in such as manufacture of semiconductor to necessary organic resist lower membrane in semiconductor device substrate and patterning process, and easily with wet type removes the silicon ingredient residue of modification together due to dry ecthing.Organic film formation composition includes high-molecular compound and organic solvent, the high-molecular compound has any a kind or more in the repetitive unit indicated by the following general formula (1)~(4), in the organic solvent, total amount accounted for more than the 30wt% in whole organic solvents selected from one or more of propylene glycol ester, ketone and lactone.[chemical formula 1]

Description

Composition is used in organic film formation

Technical field

The present invention relates to one kind on semiconductor device producing substrate formed line pattern when used multilayer it is against corrosion Composition is used in agent membrane material, in particular to a kind of organic film formation.

Background technique

In the past, semiconductor was drawn in the fining of the pattern dimension of the short wavelengthization based on light source in lithography technique The high performance of the processing capacity of device.However, in recent years, since the speed of the later short wavelengthization of ArF light source is slow, Seeking the high performance of the processing capacity of the semiconductor device instead of fining always.As one of its method, it has been suggested that one Kind of processing capacity high semiconductor device, being configured with can be transported to high-density compared with planar ransistor with higher speed The three-dimensional transistor of work.For manufacturing the substrate (hereinafter, being set as substrate) of such semiconductor device, for by than well known base The three-dimensional structure of the more complicated segment difference processing of plate and formation.Therefore, if forming previous planar ransistor when institute by utilizing The pattern forming method of the single layer photoresist used forms pattern, then photoresist film can follow substrate process Formed in segment difference, cause photoresist film surface generate segment difference, as a result can not obtain flat resist film.Thus When being exposed to form pattern to photoresist, become focus can not be made to be properly aligned on photoresist, As a result, the yield rate of substrate processing can reduce.Seeking for the anti-new material of problem and method etc. here.

As one of the method for solving such problems point, there is multilayer resist method.The method, which passes through, utilizes planarization property Lower membrane that can be high forms photoresist film in this planar film to make the substrate planarization with segment difference, can make to expose When focus nargin become wide, the yield rate for preventing substrate from processing reduces.Further, in the method, if selection is photic to upper layer anti- The respectively different lower membrane of the etching selectivity of agent film and substrate is lost, then pattern can be formed in on resistant upper layer film it Afterwards, using resistant upper layer film figure as dry ecthing exposure mask, and pattern is transferred to intermediate coat using dry ecthing, further will under Pattern is transferred to processed substrate as dry ecthing exposure mask, and using dry ecthing by tunic.

This multilayer resist method is usually three layers of resist method, which may be used in single layer resist method Used common anti-corrosion agent composition and carry out.For example, making flatness high on being processed substrate and processing substrate to have There is organic resist lower membrane of sufficient dry etching resistance to form a film, makes the siliceous resist lower layer as intermediate coat above Film forms a film (hereinafter referred to as siliceous resist intermediate coat), forms the photoresist film as resistant upper layer film above. Due to that can obtain the resistant upper layer film of the dry ecthing based on fluorine-based gas plasma, organic relative to siliceous anti- Lose agent intermediate coat good etching selectivity, therefore can by using the dry ecthing based on fluorine-based gas plasma and incite somebody to action Corrosion-resisting pattern is transferred to siliceous resist intermediate coat.Further, since for the dry ecthing based on oxygen system gaseous plasma, silicon class Resist intermediate coat can obtain the good etching selectivity relative to organic resist lower membrane, therefore can be by making Film figure among siliceous resist is transferred to organic resist lower membrane with the dry ecthing based on oxygen system gaseous plasma. According to the method, have even with being difficult to be formed for being sufficient film thickness directly for processed substrate is processed The resistant upper layer film formation composition of pattern or for insufficient against corrosion of dry etching resistance for substrate is processed Agent upper layer film formed use composition, as long as pattern can be only transferred to silicon-containing film, can also obtain have for processing and Say the pattern of organic resist lower membrane of sufficient dry etching resistance.Such pattern transfer based on dry ecthing, due to not Pattern collapse such problems of developer solution bring friction when can generate due to because of resist development etc., therefore even if be Depth-width ratio can also obtain the pattern give full play to the organic film of thickness of dry ecthing exposure mask.Moreover, pass through by The pattern for the organic resist lower membrane being thusly-formed is used as dry ecthing exposure mask, and can be transferred to pattern has in the presence of complicated section On the substrate of the three-dimensional transistor structure of difference.As above-mentioned such organic resist lower membrane, it is known to such as patent document 1 The multiple film of the film of middle record etc..

In general, in three layers of resist method, in order to stabilize processing dimension, for based on dry ecthing to organic against corrosion The pattern of agent lower membrane transfers, it usually needs the siliceous resist intermediate coat of several nm thickness is remained in organic resist lower membrane On pattern.Due to using organic resist lower layer film figure as exposure mask and pattern is transferred to substrate way in, this is remaining The dry etching gas etching removal that silicon is processed substrate at branch, therefore will not remain in after processing substrate organic On resist lower layer film figure.Therefore, even if carrying out dry corrosion to remaining organic resist lower layer film figure after processing substrate (ashing) or wet type removal are carved, which will not remain on substrate as residue.

As noted previously, as multilayer resist method can also be suitable for substrate even for the substrate for being formed with larger segment difference Processing method, therefore be used in extensive substrate processing.Here, expecting to be used as tubular as three-dimensional crystal using this feature At the ion implanting shadow mask of the ion injecting process of a part of process.However, using three layers of resist method formed from Organic resist lower layer film figure of sub- injection, since organic resist lower layer film figure is not carried out base as exposure mask Plate processing, therefore in fact, as described above, silicon remains on organic resist lower layer film figure at branch.Therefore, if by this Organic resist lower layer film figure of sample is as shadow mask and carries out ion implanting, then remains in organic resist lower membrane figure Silicon in case is modified at branch because of the ion of injection, in cleaning process after injection process, can not with it is organic against corrosion The substance that agent lower layer film figure is removed simultaneously, and not can be removed can remain on substrate as foreign matter, so as to cause ion note The yield rate for entering process reduces.This problem in order to prevent, it is necessary in the feelings not impacted to organic resist lower layer film figure Under condition, the silicon ingredient remained on organic resist lower layer film figure is selectively cleaned into removal before ion implantation.However, This silicon ingredient is modified because carrying out the dry etching gas used when pattern transfer to organic resist lower membrane, can not pass through half Ammonia spirit usually applicable in conductor manufacturing process, as the cleaning solution for not causing damage to substrate containing hydrogen peroxide (hereinafter also referred to as ammonia aquae hydrogenii dioxidi) and clean removal.In order to which the silicon ingredient for being modified this cleans removal completely, need to fit When using hydrofluoric acid based cleaning liquid, but this cleaning solution can cause to damage to semiconductor substrate surface, cause the manufacturing procedure at Product rate reduces.Therefore, seek a kind of after the pattern to organic resist lower membrane based on dry ecthing transfers, Neng Gou Not to substrate cause damage in the case where by the silicon ingredient remained on organic resist lower layer film figure removal method and It is suitble to the material of this method.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2016-094612 bulletin (U.S. Patent Application Publication No. 2013/0337649 (A1) number specification)

Summary of the invention

The technical problem to be solved in the present invention

The present invention is to carry out in view of the above problems, and it is an object of the present invention to provide a kind of organic film shape that can form organic film At with composition, which can be by using will not be to necessary organic in semiconductor device substrate and patterning process Resist lower membrane causes the stripper of damage, commonly used in such as manufacture of semiconductor is referred to as SC1 (Standard Cleaner 1) the ammonia spirit containing hydrogen peroxide, easily with the silicon ingredient residue of the modification wet type together due to dry ecthing Removal.

Solve the technological means of technical problem

In order to solve the above technical problem, the present invention provides a kind of organic film formation compositions, and it includes producing high-moleculars Object and organic solvent are closed, which has any a kind in the repetitive unit indicated by the following general formula (1)~(4) More than, in the organic solvent, total account for selected from one or more of propylene glycol ester, ketone and lactone is more than whole organic solvents In 30wt% amount.

[chemical formula 1]

In formula, R₁For carbon atom number be 1~19 alkyl, halogen atom, alkoxy, carboxyl, sulfo group, methoxycarbonyl group, hydroxyl Phenyl or amino, R₂It is the group that acidic functionality is generated by heating or the effect of acid, R for hydrogen atom or AL, AL₃For hydrogen Atom, furyl can have the alkyl that chlorine atom or the carbon atom number of nitro are 1~16；k₁、k₂And k₃For 1~2, l be 1~ 3, m be 0~3, n be 0 or 1.

If such organic film formation composition, then following organic film is capable of forming: can be by using will not The stripper of damage, such as half are caused to necessary organic resist lower membrane in semiconductor device substrate and patterning process The commonly used ammonia spirit containing hydrogen peroxide for being referred to as SC1, easily with changes because of dry ecthing in conductor processing procedure Property silicon ingredient residue together wet type removal organic film.In addition, can then be fitted if such organic film formation composition As ion implanting shadow mask material when forming three-dimensional transistor.

At this point, it is preferred that: the organic film formation is the composition for being used to form following organic film with composition: being directed into can It is dissolved in the underface of the siliceous resist intermediate coat of ammonia aquae hydrogenii dioxidi and is insoluble under organic resist of ammonia aquae hydrogenii dioxidi The organic film of the surface of tunic.

Organic film formation of the invention with composition be capable of forming following organic film composition (hereinafter also referred to as This composition): in three layers of resist method being formed on substrate, it is formed in organic resist lower membrane and is formed in photic anti- The organic film (hereinafter also referred to as this organic film) between the siliceous resist intermediate coat immediately below agent is lost, to be capable of forming essence It is upper to use composition for the organic film formation of 4 layers of resist.Organic resist lower membrane can be formed on substrate, organic against corrosion This organic film is formed between agent lower membrane and siliceous resist intermediate coat, then forms siliceous resist intermediate coat, further shape After the resist of upper layer, pattern is formed on the resist of upper layer, and this pattern is transferred in siliceous resist using dry ecthing Between film, dry ecthing disposably is carried out to this organic film and organic resist lower membrane using the pattern of the transfer as exposure mask, from And carry out pattern transfer.Herein, if siliceous resist intermediate coat dissolves in ammonia aquae hydrogenii dioxidi and organic resist lower membrane is difficult It is dissolved in ammonia aquae hydrogenii dioxidi, then the silicon that can will remain on the pattern transferred in the above described manner using ammonia hydrogen peroxide water process Ingredient removes together with this organic film, and thereby, it is possible to obtain organic resist lower layer film figure of no silicon ingredient residue.If by this Organic resist lower layer film figure is suitable for ion implanting shadow mask, then the three-dimensional transistor big even for segment difference, also can Accurate ion implanting is enough carried out, three-dimensional transistor processing can be carried out with high finished product rate.

In addition, at this point, it is preferred that: the siliceous resist intermediate coat includes any one in boron and phosphorus or both.

If the siliceous resist intermediate coat for having formed pattern is disposably turned pattern as exposure mask, and using dry ecthing Print to this organic film and organic resist lower membrane, then sometimes siliceous resist centre film figure can because in dry ecthing gas or The effect of plasma and recurring structure changes, so that the dissolubility to ammonia aquae hydrogenii dioxidi reduces.However, siliceous anti-by making Lose agent intermediate coat include in boron and phosphorus any one or both, no matter the gas or condition of dry ecthing, after dry ecthing The siliceous resist intermediate coat and/or silicon ingredient residue for dissolving in ammonia aquae hydrogenii dioxidi can be become.

In addition, at this point, it is preferred that: the organic film formation with composition further include in thermal acid generator and crosslinking agent appoint Meaning one or both.

If organic film formation of the invention any one that composition includes in thermal acid generator and crosslinking agent or both, This organic film that homogeneous film thickness can not only be formed in organic resist lower membrane and uniformly formed, additionally it is possible to which inhibition will contain Occur when silicon resist intermediate coat is formed on the organic film mutually mixed.

In addition, at this point, it is preferred that: by being heated after being spun on the organic film formation on substrate with composition, from And organic film is obtained, the organic film is by utilizing with the mixing of 29% ammonium hydroxide/35% aquae hydrogenii dioxidi/water=1/1/8 ratio Made of 65 DEG C of solution when being handled, with 5nm/ minutes or more solution rate.

If the organic film formation composition for the organic film that can obtain having such performance, then can not half-and-half lead In the case that body device manufacture causes damage with substrate, using ammonia aquae hydrogenii dioxidi by the silicon on this organic film and this organic film at Residue is divided sufficiently to remove.

Further, preferably: it is 10nm more than and less than 100nm's that the organic film formation, which can obtain film thickness with composition, Organic film.

If the organic film formation composition for the organic film that can obtain having such film thickness, even if then will be siliceous against corrosion Agent intermediate coat is transferred to this organic film and organic resist lower membrane as dry ecthing mask and disposably by pattern, also can be It keeps transferring pattern in the state of the precision of the pattern formed by upper layer resist.

Invention effect

If such organic film formation composition, then following organic film is capable of forming: can be by using will not The stripper of damage, such as half are caused to necessary organic resist lower membrane in semiconductor device substrate and patterning process In conductor processing procedure it is commonly used be referred to as SC1 ammonia aquae hydrogenii dioxidi, easily with due to dry ecthing modification silicon at Divide the residue organic film that wet type removes together.In addition, by being applied organic film formation of the invention with composition organic anti- It loses between agent lower membrane and siliceous resist intermediate coat, can be formed on pattern not when forming ion implanting shadow mask The ion implantation mask of residual silicon ingredient.Thereby, it is possible to prevent the reduction of the yield rate of the manufacturing process of three-dimensional transistor, Neng Goujie Manufacture to cost-saving the semiconductor device of higher performance.

Specific embodiment

As described above, being seeking to a kind of organic film formation composition for being capable of forming following organic film: Neng Goutong It crosses using the stripping that will not cause damage to necessary organic resist lower membrane in semiconductor device substrate and patterning process The commonly used ammonia aquae hydrogenii dioxidi for being referred to as SC1 in chaotropic, such as manufacture of semiconductor, easily and due to dry ecthing The modified silicon ingredient residue organic film that wet type removes together.

The present inventor endeavours to study in view of the above technical problems repeatedly, as a result, it has been found that being formed if following organic film With composition, then it is able to solve above-mentioned technical problem, so as to complete the present invention, wherein the organic film formation composition packet Pbz polymer compound and organic solvent, the high-molecular compound have the repetitive unit that is indicated by the following general formula (1)~(4) it In any a kind or more, and in the organic solvent, total account for selected from one or more of propylene glycol ester, ketone and lactone is more than The amount of 30wt% in whole organic solvents.

That is, the present invention is that following organic film is formed with composition: the organic film formation composition includes producing high-molecular Object and organic solvent are closed, which has any a kind in the repetitive unit indicated by the following general formula (1)~(4) More than, in the organic solvent, total account for selected from one or more of propylene glycol ester, ketone and lactone is more than whole organic solvents In 30wt% amount.

[chemical formula 2]

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited by these embodiments.

[organic film, which is formed, uses composition]

Organic film formation composition of the invention contains high-molecular compound and organic solvent.Hereinafter, to each ingredient into Row is further described in detail.

<high-molecular compound>

High-molecular compound in organic film formation composition of the invention has by the following general formula (1)~(4) expression Repetitive unit in any a kind or more.

[chemical formula 3]

Herein, as the repetitive unit indicated by general formula (1), the repetitive unit with flowering structure can be exemplified.

[chemical formula 4]

As the repetitive unit indicated by general formula (2), the repetitive unit with flowering structure can be exemplified.

[chemical formula 5]

As the repetitive unit indicated by general formula (3), the repetitive unit with flowering structure can be exemplified.

[chemical formula 6]

As the repetitive unit indicated by general formula (4), the repetitive unit with flowering structure can be exemplified.

[chemical formula 7]

Wherein, as preferred repetitive unit, the repetitive unit by above-mentioned general formula (2) or (3) expression can be exemplified.If Organic film formation composition comprising the high-molecular compound with such repetitive unit, then the carboxyl position high due to polarity In effective position, therefore it is capable of forming the organic film excellent based on the wet type removal of ammonia aquae hydrogenii dioxidi.

Herein, as the repetitive unit for obtaining the n=0 in the repetitive unit indicated by above-mentioned general formula (1)~(4) Monomer can enumerate phenol, o-cresol, metacresol, paracresol, 2,3- xylenol, 2,5- xylenol, 3,4- diformazan Base phenol, 3,5- xylenol, 2,4- xylenol, 2,6- xylenol, 2,3,5- pseudocuminol, 3,4,5- tri- Methylphenol, 2-TBP, 3- tert-butyl phenol, 4-TBP, resorcinol, 2- methyl resorcinol, 4- first Base resorcinol, oreinol diphenol, catechol, 4- tert-butyl catechol, 2- metoxyphenol, 3- methoxybenzene Phenol, 2- propylphenol, 3- propylphenol, 4- propylphenol, 2- isopropyl-phenol, 3- isopropyl-phenol, 4- isopropyl-phenol, 2- In methoxyl group -5- methylphenol, 2- tert-butyl -5- methylphenol, 4- phenylphenol, trityl phenol, pyrogallol, hundred Phenol, glycidyloxyphenyl ether, 4- fluorophenol, 3,4- difluorophenol, 4- trifloro methyl phenol, 4- chlorophenol, 4- hydroxy benzenes sulphur Acid, 4-Vinyl phenol, 1- (4- hydroxyphenyl) naphthalene etc..

As the monomer of the repetitive unit for obtaining n=1, can enumerate 1- naphthols, beta naphthal, 2- methyl-1-naphthols, 4- methoxyl group -1- naphthols, 7- methoxyl group-beta naphthal, 1,2- dihydroxy naphthlene, 1,3- dihydroxy naphthlene, 2,3- dihydroxy naphthlene, 1,4- bis- Hydroxyl naphthalene, 1,5- dihydroxy naphthlene, 1,6- dihydroxy naphthlene, 2,6- dihydroxy naphthlene, 1,7- dihydroxy naphthlene, 2,7 dihydroxy naphthalene, 1,8- Dihydroxy naphthlene, 5- amino -1- naphthols, 2- methoxycarbonyl -1- naphthols, 6- (4- hydroxyphenyl)-beta naphthal, 6- (cyclohexyl) -2- Naphthols, 1,1 '--2,2 '-naphthols of connection, 6,6 '-connection -2,2 '-naphthols, bis- (6- hydroxyl -2- naphthalene) fluorenes of 9,9-, 6- hydroxyl -2- second Alkenyl naphthalene, 1- methylol naphthalene, 2- methylol naphthalene, 8- hydroxyl naphthalene -1- sulfonic acid, 2 hydroxy naphthalene -7- sulfonic acid, 2,3- dihydroxy naphthlene -7- Sulfonic acid, 1,7- dihydroxy naphthlene -3- sulfonic acid etc..

These monomers can use individually, can also be applied in combination to control n value, k value and elching resistant 2 kinds with On.

As the condensing agent for carrying out condensation reaction with these monomers, aldehyde compound as described below can be exemplified.Such as first Aldehyde, trioxane, paraformaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, pentamethylene formaldehyde, cyclopentene formaldehyde, cyclohexanecarboxaldehyde, cyclohexene first Aldehyde, norbornane formaldehyde, norbornene formaldehyde, adamantane formaldehyde, benzaldehyde, phenylacetaldehyde, α-hydrocinnamicaldehyde, beta-phenyl propionic aldehyde, Benzaldehyde,2-hydroxy, 3- hydroxy benzaldehyde, 4- hydroxy benzaldehyde, 2,3- 4-dihydroxy benzaldehyde, 2,4- 4-dihydroxy benzaldehyde, 3,4- 4-dihydroxy benzaldehyde, 2- chlorobenzaldehyde, 3- chlorobenzaldehyde, 4- chlorobenzaldehyde, 2- nitrobenzaldehyde, 3- nitrobenzaldehyde, 4- nitre Benzaldehyde, 2- tolyl aldehyde, 3- tolyl aldehyde, 4- tolyl aldehyde, 2- ethylo benzene formaldehyde, 3- ethylo benzene formaldehyde, 4- Ethylo benzene formaldehyde, Benzaldehyde,2-methoxy, m-methoxybenzaldehyde, 4-methoxybenzaldehyde, anthraldehyde, pyrene formaldehyde, furfural etc..

In addition to this, the compound that can be indicated by following chemical formula can also be exemplified.

[chemical formula 8]

The ratio of aldehyde compound about monomer and as condensing agent, 1 mole of the total amount of the mole relative to monomer, Preferably 0.01~5 mole, more preferably 0.05~2 mole.

It, will be whole as the ratio that the repetitive unit indicated by above-mentioned general formula (1)~(4) is occupied in whole repetitive units When body is set as 100%, preferably 10% or more, more preferably 30% or more.

When using raw material as described above to carry out polycondensation reaction, usually can with it is solvent-free or in a solvent using acid Or alkali is as catalyst, and carries out under cooling or heating in room temperature or as needed, thus, it is possible to obtain macromolecule chemical combination Object (polymer).It as used solvent, can exemplify: methanol, ethyl alcohol, isopropanol, butanol, ethylene glycol, propylene glycol, diethyl The alcohols such as glycol, glycerol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether；Diethyl ether, two fourths The ethers such as ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, 1,4- dioxanes；Methylene chloride, chloroform, The chlorine class solvent such as dichloroethanes, trichloroethanes；The hydro carbons such as hexane, heptane, benzene,toluene,xylene, isopropylbenzene；The nitriles such as acetonitrile Class；The ketones such as acetone, ethyl methyl ketone, isobutyl methyl ketone；Ethyl acetate, n-butyl acetate, methyl proxitol acetate Etc. esters；The lactones such as gamma-butyrolacton；The aprotics such as dimethyl sulfoxide, N,N-dimethylformamide, hexamethylphosphoramide Polar solvent class, these solvents can be used alone or be used in mixed way two or more.Relative to 100 mass parts of reaction raw materials, these Solvent can use in the range of 0~2,000 mass parts.

As acid catalyst, it is able to use the inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, heteropoly acid；Grass The organic acids such as acid, trifluoroacetic acid, methanesulfonic acid, benzene sulfonic acid, p-methyl benzenesulfonic acid, trifluoromethanesulfonic acid；It is alchlor, aluminium ethylate, different Aluminium propoxide, boron trifluoride, boron chloride, Boron tribromide, tin tetrachloride, tin tetrabromide, dibutyl tin dichloride, dibutyl diformazan Oxygroup tin, Dibutyltin oxide, titanium tetrachloride, titanium tetrabromide, methanol titanium (IV), titanium ethanolate (IV), isopropyl titanate (IV), oxidation Louis' acids such as titanium (IV).Base catalyst is able to use sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, bicarbonate The inorganic bases such as sodium, potassium carbonate, lithium hydride, sodium hydride, hydrofining, calcium hydride；Lithium methide, n-BuLi, methylmagnesium-chloride, bromine Change the metal alkyls classes such as magnesium ethide；The alcohol salt such as sodium methoxide, sodium ethoxide, potassium tert-butoxide；Triethylamine, diisopropyl ethyl amine, N, The organic bases such as accelerine, pyridine, 4-dimethylaminopyridine.Relative to raw material, usage amount is preferably 0.001~ The range of 100 weight %, the more preferably range of 0.005~50 weight %.Reaction temperature is preferably -50 DEG C of boiling points to solvent Left and right, further preferably room temperature is to 100 DEG C.

As the method for polycondensation reaction, the method that monomer, condensing agent, catalyst are added together can be enumerated, and is being urged The method of monomer, condensing agent is gradually added dropwise in the presence of agent.

In addition, after polycondensation reaction, it, can root in order to will be present in the removal such as the unreacting material in system, catalyst Following methods are used respectively according to the property of obtained reaction product: the temperature of reaction kettle being made to be warming up to 130~230 DEG C, and The method that will volatilize ingredient removal with 1~50mmHg or so；And solvent or water appropriate is added by the method for polymer fractionation；Make Polymer makes the method etc. of its reprecipitation in lean solvent after being dissolved in good solvent.

The molecular weight that polystyrene as the polymer obtained in the above described manner converts, preferable weight-average molecular weight (Mw) are 500~500,000, particularly preferably 1,000~100,000.In addition, the dispersion degree of molecular weight, preferably 1.2~20 range Interior use.It, can by being 1,000 low-molecular weight separation below by monomer component, oligomer ingredient or molecular weight (Mw) Inhibit the volatile ingredient in baking, can prevent from being fallen on wafer by the pollution on baking cup periphery or the volatile ingredient of accumulation and Caused surface defect.

Organic film formation of the invention composition includes organic solvent.As the concrete example of organic solvent, can enumerate The ketones such as cyclopentanone, cyclohexanone, methyl -2- amyl ketone；3- methoxybutanol, 3- methyl -3- methoxybutanol, 1- methoxyl group - 2- propyl alcohol, 1- ethyoxyl -2- propyl alcohol, propylene glycol monomethyl ether, ethylene glycol single methyl ether, propylene glycol monoethyl, ethylene glycol list The alcohols such as ethylether；The ethers such as propylene glycol dimethyl ether, diethylene glycol dimethyl ether；Propylene glycol monomethyl ether, the third two Alcohol list monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, 3- methoxy methyl propionate, 3- ethoxy-propionic acid second The esters such as ester, tert-butyl acetate, propanoic acid tert-butyl ester, propylene glycol list tertbutyl ether acetic acid esters；Gamma-butyrolacton etc., these are organic molten Agent is able to use a kind or is mixed with two or more, but is not limited to these.

Herein, in organic solvent, (such as foregoing illustrative organic selected from one or more of propylene glycol ester, ketone, lactone In solvent, a kind in propylene glycol monomethyl ether, cyclopentanone, cyclohexanone, methyl -2- amyl ketone, gamma-butyrolacton More than) it is total must account for be more than 30wt% in whole organic solvents amount.It, can not when organic solvent is unsatisfactory for this condition Uniform organic film is formed in the surface of organic resist lower membrane.

In addition, organic film of the invention is formed in composition, the production for further promoting cross-linking reaction can be added Sour agent and crosslinking agent.As acid agent, has and the acid agent (thermal acid generator) of acid is generated by thermal decomposition and is irradiated by light The acid agent for generating acid, can add any of them.

As acid agent, can enumerateSalt, diazomethane derivative, glyoxime derivative, bis sulfone derivative, N- hydroxyl Sulphonic acid ester, β -one sulfonic acid, two sulfone derivatives, the nitrobenzyl sulfonate esters derivative, sulfonate, sulphur of imide compound Acid ester derivant etc..Japanese Unexamined Patent Publication 2008-65303 bulletin (U.S. Patent Application Publication No. 2008/ can specifically be enumerated 0038662 (A1) number specification) (0081)~(0111) section in documented acid agent.

As crosslinking agent, can enumerate by selected from least one of methylol, alkoxy methyl, pivaloyloxymethyl group Melamine compound made of substitution, guanamines compound, glycoluril compounds or carbamide compound, epoxide, epithio chemical combination Object, isocyanate compound, azide chemical compound, compound of double bond comprising alkenyl ether etc. etc..It can specifically arrange Enumerate the of Japanese Unexamined Patent Publication 2008-65303 bulletin (U.S. Patent Application Publication No. 2008/0038662 (A1) number specification) (0074)~(0080) documented crosslinking agent in section.

Further, it is also possible to organic film formation of the invention with addition in composition for improving coating when carrying out spin coating The surfactant of property.As surfactant, polyoxyethylene ethers, polyoxyethylene allyl can be enumerated Ethers, polyoxyethylene polyoxypropylene block copolymer analog, sorbitan fatty acid ester class, polyoxy ethylene sorbitol alcohol The nonionic surface active agent of acid anhydride aliphatic ester；Fluorine class surfactant；Partially fluorinated Cationic Ring-opening Polymerization of Substituted Oxetane species Surfactant etc..Japanese Unexamined Patent Publication 2009-269953 bulletin (U.S. Patent Application Publication No. can specifically be enumerated 2009/0274978 (A1) number specification) (0142)~(0147) section in documented surfactant.

Further, the alkali for improving storage stability can also be added into organic film formation composition of the invention Property compound.Alkali compounds can play acid the effect of quencher (quencher), micro- to prevent from being generated by acid agent The acid of amount carries out cross-linking reaction.As such alkali compounds, primary, secondary, uncle aliphatic amine can be enumerated, blend together amine Class, aromatic amine, heterocyclic amine, the nitrogenous compound with carboxyl, the nitrogenous compound with sulfonyl, with hydroxyl Nitrogenous compound, the nitrogenous compound with hydroxyphenyl, alcohol nitrogenous compound, amide derivatives, imide derivative etc..Tool Japanese Unexamined Patent Publication 2008-65303 bulletin can be enumerated for body, and (U.S. Patent Application Publication No. 2008/0038662 (A1) number is said Bright book) (0112)~(0119) section in documented alkali compounds.

Organic film formation composition of the invention can be suitable for the formation of following organic film as described above: lead Enter to the underface for the siliceous resist intermediate coat for dissolving in ammonia aquae hydrogenii dioxidi and is insoluble in the organic anti-of ammonia aquae hydrogenii dioxidi Lose the organic film of the surface of agent lower membrane.

In addition, it is 10nm more than and less than 100nm's that organic film formation of the invention, which preferably forms film thickness with composition, The composition of organic film, further preferred film thickness are 20nm or more and 80nm or less.If the film thickness of organic film is 10nm or more, The removal effect of the silicon ingredient based on wet processed can be sufficiently obtained, in addition, being able to suppress and being done if being less than 100nm Lateral erosion when etching and processing, thus will not work in-process generation undesirable condition.

[organic film]

Organic film can be formed by organic film formation composition of the invention.It is used as using organic film of the invention to be formed Composition and the method for forming organic film, can enumerate the organic film formation composition using spin-coating method etc. by aforementioned present invention The method being coated on processed substrate.After spin coating, in order to evaporate solvent, prevent among resistant upper layer film or resist The mutual of film mixes or in order to promote cross-linking reaction, is toasted.Baking carries out in 100 DEG C or more and 400 DEG C or less of range, 10~600 seconds, preferably at 10~300 seconds in the range of carry out.Baking temperature is more preferably 150 DEG C or more and 350 DEG C or less.

As described above, the organic film formed by organic film formation of the invention with composition can suitably be directed into siliceous resist Lose the underface of agent intermediate coat and the surface of organic resist lower membrane.

As such siliceous resist intermediate coat, preferably: dissolving in ammonia aquae hydrogenii dioxidi and ammonia peroxidating can be utilized Hydrogen water and the film for dissolving or removing.It is preferable to use such as Japanese Unexamined Patent Publication 2010-085912 bulletin (U.S. Patent Application Publication No.s 2010/0086870 (A1) number specification), Japanese Unexamined Patent Publication 2010-085893 bulletin (U.S. Patent Application Publication No. 2010/ 0086872 (A1) number specification), Japanese Unexamined Patent Publication 2015-028145 bulletin (U.S. Patent Application Publication No. 2015/0004791 (A1) number specification), International Publication No. No. 2010/068336 bulletin (U.S. Patent Application Publication No. 2011/0233489 (A1) Number specification), Japanese Unexamined Patent Publication 2016-074772 bulletin (U.S. Patent Application Publication No. 2016/0096977 (A1) number explanation Book), institute in Japanese Unexamined Patent Publication 2016-074774 bulletin (U.S. Patent Application Publication No. 2016/0096978 (A1) number specification) The siliceous resist lower membrane recorded, as the siliceous resist intermediate coat in the present invention.Wherein, due to comprising in boron and phosphorus The siliceous resist intermediate coat of any one or both it is excellent using the wet type removal of ammonia aquae hydrogenii dioxidi therefore especially excellent Choosing.

In addition, preferably having to ammonia aquae hydrogenii dioxidi indefatigable as organic resist lower membrane is suitable for the invention Film (is insoluble in the film of ammonia aquae hydrogenii dioxidi).Such as can be used Japanese Unexamined Patent Publication 2004-205685 bulletin (U.S. Patent No. 7, 427,464 (B2) number specifications), Japanese Unexamined Patent Publication 2010-122656 bulletin (U.S. Patent Application Publication No. 2010/0099044 (A1) number specification and U.S. Patent Application Publication No. 2013/0184404 (A1) number specification), Japanese Unexamined Patent Publication 2012-214720 Number bulletin (U.S. Patent Application Publication No. 2012/0252218 (A1) number specification), Japanese Unexamined Patent Publication 2016-094612 bulletin Organic resist lower membrane disclosed in (U.S. Patent Application Publication No. 2013/0337649 (A1) number specification).

Above-mentioned organic resist lower membrane by using spin-coating method etc. by organic resist lower layer film composition be coated on by It is formed on processing substrate.By using spin-coating method etc., good insertion characteristic can be obtained.After spin coating, in order to steam solvent Hair prevents from mixing with the mutual of resistant upper layer film or siliceous resist intermediate coat or in order to promote cross-linking reaction, being toasted.It dries Bake and carried out in 100 DEG C or more and 600 DEG C or less of range, 10~600 seconds, preferably at 10~300 seconds in the range of carry out. Baking temperature is more preferably 200 DEG C or more and 500 DEG C or less.When in view of being influenced caused by element damage and wafer distortion, The upper limit of heating temperature in the silicon wafer process of lithographic printing is preferably 600 DEG C hereinafter, more preferably 500 DEG C or less.

In the method for forming organic resist lower membrane in the above described manner, by utilizing spin-coating method etc. by organic resist Lower layer's film composition is coated on processed substrate, and in air, N₂, Ar, He etc. atmosphere under this composition is burnt into To make its solidification, organic resist lower membrane thus can be formed.By under the atmosphere comprising oxygen to this organic resist Lower layer's film composition is burnt into, and can obtain and have indefatigable cured film to ammonia aquae hydrogenii dioxidi.

By forming organic resist lower membrane in the above described manner, due to its excellent insertion/planarization characteristics, nothing The bumps for being processed substrate are closed, flat cured film can be obtained, thus for being the structure of 30nm or more having height It is exceedingly useful for being formed for flat cured film on body or the substrate of segment difference.

In addition, the thickness of organic resist lower membrane of this semiconductor device manufacture planarization can be suitably selected, But preferably 5~500nm, particularly preferably 10~400nm.

Organic film formation of the invention is suitable for the formation of organic film with composition, which is fed to siliceous anti- The underface of agent intermediate coat and the surface of organic resist lower membrane are lost, and when forming ion implanting shadow mask, is Wet type removes above-mentioned organic film and siliceous resist intermediate coat, preferably comprises the stripper of hydrogen peroxide.At this point, in order to promote Acid or alkali is added further preferably into stripper to adjust pH in removing.As such pH adjusting agent (acid or alkali), can illustrate The inorganic acids such as hydrochloric acid or sulfuric acid out；The organic acids such as acetic acid, oxalic acid, tartaric acid, citric acid, lactic acid；Ammonium hydroxide, ethanol amine, hydroxide The nitrogenous alkali such as tetramethylammonium；EDTA (ethylenediamine tetra-acetic acid) etc. nitrogenous organic acid compound etc..Particularly preferred ammonium hydroxide.That is, making For the preferred ammonia aquae hydrogenii dioxidi of above-mentioned stripper.

Ratio when using ammonia aquae hydrogenii dioxidi as stripper, as ammonium hydroxide, hydrogen peroxide and dilution deionized water Example, relative to 100 mass parts of deionized water, ammonium hydroxide is 0.01~20 mass parts, preferably 0.05~15 mass parts, more preferably 0.1~10 mass parts, hydrogen peroxide are 0.01~20 mass parts, preferably 0.05~15 mass parts, more preferably 0.1~10 matter Measure part.

As long as wet type removal utilizes following manner: preparing 0 DEG C~80 DEG C, preferably 5 DEG C~70 DEG C of stripper, by shape At there is the Silicon Wafer for the processed substrate for being intended to be handled to be impregnated in this stripper.Furthermore, it is desirable to when, it can be by by stripper The process for being sprayed on surface or being coated with the conventional process of stripper etc. while rotating wafer, easily by siliceous resist Intermediate coat and the organic film removal formed by organic film formation of the invention composition.

Particularly preferably by being heated after being spun on organic film formation of the invention on substrate with composition, thus To following organic film: 65 DEG C mixed when utilization with 29% ammonium hydroxide/35% aquae hydrogenii dioxidi/water=1/1/8 ratio Solution when being handled with the organic film of 5nm/ minutes or more solution rate.

In addition, preferably determining the silicon on the surface for remaining in organic resist lower membrane after ammonia hydrogen peroxide water process Amount, to confirm the removal degree of silicon ingredient.It can be for example, by Japanese Unexamined Patent Publication 2016-177262 bulletin (U.S. Patent application 2016/0276152nd (A1) number specification disclosed) in documented method analyzed.

As described above, being then capable of forming following organic film: Neng Goutong if organic film formation composition of the invention It crosses using the stripping that will not cause damage to necessary organic resist lower membrane in semiconductor device substrate and patterning process The commonly used ammonia aquae hydrogenii dioxidi for being referred to as SC1 in chaotropic, such as manufacture of semiconductor, easily and due to dry ecthing The modified silicon ingredient residue organic film that wet type removes together.In addition, by the way that organic film formation of the invention is answered with composition For that can be formed when forming ion implanting shadow mask between organic resist lower membrane and siliceous resist intermediate coat The ion implantation mask of non-residual silicon ingredient on pattern.Thereby, it is possible to prevent the yield rate of the manufacturing process of three-dimensional transistor from dropping It is low, it can cost-effectively manufacture the semiconductor device of higher performance.

Embodiment

Hereinafter, enumerating synthesis example, Examples and Comparative Examples to illustrate the present invention, but the present invention is not by these examples Record restriction.In addition, % indicates quality % in following examples, molecule measuring has been carried out using gel permeation chromatography (GPC) It is fixed.In GPC measurement, detected using RI (differential refraction detector), eluent is tetrahydrofuran, has thus found out polyphenyl second The molecular weight of alkene conversion.

[synthesis of high-molecular compound]

[synthesis example (A1)]

In the three-neck flask of 500mL measure resorcinol 40.00g (0.36mol), p-methyl benzenesulfonic acid monohydrate 20 Quality %PGME solution 10.00g and 2- methoxy-1-propanol 72.00g, is heated to 80 DEG C while stirring.It is added thereto 37% Formalin 23.59g (formaldehyde 0.29mol), and stirred 11 hours.Ultrapure water 160g and acetic acid second are added into reaction solution Ester 200g simultaneously moves to separatory funnel, in order to remove acid catalyst and metal impurities, has been washed 10 times using ultrapure water 150g.It will After obtained organic layer is concentrated under reduced pressure into 76g, ethyl acetate is added and obtains the solution of 150g, and joined n-hexane 217g. N-hexane layer becomes upper layer, high concentration polymer solution becomes lower layer, is thus separated, this upper layer is removed.Repeat 2 Secondary identical operation, obtained polymer solution is concentrated, and is further dried under reduced pressure 13 hours with 80 DEG C, to obtain High-molecular compound A1.Weight average molecular weight (Mw), dispersion degree (Mw/Mn), result Mw=800, Mw/Mn=are found out by GPC 1.3.This high-molecular compound A1 has the repetitive unit indicated by general formula (4).

[synthesis example (A2)]

In the three-neck flask of 1,000mL, by 1,5- dihydroxy naphthlene 80.1g (0.50mol), 37% Formalin 26.4g (0.24mol) and 2- methoxy-1-propanol 250g are slowly added into after homogeneous solution is made with 80 DEG C of liquid temperature under nitrogen atmosphere 20% p-methyl benzenesulfonic acid 2- methoxy-1-propanol solution 18g, and stirred 12 hours with 110 DEG C of liquid temperature.After being cooled to room temperature, Methyl iso-butyl ketone (MIBK) 500g is added, and organic layer is dried under reduced pressure solidification by after organic layer washing 5 times using pure water 200g. THF 300mL is added into residue, and utilizes hexane 2,000mL makes polymer reprecipitation.The polymer filtration of precipitating is separated And be dried under reduced pressure, to obtain high-molecular compound A2.Weight average molecular weight (Mw), dispersion degree (Mw/Mn) are found out by GPC, Its result Mw=3,000, Mw/Mn=2.7.This high-molecular compound A2 has the repetitive unit indicated by general formula (4).

[synthesis example (A3)]

In the three-neck flask of 2,000mL, by 1,5- dihydroxy naphthlene 80.1g (0.50mol), 3,4- bis- (tert-butoxy) benzene Formaldehyde 100.1g (0.40mol) and 2- methoxy-1-propanol 600g, is made homogeneous solution under nitrogen atmosphere with 80 DEG C of liquid temperature Afterwards, it is slowly added into 25% sodium hydrate aqueous solution 6.4g, and has been stirred 24 hours with 110 DEG C of liquid temperature.After being cooled to room temperature, it is added Ethyl acetate 1,500g, and after utilization 3% aqueous solution of nitric acid 300g washing organic layer, further utilize pure water 300g by organic layer Washing 5 times, and organic layer is dried under reduced pressure solidification.THF 400mL is added into residue, and utilizes hexane 3,000mL makes to gather Close object reprecipitation.The polymer filtration of precipitating is separated and is dried under reduced pressure, to obtain high-molecular compound A3.Pass through GPC Find out weight average molecular weight (Mw), dispersion degree (Mw/Mn), result Mw=2,900, Mw/Mn=2.9.This high-molecular compound A3 With the repetitive unit indicated by general formula (1).

[synthesis example (A4)]

1,5- dihydroxy naphthlene 80g (0.50mol), 4- hydroxy benzaldehyde 36.6g are added into the flask of 1,000mL (0.30mol) and methyl cellosolve 145g, and 20 mass % methyl of p-methyl benzenesulfonic acid are added to while with 70 DEG C of stirrings Cellosolve solution 20g.Raise the temperature to 85 DEG C and stir 6 hours after, be cooled to room temperature, and using ethyl acetate 800mL into Dilution is gone.Change and move to separatory funnel, and repeats to wash using deionized water 200mL, catalysts and metal are miscellaneous Matter removal.After obtained solution is concentrated under reduced pressure, ethyl acetate 600mL is added into residue, and utilize hexane 2,400mL makes Polymer reprecipitation.After the polymer filtration separation of precipitating, recycling, it is dried under reduced pressure, to obtain macromolecule chemical combination Object A4.Weight average molecular weight (Mw), dispersion degree (Mw/Mn) are found out by GPC, result Mw=3,800, Mw/Mn=2.4.This is high Molecular compound A4 has the repetitive unit indicated by general formula (1).

[synthesis example (A5)]

In the three-neck flask of 2,000mL, by 2,7- dihydroxy naphthlene 80.1g (0.50mol), the terephthalaldehydic acid tert-butyl ester 100.1g (0.40mol) and 2- methoxy-1-propanol 600g after homogeneous solution is made with 80 DEG C of liquid temperature under nitrogen atmosphere, delays It is slow that 25% sodium hydrate aqueous solution 6.4g is added, and stirred 24 hours with 110 DEG C of liquid temperature.After being cooled to room temperature, acetic acid is added Ethyl ester 1,500g, and after utilization 3% aqueous solution of nitric acid 300g washing organic layer, further organic layer is washed using pure water 300g It 5 times, has carried out being dried under reduced pressure solidification.THF 400mL is added into residue, and utilizes hexane 3,000mL makes polymer sink again It forms sediment.The polymer filtration of precipitating is separated and is dried under reduced pressure, to obtain high-molecular compound A5.It is equal that weight is found out by GPC Molecular weight (Mw), dispersion degree (Mw/Mn), result Mw=2,900, Mw/Mn=2.9.This high-molecular compound A5 has by leading to The repetitive unit that formula (2) indicates.

[synthesis example (A6)]

In the three-neck flask of 2,000mL, by 6-Hydroxy-2-naphthoic acid 94.4g (0.50mol), terephthalaldehydic acid uncle Butyl ester 100.1g (0.40mol) and 2- methoxy-1-propanol 600g, is made homogeneous solution under nitrogen atmosphere with 80 DEG C of liquid temperature Afterwards, it is slowly added into 25% sodium hydrate aqueous solution 6.4g, and has been stirred 24 hours with 110 DEG C of liquid temperature.After being cooled to room temperature, it is added Ethyl acetate 1,500g, and after utilization 3% aqueous solution of nitric acid 300g washing organic layer, further utilize pure water 300g by organic layer Washing 5 times, has carried out being dried under reduced pressure solidification.THF 400mL is added into residue, and utilizes hexane 3,000mL makes polymer Reprecipitation.The polymer filtration of precipitating is separated and is dried under reduced pressure, to obtain high-molecular compound A6.It is found out by GPC Weight average molecular weight (Mw), dispersion degree (Mw/Mn), result Mw=3,500, Mw/Mn=2.8.This high-molecular compound A6 has The repetitive unit indicated by general formula (2).

[synthesis example (A7)]

In the three-neck flask of 2,000mL, by 1,5- dihydroxy naphthlene 80.1g (0.50mol), terephthalaldehydic acid 60.1g (0.40mol) and 2- methoxy-1-propanol 600g are slowly added into after homogeneous solution is made with 80 DEG C of liquid temperature under nitrogen atmosphere 25% sodium hydrate aqueous solution 6.4g, and stirred 24 hours with 110 DEG C of liquid temperature.After being cooled to room temperature, ethyl acetate 1 is added, 500g, and after utilization 3% aqueous solution of nitric acid 300g washing organic layer, further organic layer is washed 5 times using pure water 300g, into It has gone and has been dried under reduced pressure solidification.THF 400mL is added into residue, and utilizes hexane 3,000mL makes polymer reprecipitation.It will sink The polymer filtration in shallow lake is separated and is dried under reduced pressure, to obtain high-molecular compound A7.Weight average molecular weight is found out by GPC (Mw), dispersion degree (Mw/Mn), result Mw=2,200, Mw/Mn=2.9.This high-molecular compound A7 has by general formula (2) table The repetitive unit shown.

[synthesis example (A8)]

In the three-neck flask of 200mL, by 6-Hydroxy-2-naphthoic acid 9.4g (0.05mol), terephthalaldehydic acid 5.3g (0.05mol) and 2- methoxy-1-propanol 60g are slowly added into after homogeneous solution is made with 80 DEG C of liquid temperature under nitrogen atmosphere 25% sodium hydrate aqueous solution 0.6g, and stirred 24 hours with 110 DEG C of liquid temperature.After being cooled to room temperature, ethyl acetate is added 150g, and using 3% aqueous solution of nitric acid 30g washing organic layer after, further using pure water 30g by organic layer wash 5 times, carry out It is dried under reduced pressure solidification.THF 40mL is added into residue, and makes polymer reprecipitation using hexane 300mL.By precipitating Polymer filtration is separated and is dried under reduced pressure, to obtain high-molecular compound A8.By GPC find out weight average molecular weight (Mw), Dispersion degree (Mw/Mn), result Mw=2,000, Mw/Mn=2.6.This high-molecular compound A8 has and is indicated by general formula (2) Repetitive unit.

[synthesis example (A9)]

In the three-neck flask of 2,000mL, by o-cresol 54.1g (0.50mol), 3,4- bis- (tert-butoxyCarbonylmethoxies) Benzaldehyde 140.2g (0.40mol) and 2- methoxy-1-propanol 600g, is made homogeneous solution under nitrogen atmosphere with 80 DEG C of liquid temperature Afterwards, it is slowly added into 25% sodium hydrate aqueous solution 6.4g, and has been stirred 24 hours with 110 DEG C of liquid temperature.After being cooled to room temperature, it is added Ethyl acetate 1,500g, and after utilization 3% aqueous solution of nitric acid 300g washing organic layer, further utilize pure water 300g by organic layer Washing 5 times, has carried out being dried under reduced pressure solidification.THF 400mL is added into residue, and utilizes hexane 3,000mL makes polymer Reprecipitation.The polymer filtration of precipitating is separated and is dried under reduced pressure, to obtain high-molecular compound A9.It is found out by GPC Weight average molecular weight (Mw), dispersion degree (Mw/Mn), result Mw=3,200, Mw/Mn=3.0.This high-molecular compound A9 has The repetitive unit indicated by general formula (3).

[synthesis example (A10)]

In the three-neck flask of 2,000mL, by 1,6- dihydroxy naphthlene 80.1g (0.50mol), 4- tert-butoxyCarbonylmethoxy Benzaldehyde 94.5g (0.40mol) and 2- methoxy-1-propanol 600g, is made homogeneous solution under nitrogen atmosphere with 80 DEG C of liquid temperature Afterwards, it is slowly added into 25% sodium hydrate aqueous solution 6.4g, and has been stirred 24 hours with 110 DEG C of liquid temperature.After being cooled to room temperature, it is added Ethyl acetate 1,500g, and after utilization 3% aqueous solution of nitric acid 300g washing organic layer, further utilize pure water 300g by organic layer Washing 5 times, has carried out being dried under reduced pressure solidification.THF 400mL is added into residue, and utilizes hexane 3,000mL makes polymer Reprecipitation.The polymer filtration of precipitating is separated and is dried under reduced pressure, to obtain high-molecular compound A10.It is found out by GPC Weight average molecular weight (Mw), dispersion degree (Mw/Mn), result Mw=2,700, Mw/Mn=2.7.This high-molecular compound A10 has The repetitive unit indicated by general formula (3).

[Examples and Comparative Examples]

By using ratio shown in table 1 by above-mentioned high-molecular compound A1~A10, as additive crosslinking agent XL1~ 3, thermal acid generator AG1, as surfactant include 0.1 mass %FC-4430 (Sumitomo 3M Limited manufacture) Organic solvent mixing, and be filtered with the filter of 0.1 μm of fluororesin, it is thus prepared for organic film formation group respectively It closes object (Sol.1~22).In addition, Sol.1~10,15~16,20~22 formed for organic film of the invention and use composition, Sol.11~14,17~19 are the organic film formation composition compared.In addition, being formed prepared organic film with combination Total amount for accounting for whole organic solvents selected from one or more of propylene glycol ester, ketone and lactone in object, it is shown in table 1 together.

[table 1]

Hereinafter, showing thermal acid generator AG1, crosslinking agent XL1~3.

[chemical formula 9]

In addition, the organic solvent in table 1 refers to following substance.

PGMEA: methyl proxitol acetate

Cyho: cyclohexanone

PGEE: propylene-glycol ethyl ether

GBL: gamma-butyrolacton

4M2P:4- methyl -2- amylalcohol

[solvent resistance evaluation: embodiment 1-1~15, comparative example 1-1~7]

Since siliceous resist intermediate coat is spun on the organic film formed by organic film formation composition of the invention Surface be therefore formed by whether organic film is the organic film for not occurring mutually to mix to investigate, have rated to organic solvent Patience.Above-mentioned organic film formation is respectively coated on silicon substrate with composition (Sol.1~22), and with 285 DEG C of firings 60 Second, to form organic film, and determine film thickness T1.PGMEA/PGME=30/70 (mass ratio), which is spun on, obtained to be had After on machine film, is heated 30 seconds with 100 DEG C, determine film thickness T2.By the measurement result of these film thickness, T1-T2 institute has been calculated The film thickness reduction amount shown.The results are shown in Table 2.

[table 2]

It will be apparent that, had by the organic film that Sol.1~10,15~16,20~22 are formed by embodiment 1-1~15 of table 2 There is sufficient organic solvent resistance.Therefore, even if siliceous resist intermediate coat to be spun on to the surface of these organic films, also can It is enough that stacked film is formed in the case where immiscible.

[the film forming evaluation in organic resist lower membrane: embodiment 2-1~15, comparative example 2-1~7]

Due to being laminated in organic resist lower membrane by organic film formation of the invention with the organic film that composition is formed, It is thus identified that its film forming in organic resist lower membrane.By the Shin-Etsu as organic resist lower membrane The spin coating carbon film ODL-102 of Chemical Co., Ltd. manufacture is coated on Silicon Wafer, so as to form having for film thickness 200nm Machine resist lower membrane.Organic film formation is coated on it with composition (Sol.1~22), and is burnt into 60 seconds with 285 DEG C, To form organic film, it is thus identified that the film-forming state of organic film.The results are shown in Table 3.

[table 3]

As shown in embodiment 2-1~15 of table 3, Sol.1~10,15~16,20~22 can by spin coating without film forming not Film is formed in organic resist lower membrane goodly.On the other hand, as shown in comparative example 2-1~7, the alcohol comprising 70wt% or more In organic resist lower membrane crawling (はじ I) occurs for Sol.11~14 of class organic solvent, 17~19, thus not It can stacked film.

[the wet type removal based on ammonia aquae hydrogenii dioxidi of organic film: embodiment 3-1~12]

Above-mentioned organic film formation is respectively coated on silicon substrate with composition (Sol.1~10,15~16), in 285 DEG C firing 60 seconds, to form organic film as the mode of 25nm, and determine film thickness T1.By this film with 29% ammonium hydroxide/35% Aquae hydrogenii dioxidi/water=1/1/8 ratio, which is mixed and is maintained in 65 DEG C of ammonia aquae hydrogenii dioxidi, to be impregnated 5 minutes, and is utilized pure After water is cleaned, with 100 DEG C heat drying 60 seconds, determine film thickness T3.In addition, finding out film removal speed at this time.These The results are shown in Table 4.

[table 4]

As shown in Table 4 it is found that can using ammonia aquae hydrogenii dioxidi with 5nm/ minute or more speed remove by Sol.1~ 10,15~16 organic film formed.

[the residue evaluation after organic resist lower membrane ashing: embodiment 4-1~15, comparative example 4-1]

The Shin-Etsu Chemical as organic resist lower membrane is formd using film thickness 200nm on Silicon Wafer Co., the spin coating carbon film ODL-102 of Ltd. manufacture.By organic film formation of the invention with composition (Sol.1~10,15~16, 20~22) it is respectively coated on it, and is heated 60 seconds with 285 DEG C, so that organic film be laminated.On the other hand, comparative example 4-1 In do not import organic film.

Then, it is coated with siliceous resist intermediate coat formation shown in following table 5 and uses composition (SiARC-1), and with 220 DEG C Heating 60 seconds, so that the siliceous resist intermediate coat that film thickness is 35nm be laminated.ArF is used into the development of eurymeric shown in following table 6 Resist solution (PR-1) is coated on it, and is heated 60 seconds with 110 DEG C, so as to form photoresist film, further, Liquid shown in following table 7 is soaked protection film composition (TC-1) to be coated on this photoresist film, and is heated 60 seconds with 90 DEG C, The protective film for being 50nm so as to form film thickness.

Then, using the ArF liquid immersion exposure apparatus (NSR-S610C, NA1.30, σ of Nikon Corporation manufacture 0.98/0.65,35 degree of dipole polarization illuminations, 6% halftoning phase shifting mask) these wafers are exposed, and dried with 100 DEG C Roasting (PEB) 60 seconds, using 2.38% tetramethylammonium hydroxide (TMAH) aqueous development 30 seconds, to obtain 160nm 1:1's Line width/pitch pattern of eurymeric.For the wafer obtained in the above described manner, Hitachi, the electron microscope of Ltd. manufacture are used (S-4800) section shape of pattern is observed, and is manufactured using Hitachi High-Technologies Corporation. Electron microscope (CG4000) observe collapsing for pattern.

The Etaching device Telius manufactured using Tokyo Electron Limited., the treatment conditions shown in table 8,9 Under, dry ecthing is carried out to these wafers for having obtained photoresist pattern, siliceous resist intermediate coat is resisted with organic respectively Erosion agent lower membrane is processed.In addition, the electron microscope (S-9380) of Ltd. manufacture observes gained using Hitachi To wafer in pattern section shape.

Then, in order to remaining siliceous resist intermediate coat wet type will be gone after being processed to organic resist lower membrane It removes, utilization is mixed with 29% ammonium hydroxide/35% aquae hydrogenii dioxidi/water=1/1/8 ratio and is maintained at 65 DEG C of ammonia hydrogen peroxide Water handle within 5 minutes to above-mentioned wafer.It is cleaned after processing using pure water, and with 100 DEG C of heat dryings 60 seconds. In addition, using Thermo Fisher to be confirmed whether to remove silicon ingredient by ammonia hydrogen peroxide water process The K-ALPHA of Scientific Inc. manufacture carries out XPS (x-ray photoelectron spectroscopy) point to organic resist lower layer film surface Analysis, quantifies the silicon in organic resist lower membrane.

The Etaching device Telius manufactured using Tokyo Electron Limited., the treatment conditions shown in table 10 Under the organic resist lower layer film figure obtained with above-mentioned operation is handled, remaining organic resist lower membrane is carried out Ashing removal.The electron microscope (CG4000) manufactured using Hitachi High-Technologies Corporation. Observation ashing treated wafer, it is thus identified that whether there is or not residues.As a result as shown in table 11.

Above-mentioned siliceous resist intermediate coat forms as described in Table 5 with the composition of composition (SiARC-1).

[table 5]

TPSNO₃: nitric acid triphenylsulfonium

The molecular weight of SiARC polymer 1 and structural formula shown in table 5 are as follows.

SiARC polymer 1: molecular weight (Mw)=2,800

[chemical formula 10]

The molecular weight of SiARC polymer 2 and structural formula shown in table 5 are as follows.

SiARC polymer 2: molecular weight (Mw)=2,800

[chemical formula 11]

Above-mentioned eurymeric development is as described in Table 6 with the composition of ArF resist solution (PR-1).

[table 6]

The molecular weight of ArF imaging polymers 1, dispersion degree and structural formula shown in table 6 are as follows.

ArF imaging polymers 1: molecular weight (Mw)=7,800

Dispersion degree (Mw/Mn)=1.78

[chemical formula 12]

Acid agent shown in table 6: the structural formula of PAG1 is as follows.

[chemical formula 13]

Alkali shown in table 6: the structural formula of quencher is as follows.

[chemical formula 14]

The composition of above-mentioned liquid leaching protection film composition (TC-1) used in patterning test based on eurymeric development is as follows It states shown in table 7.

[table 7]

Protect the molecular weight, dispersion degree and structural formula of membrane polymer as follows shown in above-mentioned table 7.

Protect membrane polymer: molecular weight (Mw)=8,800

Dispersion degree (Mw/Mn)=1.69

[chemical formula 15]

The dry ecthing processing conditions of siliceous resist intermediate coat is as described in Table 8.

[table 8]

Chamber pressure	10Pa
		RF power	200W
CF₄Flow	50mL/min
		CHF₃Flow	50mL/min
N₂Flow	100mL/min
		Time	20 seconds

The dry ecthing processing conditions of organic resist lower membrane is as described in Table 9.

[table 9]

Chamber pressure	2.7Pa
		RF power	1000W
N₂Flow	500mL/min
		H₂Flow	30mL/min
Time	60 seconds

The ashing removal condition of organic resist lower membrane is as described in Table 10.

[table 10]

Chamber pressure	2.7Pa
		RF power	1000W
N₂Flow	500mL/min
		H₂Flow	30mL/min
Time	180 seconds

It is cutd open about obtained, photoresist pattern in the residue evaluation after above-mentioned organic resist lower membrane ashing The observation result of pattern section shape after face shape and the observation result of pattern collapsed, dry ecthing processing, ammonia hydrogen peroxide The silicon residual quantity of organic resist lower layer film surface after water process and after being ashed to organic resist lower layer film figure Whether there is or not residues, as shown in table 11.

[table 11]

As shown in table 11, when being imported with being formed by Sol.1~10,15~16 of can removing by ammonia aquae hydrogenii dioxidi When organic film, silicon does not remain in organic resist lower membrane after ammonia hydrogen peroxide water process, and to organic resist lower layer Film figure becomes that residue will not be generated after being ashed.Furthermore, it is thus identified that organic in embodiment 4-13~15, comparative example 4-1 The influence of the film thickness of film, as a result, as shown in embodiment 4-13, when organic film is relatively thin, that treated is organic for ammonia aquae hydrogenii dioxidi Resist lower layer film surface does not observe silicon ingredient residue, and does not generate after being ashed to organic resist lower layer film figure Residue.In addition, as shown in embodiment 4-15, when film is thicker, though there is lateral erosion in organic membrane part when carrying out dry ecthing processing, Residue is not generated after being ashed to organic resist lower layer film figure.On the other hand, as shown in comparative example 4-1, without organic The removal effect of silicon ingredient residue can not be obtained when film, and is produced after being ashed to organic resist lower layer film figure residual Slag.

It will be apparent that, if organic film formation composition of the invention, then following organic film is capable of forming by above-mentioned: Can by using will not to semiconductor device substrate and patterning process in necessary organic resist lower membrane cause to damage The stripper of wound can be applicable in easily with the silicon ingredient residue of the modification organic film that wet type removes together due to dry ecthing Form ion implanting shadow mask material when three-dimensional transistor.It it will be apparent that, is especially 10nm by importing film thickness Organic film more than and less than 100nm can more reliably construct the procedure for processing that will not generate residue.Thereby, it is possible to prevent Yield rate in the manufacturing process of three-dimensional transistor reduces, and can cost-effectively manufacture the semiconductor device of higher performance.

In addition, the present invention is not limited by above embodiment.Above embodiment only illustrate, as long as have with Substantially the same skill constituted and generate identical function and effect of documented technical concept in claims of the present invention Art scheme is all contained in technical scope of the invention.

Claims

1. a kind of organic film, which is formed, uses composition, which is characterized in that

Organic film formation composition includes high-molecular compound and organic solvent, which has by following logical Any a kind or more in repetitive unit that formula (1)~(4) indicate,

In the organic solvent, total account for selected from one or more of propylene glycol ester, ketone and lactone is more than in whole organic solvents 30wt% amount,

[chemical formula 1]

In formula, R₁For carbon atom number be 1~19 alkyl, halogen atom, alkoxy, carboxyl, sulfo group, methoxycarbonyl group, hydroxyphenyl, Or amino, R₂It is the group that acidic functionality is generated by heating or the effect of acid, R for hydrogen atom or AL, AL₃For hydrogen atom, Furyl can have the alkyl that chlorine atom or the carbon atom number of nitro are 1~16；k₁、k₂And k₃It is that 1~3, m is for 1~2, l 0~3, n are 0 or 1.

2. organic film according to claim 1, which is formed, uses composition, which is characterized in that composition is used in the organic film formation Be used to form organic film, the organic film be imported into the siliceous resist intermediate coat for dissolving in ammonia aquae hydrogenii dioxidi underface and It is insoluble in the surface of organic resist lower membrane of ammonia aquae hydrogenii dioxidi.

3. organic film according to claim 2, which is formed, uses composition, which is characterized in that the siliceous resist intermediate coat packet In boracic and phosphorus any one or both.

4. organic film according to claim 1, which is formed, uses composition, which is characterized in that composition is used in the organic film formation Further include any one in thermal acid generator and crosslinking agent or both.

5. organic film according to claim 2, which is formed, uses composition, which is characterized in that composition is used in the organic film formation Further include any one in thermal acid generator and crosslinking agent or both.

6. organic film according to claim 3, which is formed, uses composition, which is characterized in that composition is used in the organic film formation Further include any one in thermal acid generator and crosslinking agent or both.

7. organic film according to any one of claim 1 to 6, which is formed, uses composition, which is characterized in that by will be described Organic film formation is heated after being spun on substrate with composition, can obtain organic film, and the organic film is passing through utilization When being handled with 65 DEG C of the solution that 29% ammonium hydroxide/35% aquae hydrogenii dioxidi/water=1/1/8 ratio mixes, have 5nm/ minutes or more solution rate.

8. organic film according to any one of claim 1 to 6, which is formed, uses composition, which is characterized in that the organic film It is organic film of the 10nm more than and less than 100nm that formation, which can obtain film thickness with composition,.

9. organic film according to claim 7, which is formed, uses composition, which is characterized in that composition is used in the organic film formation Can obtain film thickness is organic film of the 10nm more than and less than 100nm.