CN101010634A - Composition including polyamide acid for forming lower layer reflection preventing film - Google Patents
Composition including polyamide acid for forming lower layer reflection preventing film Download PDFInfo
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- 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
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- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
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Abstract
The invention provides a lower layer reflection preventing film forming composition, which is to be used in a lithography process of semiconductor device manufacture for forming a lower layer reflection preventing film which can be developed by an alkaline developer used for photoresist development, and to provide a method for forming a photoresist pattern using the lower layer reflection preventing film forming composition. A lower layer reflection preventing film forming composition includes a polyamide acid, a compound having at least two epoxy groups, a light absorbing compound having a molar light absorption coefficient of 5,000-100,000 (l/molm) to light having a wavelength of 365nm, and a solvent.
Description
Technical field
The present invention relates to the composition of the formation lower layer reflection preventing film that in making the photoetching process of semiconductor devices, uses and use the formation method of photoresist pattern of the composition of this formation lower layer reflection preventing film.Be particularly related to the composition of the formation lower layer reflection preventing film that in the photoetching process of using i line (wavelength 365nm) or g line (wavelength 432nm), uses.In more detail, relate to the formation lower layer reflection preventing film composition that is used to form the lower layer reflection preventing film that under the alkaline-based developer effect that photoresist is used, can develop and use this formation lower layer reflection preventing film composition to form the photoresist method of patterning by photoresist and lower layer reflection preventing film are developed simultaneously.
Background technology
In the manufacturing of semiconductor devices, carry out microfabrication by the photoetching process of using photoresist.So-called microfabrication is meant following job operation; promptly; on semiconductor substrates such as silicon wafer, form the film of photoresist; mask by describing device pattern is to the active ray of irradiation ultraviolet radiation on it etc. then; develop; as diaphragm, the etch processes substrate is by forming the micro concavo-convex of corresponding above-mentioned pattern like this on substrate surface with the resist pattern that obtains.Yet in the photoetching process of photoresist, the irreflexive influence that exists the jump of the influence of the standing wave that light that exposure uses brings from the substrate reflection and substrate to cause causes the low inferior problem of dimensional accuracy of photoresist pattern.Therefore, in order to deal with problems, broad research is a kind of method that lower layer reflection preventing film (Bottom Anti-Reflective Coating:BARC) is set between photoresist and substrate now.
Such lower layer reflection preventing film in order to prevent and be coated on the photoresist generation internal mix above it, uses the heat cross-linking composition to form more.Antireflection film is insoluble with alkaline-based developer to photoresist as a result, need carry out remove (for example, the referring to Patent Document 1) of lower layer reflection preventing film before semiconductor substrate processing by dry ecthing.
Yet when removing lower layer reflection preventing film by dry ecthing, photoresist also is removed by etching.Therefore, the problem of the thickness of the photoresist of necessity in the substrate processing has appearred being difficult to guarantee.Be that purpose is used under the situation of thin photoresist film the problem especially severe to improve the image resolution.
In addition, in the manufacturing of semiconductor devices, ion injecting process is that the photoresist pattern is imported the operation of impurity as mold to semiconductor substrate, for fear of bringing damage to substrate surface, can not carry out the dry ecthing operation when forming the photoresist pattern.Therefore, in the formation of the photoresist pattern that is used for ion injecting process, can not use the antireflection film that to remove by dry ecthing in the lower floor of photoresist.Up to now, in ion injecting process, be used as the photoresist pattern of mold, irreflexive influence of the exposure light that wire spoke is wide in order to enlarge, the jump of the influence that reduces the standing wave that exposure light brings from the substrate reflection and substrate causes has added the photoresist of dyestuff or has used antireflection film to solve the problem that reflection causes on the upper strata of photoresist by use.Yet along with the miniaturization of in recent years pattern dimension, the photoresist that is used for ion injecting process also begins needs and forms fine pattern, need use antireflection film in the lower floor of photoresist.
Present situation is set out thus, and people expectation is developed in the alkaline-based developer of the development that is used for photoresist and dissolved, the lower layer reflection preventing film that can develop simultaneously and remove with photoresist.Yet, though now to can (for example developing the existing research of lower layer reflection preventing film of removing simultaneously with photoresist, refer to Patent Document 2, patent documentation 3, patent documentation 4, patent documentation 5, patent documentation 6), but to the adaptability of microfabrication with form the viewpoints such as shape of pattern, the scheme of still fully not satisfying the demand.
Patent documentation 1: No. 6156479 instructions of United States Patent (USP)
Patent documentation 2: No. 2686898 communique of Jap.P.
Patent documentation 3: the spy opens flat 9-78031 communique
Patent documentation 4: the spy opens flat 11-72925 communique
Patent documentation 5: the international text that discloses No. 03/057678
Patent documentation 6: the international text that discloses No. 03/058345
Summary of the invention
The present invention is based on above-mentioned present situation and the invention made, and purpose is to provide lower layer reflection preventing film that dissolves in the alkaline-based developer that uses in the development of photoresist and the composition that is used to form this lower layer reflection preventing film.
That is, the objective of the invention is to, be provided at the composition of the formation lower layer reflection preventing film that uses in the manufacturing of semiconductor devices.That is, provide that the photoresist that does not occur forming with being coated on the upper strata mixes, is dissolved in alkaline-based developer, the lower layer reflection preventing film that can develop the lower layer reflection preventing film removed simultaneously and be used to form this lower layer reflection preventing film with photoresist forms composition.
In addition, the objective of the invention is to, provide to i line (wavelength 365nm) show excellent absorption, soluble lower layer reflection preventing film in alkaline-based developer.
In addition, the objective of the invention is to, provide the composition that uses this formation lower layer reflection preventing film, the formation method of the photoresist pattern that in the manufacturing of semiconductor devices, uses.
The present invention, as the 1st viewpoint, be a kind of composition that forms lower layer reflection preventing film, said composition is used to form the lower layer reflection preventing film that can develop with photoresist by alkaline-based developer, it is characterized in that, contain the polyamic acid of the structure shown in (1) and the formula (2) that has formula:
(in the formula, A
1And A
2The organic group of representing 4 valencys, B
1The organic group of representing 3 valencys, B
2The organic group of expression divalent), have the compound of at least two epoxy radicals, be that the molar absorptivity of the light of 365nm is the light-absorbing compound and the solvent of 5000～100000 (1/molcm) to wavelength.
As the 2nd viewpoint, it is composition as the described formation lower layer reflection preventing film of the 1st viewpoint, it is characterized in that above-mentioned polyamic acid is to have the diamine compound of at least 1 carboxyl and (c) polyamic acid made of diamine compound reaction by (a) tetracarboxylic dianhydride compound, (b).
As the 3rd viewpoint, be as the composition of the described formation lower layer reflection preventing film of the 2nd viewpoint, it is characterized in that above-mentioned (a) tetracarboxylic dianhydride compound is the tetracarboxylic dianhydride's compound with at least one benzene ring structure.
As the mat woven of fine bamboo strips 4 viewpoints, be as the composition of the described formation lower layer reflection preventing film of the 2nd viewpoint, it is characterized in that the diamine compound that above-mentioned (b) has at least 1 carboxyl is the diamine compound with at least one benzene ring structure.
As the 5th viewpoint, be as the composition of the described formation lower layer reflection preventing film of the 2nd viewpoint, it is characterized in that above-mentioned (c) diamine compound is the diamine compound with 2 benzene ring structures.
As the 6th viewpoint, be as the composition of the described formation lower layer reflection preventing film of the 1st viewpoint, it is characterized in that above-mentioned compound with at least two epoxy radicals is the compound with 3 to 5 epoxy radicals.
As the 7th viewpoint; it is composition as the described formation lower layer reflection preventing film of the 1st viewpoint; it is characterized in that; above-mentioned light-absorbing compound is to be selected from 2-(4-diethylamino-2-hydroxy benzoyl) benzoic acid; 2-(4-dibutylamino-2-hydroxy benzoyl) benzoic acid; 2; 2 '; 4; 4 '-tetrahydroxybenzophenone; 2; 3; 3 ', 4,4 '; 5 '-hexahydroxy benzophenone; lichenic acid (usnic acid); phenylfluorone; rosolic acid (rosolicaid); 1; 8,9-trihydroxy anthracene; 2-(4-hydroxy phenyl azo) benzoic acid; methyl red; 4,4 '-diaminobenzophenone; 5; 5 '-methylene-two (2-hydroxyl-4-methoxy benzophenone); 3, the 4-diaminobenzophenone; compound in curcumin (curcumine) and alpha-amido-4-hydroxycinnamic acid.
As the 8th viewpoint, be as the composition of the described formation lower layer reflection preventing film of the 1st viewpoint, it is characterized in that, further contain the naphthoic acid compound.
As the 9th viewpoint, be as the composition of the described formation lower layer reflection preventing film of the 1st viewpoint, it is characterized in that, further contain the diazo naphthoquinone sulfoacid compound.
As the 10th viewpoint, it is a kind of formation method of the photoresist pattern that is used for producing the semiconductor devices, comprise following operation: will be coated on the semiconductor substrate at the composition of the formation lower layer reflection preventing film described in each of the 1st viewpoint to the 9 viewpoints, toast the operation that forms lower layer reflection preventing film; On above-mentioned lower layer reflection preventing film, form the operation of photoresist layer; The expose operation of the semiconductor substrate that above-mentioned lower layer reflection preventing film and above-mentioned photoresist layer be covered; After exposure, by the operation of alkaline-based developer development.
As the 11st viewpoint, be as the formation method of the described photoresist pattern of the 10th viewpoint, it is characterized in that above-mentioned exposure is that the light by 365nm or 432nm wavelength carries out.
The composition of the formation lower layer reflection preventing film of the application of the invention, the lower layer reflection preventing film that can form the alkaline-based developer that uses in the development that mixes, is dissolved in photoresist that does not take place with photoresist, can develop and remove with photoresist simultaneously.
The composition of the formation lower layer reflection preventing film of the application of the invention can form the lower layer reflection preventing film that i line (wavelength 365nm) is shown excellent absorption.
Because can not carrying out dry ecthing, the lower reflecting film that the composition by formation lower layer reflection preventing film of the present invention forms removes, so can in the manufacturing process of the semiconductor devices of the operation that the substrate surface that contains ion injecting process etc. is easy to damage by dry ecthing, use.
In addition, when using formation lower layer reflection preventing film composition of the present invention to form lower layer reflection preventing film, baking condition when forming antireflection film by changing can change the dissolution velocity that the alkalescence of using in the development of lower layer reflection preventing film with respect to photoresist shows shadow liquid.
Embodiment
The composition of formation lower layer reflection preventing film of the present invention, be contain the polyamic acid with structure shown in above-mentioned formula (1) and the above-mentioned formula (2), compound with at least two epoxy radicals, be the light-absorbing compound of 5000～100000 (1/molcms) and the composition of solvent as the molar absorptivity that is the light of 365nm to wavelength.In addition, the composition of formation lower layer reflection preventing film of the present invention can also contain aromatic carboxy acid compounds such as photosensitive compounds, naphthoic acid compounds such as diazo naphthoquinone sulfoacid compound and surfactant etc.
Solid shape components in proportions in the composition of formation lower layer reflection preventing film of the present invention as long as can make each uniform component dissolving, just is not particularly limited, and for example is 0.5～50 quality %, or 1～30 quality %, or 5～25 quality % or 10～20 quality %.Said herein solid formation divided, and is meant the composition that removes from total composition of the composition that forms lower layer reflection preventing film behind the solvent composition.
Composition to formation lower layer reflection preventing film of the present invention specifically describes below.
＜polyamic acid 〉
The composition of formation lower layer reflection preventing film of the present invention contains the polyamic acid with structure shown in structure shown in the above-mentioned formula (1) and the above-mentioned formula (2).
In formula (1), A
1The organic group of representing 4 valencys, B
1The organic group of representing 3 valencys is as A
1, (in the formula, X represents that carbon number is that 1～5 alkyl, chlorine atom, bromine atoms, fluorine atom, carbon number are 1～5 alkoxy, hydroxyl, carboxyl, phenoxy group, trifluoromethyl or nitro, m for example can to enumerate formula (3)～(10)
1Expression 0,1 or 2).
As carbon number is 1～5 alkyl, is methyl, ethyl, isopropyl, cyclopentyl and n-pentyl etc.As carbon number is 1～5 alkoxy, is methoxyl, ethoxy, isopropoxy, cyclopentyloxy and n-pentyl oxygen base etc.
As B
1, for example can enumerate, (in the formula, Y represents that carbon number is that 1～5 alkyl, chlorine atom, bromine atoms, fluorine atom, carbon number are 1～5 alkoxy, hydroxyl, carboxyl, phenoxy group, trifluoromethyl or nitro, m in formula (11)～(18)
2Expression 0,1 or 2).
In formula (2), A
2The organic group of representing 4 valencys, B
2The organic group of expression divalent is as A
2, can enumerate for example above-mentioned formula (3)～(10).
As B
2, for example can enumerate, (in the formula, Z represents that carbon number is that 1～5 alkyl, chlorine atom, bromine atoms, fluorine atom, carbon number are 1～5 alkoxy, hydroxyl, carboxyl, phenoxy group, trifluoromethyl or nitro, m in formula (19)～(27)
3Expression 0,1 or 2).
As the weight-average molecular weight of the polyamic acid that uses among the present invention, with polystyrene conversion, be for example 1000～100000, or 2000～50000, or 3000～30000, or 5000～10000.Under the situation of weight-average molecular weight less than above-mentioned value of polyamic acid, the lower layer reflection preventing film of formation becomes big to the solubleness of the solvent that uses in the photoresist, and the situation of mixing with photoresist appears in the result.Under the situation of weight-average molecular weight greater than above-mentioned value of polyamic acid, the dissolubility of the alkaline-based developer that uses in the development of the lower layer reflection preventing film of formation to photoresist becomes insufficient, occurs residue sometimes after development.
The preparation method of the polyamic acid that contains in the composition to formation lower layer reflection preventing film of the present invention is not particularly limited, and can use known method to make.For example, by with diamine compound, with tetrabasic carboxylic acid or as tetracarboxylic dianhydride's compound of its derivant, dicarboxylic acid two etherides etc. react, polymerization, can make polyamic acid.In addition, carry out polymerization, come synthesizing polyamides acid silyl ester, utilize acid that the silicyl ester moiety is decomposed then, can make polyamic acid by using dimethyl silanyl diamine compound and tetracarboxylic dianhydride's compound.
The polyamic acid that contains in the composition of formation lower layer reflection preventing film of the present invention, can from (a) tetracarboxylic dianhydride compound, (b) have the diamine compound of at least 1 carboxyl and (c) diamine compound make.
(a) tetracarboxylic dianhydride compound that is used for making the polyamic acid that the present invention uses there is not particular determination.(a) tetracarboxylic dianhydride's compound can use a kind ofly, in addition, also can use two or more simultaneously.
Can use the tetracarboxylic dianhydride's compound that has at least one benzene ring structure, for example has 1 to 4 benzene ring structure.
As object lesson, can list pyromellitic dianhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-diphenyl ether tetraformic dianhydride, 4,4 '-(hexafluoro isopropylidene) two O-phthalic acid dianhydrides, with 3,3 ', 4, aromatic series tetracarboxylic dianhydrides such as 4 '-diphenyl sulfone tetracarboxylic acid dianhydride, 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,3,4-cyclohexane tetracarboxylic dianhydride, with 3,4-dicarboxyl-1,2,3, the tetracarboxylic dianhydride of the alicyclic ring shape that 4-tetrahydrochysene-1-naphthyl succinic acid dianhydride is such, 1,2,3, the aliphatics tetracarboxylic dianhydride that 4-butane tetracarboxylic dianhydride is such.
(b) that is used for making the polyamic acid that the present invention uses had the diamine compound of at least one carboxyl, be not particularly limited.As the number of carboxyl, for example be 1～4.(b) diamine compound with at least one carboxyl can use a kind ofly, in addition, also can use simultaneously more than 2 kinds.
Have the diamine compound of at least one carboxyl as (b), can use have at least 1 benzene ring structure, the diamine compound of 1 to 3 benzene ring structure for example.
As object lesson, can list 2, the 4-diaminobenzoic acid, 2, the 5-diaminobenzoic acid, 3, the 5-diaminobenzoic acid, 4, the 6-diaminostilbene, the 3-phthalic acid, 2, the 5-diaminostilbene, the 4-phthalic acid, two (4-amino-3-carboxyl phenyl) ether, two (4-amino-3,5-dicarboxyl phenyl) ether, two (4-amino-3-carboxyl phenyl) sulfone, two (4-amino-3,5-dicarboxyl phenyl) sulfone, 4,4 '-diamido-3,3 '-dicarboxylate biphenyl, 4,4 '-diamido-3,3 '-dicarboxyl-5,5 '-dimethyl diphenyl, 4,4 '-diamido-3,3 '-dicarboxyl-5,5 '-dimethoxy-biphenyl, 1,4-two (4-amino-3-carboxyl phenoxy group) benzene, 1,3-two (4-amino-3-carboxyl phenoxy group) benzene, two [4-(4-amino-3-carboxyl phenoxy group) phenyl] sulfone, two [4-(4-amino-3-carboxyl phenoxy group) phenyl] propane, with 2,2-two [4-(4-amino-3-carboxyl phenoxy group) phenyl] HFC-236fa etc.
In addition, use (c) diamine compound not have particular determination as being used for making the polyamic acid that the present invention uses.(c) diamine compound can use a kind ofly, in addition, also can use two or more simultaneously.
As (c) diamine compound, can use the diamine compound that has 1 to 3 benzene ring structure, for example has 2 benzene ring structures.
As concrete example, can list 2, the 4-diaminophenol, 3, the 5-diaminophenol, 2, the 5-diaminophenol, 4, the 6-diamino resorcin, 2,5-diamido quinhydrones, two (3-amino-4-hydroxy phenyl) ether, two (4-amino-3-hydroxy base) ether, two (4-amino-3, the 5-dihydroxy phenyl) ether, two (3-amino-4-hydroxy phenyl) methane, two (4-amino-3-hydroxy base) methane, two (4-amino-3, the 5-dihydroxy phenyl) methane, two (3-amino-4-hydroxy phenyl) sulfone, two (4-amino-3-hydroxy base) sulfone, two (4-amino-3, the 5-dihydroxy phenyl) sulfone, 2,2-two (3-amino-4-hydroxy phenyl) HFC-236fa, 2,2-two (4-amino-3-hydroxy base) HFC-236fa, 2,2-two (4-amino-3, the 5-dihydroxy phenyl) HFC-236fa, 4,4 '-diamido-3,3 '-dihydroxybiphenyl, 4,4 '-diamido-3,3 '-dihydroxy-5,5 '-dimethyl diphenyl, 4,4-diamido-3,3 '-dihydroxy-5,5 '-dimethoxy-biphenyl, 1,4-two (3-amino-4-hydroxy phenoxy group) benzene, 1,3-two (3-amino-4-hydroxy phenoxy group) benzene, 1,4-two (4-amino-3-hydroxy oxygen base) benzene, 1,3-two (4-amino-3-hydroxy oxygen base) benzene, two [4-(3-amino-4-hydroxy phenoxy group) phenyl] sulfone, two [4-(3-amino-4-hydroxy phenoxy group) phenyl] propane, with 2,2-two [4-(3-amino-4-hydroxy phenoxy group) phenyl] HFC-236fa etc. has the diamine compound of phenol hydroxyl; 1,3-diamido-4-sulfydryl benzene, 1,3-diamido-5-sulfydryl benzene, 1,4-diamido-2-sulfydryl benzene, two (4-amino-3-sulfydryl phenyl) ether, with 2,2-two (3-amino-4-sulfydryl phenyl) HFC-236fa etc. has the diamine compound of benzenethiol base, 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-5-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, two (4-amino-3-sulfo group phenyl) ether, 4,4 '-benzidine-3,3 '-disulfonic acid, with 4,4 '-diamido-3,3 '-dimethyl diphenyl-6,6 '-disulfonic acid etc. have sulfonic diamine compound; 3, the 5-diaminobenzoic acid tert-butyl ester, 3,5-diaminobenzoic acid ethoxyl methyl ester, 3,5-diamino-methyl benzoate, 3,5-diaminobenzoic acid n-propyl and 3,5-diaminobenzoic acid isobutyl ester etc. contains the diamine compound of carboxylic acid ester groups.In addition, can enumerate p-phenylenediamine (PPD), m-phenylene diamine, 4,4 '-methylene-two (2, the 6-ethylaniline), 4,4 '-methylene-two (2-isopropyl-6-methylaniline), 4,4 '-methylene-two (2, the 6-diisopropyl aniline), 2,4,6-trimethyl-1, the 3-phenylenediamine, 2,3,5,6-tetramethyl-1, the 4-phenylenediamine, o-tolidine, between tolidine, 3,3 ', 5,5 '-tetramethyl benzidine, two [4-(3-amino-benzene oxygen) phenyl] sulfone, 2,2-two [4-(3-amino-benzene oxygen) phenyl] propane, 2,2-two [4-(3-amino-benzene oxygen) phenyl] HFC-236fa, 4,4 '-diamido-3,3 '-dimethyl dicyclohexyl methyl hydride, 4,4 '-diamino-diphenyl ether, 3,4-diamino-diphenyl ether, 4,4 '-diaminodiphenyl-methane, 2,2-two (4-anilino-) HFC-236fa, 2,2-two (3-anilino-) HFC-236fa, 2,2-two (3-amino-4-toluyl) HFC-236fa, 1,4-two (4-amino-benzene oxygen) benzene, 1,3-two (4-amino-benzene oxygen) benzene, two [4-(4-amino-benzene oxygen) phenyl] sulfone, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, and 2, diamine compounds such as 2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa.
In the manufacturing of polyamic acid used in the present invention, (b) the shared ratio in the whole diamine compounds that use of the diamine compound with at least 1 carboxyl is for example 1～99 quality %, or 5～80 quality %, or 10～60 quality %, or 20～50 quality % or 30～40 quality %.Have at (b) under the situation of ratio less than aforementioned proportion of diamine compound of at least 1 carboxyl, the lower layer reflection preventing film of formation becomes insufficient to the dissolubility of alkaline-based developer.
The polyamic acid of Shi Yonging has the diamine compound of at least one carboxyl by (a) tetracarboxylic dianhydride compound, (b) and (c) under the situation that diamine compound is made in the present invention, the total mole number of the diamine compound that uses and the ratio of the total mole number of tetracarboxylic dianhydride's compound are preferably 0.8～1.2.Identical with common polycondensation reaction, this mol ratio approaches 1 more, and the degree of polymerization of the polyamic acid of generation is big more, and molecular weight is big more.
In the manufacturing of polyamic acid, the temperature of reaction when diamine compound and the reaction of tetracarboxylic dianhydride's compound can be selected-20 ℃～150 ℃, preferred-5 ℃～100 ℃ arbitrary temp.In temperature of reaction is 5 ℃～40 ℃, and the reaction time is under 1～48 hour the condition, can obtain the polyamic acid of high molecular.In order to obtain the high polyamic acid of low-molecular-weight and storage stability, more preferably under 40 ℃～80 ℃, the reaction time is more than 10 hours.
The reaction of diamine compound and tetracarboxylic dianhydride's compound can be carried out in solvent.As the solvent that can use at this moment, can list N, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, the N-vinyl pyrrolidone, N-methyl caprolactone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, metacresol, gamma-butyrolacton, ethyl acetate, butyl acetate, ethyl lactate, 3-methoxypropionic acid methyl esters, 2-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 2-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, the diglycol methyl ethyl ether, the propylene glycol dimethyl ether, the dipropylene glycol dimethyl ether, the glycol monomethyl methyl ether, ethylene glycol monoethyl ether, the diglycol monotertiary methyl ether, carbiphene, propylene glycol monomethyl ether, propylene glycol list ethylether, the dipropylene glycol monomethyl ether, dipropylene glycol list ethylether, propylene glycol monomethyl ether, the carbitol acetic acid esters, ethyl cellosolve acetate, cyclohexanone, MEK, methyl isobutyl ketone, with 2-heptanone etc.They can be used alone, but also also mix together.And then, even can not dissolve the solvent of polyamic acid, also can in the scope that the polyamic acid that is generated by polyreaction is not separated out, use with above-mentioned solvent.
The solution that contains polyamic acid that obtains like this can be directly used in the modulation of the composition that forms lower layer reflection preventing film.In addition, polyamic acid can be put into poor solvents such as methyl alcohol, ethanol and precipitate, can use separately.
The polyamic acid that contains in the composition as formation lower layer reflection preventing film of the present invention is preferably except its end portion, comprises the polyamic acid of the structure shown in structure shown in the above-mentioned formula (1) and the above-mentioned formula (2) substantially.
Polyamic acid as containing in the formation lower layer reflection preventing film composition of the present invention for example can list, following polyamic acid (formula (29)～(37)) (p in the formula
1, p
2, p
3And p
4The ratio of each structure in the expression polyamic acid, they and be 1.) herein, formula (29)～(36) are by a kind of tetracarboxylic dianhydride's compound and 2 kinds of polyamic acids that diamine compound is made, formula (37) is by 2 kinds of tetracarboxylic dianhydride's compounds and 2 kinds of polyamic acids that diamine compound is made.
＜have a compound of at least 2 epoxy radicals 〉
The composition of formation lower layer reflection preventing film of the present invention contains the compound with at least 2 epoxy radicals.As this compounds,, just be not particularly limited so long as contain the compound of epoxy radicals.For example can list, three (2, the 3-glycidyl) isocyanuric acid ester, 1, the 4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxy ethyl) cyclohexane, T 55, the diglycol diglycidyl ether, 2,6-diglycidyl phenyl glycidyl ether, 1,1,3-three [p-(2, the 3-glycidoxy) phenyl] propane, 1,2-cyclohexane cyclohexanedimethanodibasic 2-glycidyl ester, 4,4 '-methylene, two (N, the N-diglycidylaniline), 3,4-epoxycyclohexyl methyl-3,4-7-oxa-bicyclo[4.1.0 formic ether, trimethylolethane trimethacrylate glycidol ether and bisphenol-A-diglycidyl ether, with pentaerythrite polyglycidyl ether etc.
In addition, as compound, can use poly-thing with epoxy radicals with at least two epoxy radicals.As this base polymer,, just can use so long as have the polymkeric substance of epoxy radicals with being not particularly limited.
This base polymer can be made by the addition polymerization that use has an addition polymerization monomer of epoxy radicals, in addition, compound with epoxy radicals such as macromolecular compound that also can be by having hydroxyl and chloropropylene oxide, toluenesulfonic acid ethylene oxidic ester reacts and makes.Can list for example multipolymer of polyacrylic acid ethylene oxidic ester, glycidyl methacrylate and Jia Jibingxisuanyizhi, the polymkeric substance of the addition polymerization of the multipolymer of glycidyl methacrylate and styrene and methacrylic acid-2-hydroxyethyl ester etc.; The polymkeric substance of polycondensations such as epoxy novolac.As the weight-average molecular weight of this base polymer, for example be 500～200000, or 1000～100000, or 3000～30000.
As compound with at least 2 epoxy radicals, can also list, have amino epoxy resin as YH-434, YH434L (Dongdu changes into (strain) system); Epoxy resin with cyclohexene oxide structure is as エ Port リ one De GT-401, エ Port リ one De GT-403, エ Port リ one De GT-301, エ Port リ one De GT-302, セ ロ キ サ イ De 2021, セ ロ キ サ イ De 3000 (グ イ セ Le chemistry (strain) system); Bisphenol A type epoxy resin is as エ ピ コ one ト 1001, エ ピ コ one ト 1002, エ ピ コ one ト 1003, エ ピ コ one ト 1004, エ ピ コ one ト 1007, エ ピ コ one ト 1009, エ ピ コ one ト 1010, エ ピ コ one ト 828 (above is ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) system); Bisphenol f type epoxy resin is as エ ピ コ one ト 807 (ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) system) etc.; Phenol novolac-type epoxy resin is as エ ピ コ one ト 152, エ ピ コ one ト 154 (above be ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) system), EPPN201, EPPN202 (above be Japanese chemical drug (strain) system) etc.; Cresols novolac-type epoxy resin is as EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (above is Japanese chemical drug (strain) system), エ ピ コ one ト 180S75 (ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) system) etc.; Alicyclic ring shape epoxy resin is as デ Na コ one Le EX-252 (Na ガ セ ケ system テ Star Network ス (strain) system), CY175, CY177, CY179 (above is CIBA-GEIGY A.G system), ア ラ Le グ イ ト CY182, ア ラ Le グ イ ト CY192, ア ラ Le グ イ ト CY184 (above is CIBA-GEIGY A.G system), エ ピ Network ロ Application 200, エ ピ Network ロ Application 400 (above is big Japanese イ Application キ chemical industry (strain) system), エ ピ コ one ト 871, エ ピ コ one ト 872 (above is ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) system)), ED-5661, ED-5662 (above is セ ラ 21 ズ コ one テ イ Application グ (strain) system) etc.; Aliphatic poly glycidol ether such as デ Na コ one Le EX-611, デ Na コ one Le EX-612, デ Na コ one Le EX-614, デ Na コ one Le EX-622, デ Na コ one Le EX-411, デ Na コ one Le EX-512, デ Na コ one Le EX-522, デ Na コ one Le EX-421, デ Na コ one Le EX-313, デ Na コ one Le EX-314, デ Na コ one Le EX-321 commercially available compounds such as (Na ガ セ ケ system テ Star Network ス (strain) systems).
As compound, not that preferred for example the use has 2 to 10, or the compound of 3 to 5 epoxy radicals under the situation of compound of polymkeric substance using with at least 2 epoxy radicals.
Above-mentioned content with compound of at least 2 epoxy radicals is for example 5～70 mass parts with respect to the polyamic acid of 100 mass parts, or be 10～60 mass parts, be preferably 15～45 mass parts or 20～40 mass parts.Under the situation of content less than above-mentioned value of the compound with at least 2 epoxy radicals, the degree of cure deficiency of lower floor's antireflection agent might be dissolved in the solvent of photoresist, causes mixing.Under the situation of content greater than above-mentioned value of compound, be difficult to obtain the sufficient dissolubility of using in the development to photoresist of alkaline-based developer sometimes with at least 2 epoxy radicals.
＜light-absorbing compound 〉
The composition of formation lower layer reflection preventing film of the present invention, containing wavelength is the light-absorbing compound that the light of 365nm has big molar absorptivity.As molar absorptivity, be 5000～100000 (1/molcm), be preferably 10000～80000 (1/molcm), or be 15000～50000 (1/molcm).Under the situation of molar absorptivity less than 5000 (1/molcm), can not get the having sufficient attenuation coefficient sometimes lower layer reflection preventing film of (k value) can not get sufficient anti-reflection effect.
The light-absorbing compound that has big molar absorptivity as the light that to wavelength is 365nm; for example can list; 2-(4-diethylamino-2-hydroxy benzoyl) benzoic acid; 2-(4-dibutylamino-2-hydroxy benzoyl) benzoic acid; 2; 2 '; 4; 4 '-tetrahydroxybenzophenone; 2; 3; 3 '; 4; 4 ', 5 '-hexahydroxy benzophenone; lichenic acid (usnic acid); phenylfluorone; rosolic acid (rosolic aid); 1,8; 9-trihydroxy anthracene; 2-(4-hydroxy phenyl azo) benzoic acid; methyl red; 4; 4 '-diaminobenzophenone; 5,5 '-methylene-two (2-hydroxyl-4-methoxy benzophenone); 3, the 4-diaminobenzophenone; curcumin (curcumine) and alpha-amido-4-hydroxycinnamic acid etc.
In addition; at light-absorbing compound is above-mentioned 2-(4-diethylamino-2-hydroxy benzoyl) benzoic acid and 2; 2 '; 4; under the situation of the light-absorbing compound that 4 '-tetrahydroxybenzophenone is such with carboxyl or phenol hydroxyl; the product of these compounds and the compound reaction with epoxy radicals promptly, makes the reaction product of epoxide ring open loop also can be as the light-absorbing compound in the composition of formation lower layer reflection preventing film of the present invention by carboxyl or phenol hydroxyl.Herein as compound with epoxy radicals, for example can list, three (2, the 3-glycidyl) isocyanuric acid ester, 1, the 4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxy ethyl) cyclohexane, T 55, the diglycol diglycidyl ether, 2,6-diglycidyl phenyl glycidyl ether, 1,1, [p-(2 for 3-three, the 3-glycidoxy) phenyl] propane, 1,2-cyclohexane cyclohexanedimethanodibasic 2-glycidyl ester, 4,4 '-methylene two (N, N-diglycidylaniline), 3,4-epoxycyclohexyl methyl-3,4-7-oxa-bicyclo[4.1.0 formic ether, trimethylolethane trimethacrylate glycidol ether and bisphenol-A-diglycidyl ether, epoxy compound with pentaerythrite polyglycidyl ether etc., and the polymkeric substance that contains epoxy radicals structure with glycidyl methacrylate etc.As with the resultant of reaction of compound with epoxy radicals, for example can list, have the polymkeric substance of the cellular construction shown in following formula (38) and (39).
Light-absorbing compound may be used alone, or two or more kinds may be used in combination.As the content of light-absorbing compound, be for example 1～300 mass parts with respect to the polyamic acid of 100 mass parts, or be 5～200 mass parts, or be 10～100 mass parts, or be 20～80 mass parts, or be 40～60 mass parts.Under the situation of content greater than above-mentioned value of light-absorbing compound, lower layer reflection preventing film is little to the dissolubility of alkaline-based developer sometimes, and in addition, lower layer reflection preventing film mixes with photoresist sometimes.
By changing the kind and the content of light-absorbing compound, can adjust the attenuation coefficient (k value) of lower layer reflection preventing film.
＜solvent 〉
The composition of formation lower layer reflection preventing film of the present invention can be dissolved in the appropriate solvent and use with solution state by the mixing of above-mentioned each uniform component is easily modulated.As such solvent, for example can use, glycol monoethyl ether, ethylene glycol monoethyl ether, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, the propylene glycol propyl ether acetic acid esters, toluene, dimethylbenzene, MEK, cyclopentanone, cyclohexanone, the 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl ethyl propionate, the ethoxy ethyl acetate, the hydroxacetic acid ethyl ester, 2-hydroxy-3-methyl methyl butyrate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, the 3-ethoxyl ethyl propionate, 3-ethoxy-propionic acid methyl esters, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, dinethylformamide, N,N-dimethylacetamide, with N-Methyl pyrrolidone etc.These solvents can use separately, or combination more than 2 kinds is used.And then, can mix high boiling solvents such as propylene glycol monobutyl ether, propylene glycol monobutyl ether acetic acid esters and use.
Tiao Zhi lower layer reflection preventing film resin combination solution preferably is that use is supplied with in the filtration backs such as filtrator about 0.2 μ m in the use aperture like this.Tiao Zhi lower layer reflection preventing film resin combination solution can at room temperature steady in a long-termly be stored like this.
In addition, in the composition of formation lower layer reflection preventing film of the present invention, can also contain aromatic carboxy acid compounds such as photosensitive compounds, naphthoic acid compounds such as diazo naphthoquinone sulfoacid compound and surfactant etc.
As photosensitive compounds, preferred diazo naphthoquinone sulfoacid compound.
As the diazo naphthoquinone sulfoacid compound of photosensitive compounds, preferably by 1, the sulfonate compound that 2-naphthoquinones-2-diazonium-5-sulfonic acid and 1, sulfoacid compound such as 2-naphthoquinones-2-diazonium-4-sulfonic acid and the compound with hydroxyl obtain.In addition, also preferably by 1,2-naphthoquinones-2-diazonium-5-sulfonic acid and 1, sulfoacid compound such as 2-naphthoquinones-2-diazonium-4-sulfonic acid with have the sulfonic acid amides compound that amino compound obtains.In addition, preferably from above-mentioned sulfoacid compound with have hydroxyl or sulphonic acid ester or sulfonic acid amides compound that amino compound obtains.
As above-mentioned compound with hydroxyl, for example can enumerate, phenol, 2-cresols, 3-cresols, 4-cresols, quinhydrones, resorcinol, catechol, 4,4-isopropylidene biphenol, 1,1-two (4-hydroxy phenyl) cyclohexane, 4,4 '-dihydroxy phenyl sulfone, 4,4-hexafluoro isopropylidene biphenol, 4,4 '; 4 "-trihydroxy triphenyl methane, 1,1,1-three (4-hydroxy phenyl) ethane, 4,4 '-[1-[4-[1-(4-hydroxy phenyl)-1-Methylethyl] phenyl] ethylidene] bis-phenol, 2, the 4-dihydroxy benaophenonel, 2,3, the 4-trihydroxybenzophenone, 2,2 ', 4,4 '-tetrahydroxybenzophenone, 2,3,4,4 '-tetrahydroxybenzophenone, 2,3,4,2 ', 4 '-pentahydroxybenzophenone, with 2, phenolic compounds such as 5-two (2-hydroxy-5-methyl base) benzyl methyl, ethanol, the 2-propyl alcohol, the 4-butanols, cyclohexanol, ethylene glycol, propylene glycol, diglycol, dipropylene glycol, 2-methyl cellosolve, butoxy ethanol, the 2-methoxypropanol, 2-butoxy propyl alcohol, ethyl lactate, with aliphatic alcohol compounds such as butyl lactates.
As above-mentioned compound with amino, can enumerate aniline, ortho-aminotoluene, meta-aminotoluene, para-totuidine, 4-ADP methylmethane, 4-aminobphenyl, o-phenylenediamine, m-phenylene diamine, p-phenylenediamine (PPD), 4,4 '-diaminodiphenyl-methane and 4, fatty amine compounds such as aniline compounds such as 4 '-diamino-diphenyl ether, cyclo-hexylamine, n-octylamine and cyclopentyl amine.
And then, as having hydroxyl and amino compound, can enumerate o-aminophenol, m-aminophenol, para-aminophenol, the 4-aminoresorcinol, 2, the 3-diaminophenol, 2, the 4-diaminophenol, 4,4 '-diamido-4 "-the hydroxyl triphenyl methane; 4-amino-4 '; 4 "-dihydroxy triphenyl methane, two (4-amino-3-carboxyl-5-hydroxy phenyl) ether, two (4-amino-3-carboxyl-5-hydroxy phenyl) methane, two (4-amino-3-carboxyl-5-hydroxy phenyl) sulfone, 2,2-two (4-amino-3-carboxyl-5-hydroxy phenyl) propane, with 2, aminophenol compounds such as 2-two (4-amino-3-carboxyl-5-hydroxy phenyl) HFC-236fa, the 2-ethylaminoethanol, the 3-aminopropanol, with chain triacontanol amine compounds such as 4-aminocyclohexanols.
Using under the situation of photosensitive compounds,, be for example 1～100 mass parts with respect to the polyamic acid of 100 mass parts, or be 3～80 mass parts, or be for example 5～50 mass parts, or be 10～40 mass parts as its addition.Under photosensitive compounds surpassed the situation of 100 mass parts, lower layer reflection preventing film was little to the dissolubility of alkaline-based developer sometimes, in addition, took place mixing of lower layer reflection preventing film and photoresist sometimes.
In order to regulate dissolution velocity, can in the composition of formation lower layer reflection preventing film of the present invention, add aromatic carboxy acid compound, aliphatic carboxylic acid compound and have compound of phenol hydroxyl etc. alkaline-based developer.
As this compounds, for example can list, trihydroxy phenyl ethane, bis-phenol-S, bisphenol-A, 4,4 '-isopropylidene-di-o-cresol, 5-tert-butyl group 1,2,3,-thrihydroxy-benzene, the hexafluoro bisphenol-A, 3,3,3 ', 3 '-tetramethyl-1,1 '-spirobindene full-5,5 ', 6,6 '-tetrol, 4,4 '-(9-fluorenylidene) biphenol, bisphenol-AP, bis-phenol-P, 5-α, alpha-alpha-dimethyl-4-hydroxybenzyl salicylic acid, α, α, α-three (4-hydroxy phenyl)-1-ethyl-4-cumene, 5,5 '-di-t-butyl-2,2 ', 4, phenolic compounds such as 4 '-tetrahydroxybenzophenone; Pyromellitic acid, 3,7-dihydroxy-2-naphthoic acid, phthalic acid, trimellitic acid, the 4-sulfosalicylic phthalate, mellitic acid, 2, the 3-naphthalenedicarboxylic acid, the 4-hydroxyl phthalic, 3,4-dihydroxy phthalic acid, 4,5-dihydroxy phthalic acid, 3,3 ', 4,4 '-bibenzene tetracarboxylic, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic acid, 3,3 ', 4,4 '-diphenyl sulfone tetracarboxylic acid, 1,2,3,4-cyclo-butane tetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetracarboxylic acid, 1,2,3,4-cyclopentane tetracarboxylic acid, 1,2,3,4-cyclohexane tetracarboxylic acid, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-carboxylic acid compounds such as 1-naphthalene succinic, polyacrylic acid, polymethylacrylic acid, polyamic acid, the phenol novolac, polycarboxylated styrene, has the polymkeric substance of carboxyl or phenol hydroxyl with naphthols novolac etc.Wherein, the naphthoic acid compound that preferably has naphthalene nucleus and carboxyl.When using these compounds,,, be for example 1～100 mass parts, or be 3～80 mass parts, or for example be 5～40 mass parts, or be 10～20 mass parts with respect to the polyamic acid of 100 mass parts as its addition.
In the composition of formation lower layer reflection preventing film of the present invention, can contain surfactant.For example can list polyoxyethylene alkyl ether classes such as polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether as surfactant; Polyoxyethylene alkylaryl ether classes such as polyoxyethylene octyl phenol ether, polyoxyethylene nonylphenyl ether; The polyoxyethylene polyoxypropylene block copolymer class; Sorbitan fatty acid esters classes such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan single-hard ester acid ester, dehydrated sorbitol mono-fatty acid ester, sorbitan trioleate, sorbitan three hard ester acid esters; Nonionics such as polyoxyethylene sorbitan fatty acid esters class such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan single-hard ester acid ester, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan three hard ester acid esters are surfactant; エ Off ト Star プ EF301, EF303, EF352 (ジ エ system コ (strain) system); メ ガ Off ア Star Network F171, F173 (big Japanese イ Application キ chemical industry (strain) system); Off ロ ラ one De FC430, FC431 (Sumitomo ス リ one エ system (strain) system); ア サ ヒ ガ one De AG710, サ one Off ロ Application S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 fluorine class surfactants such as (Asahi Glass (strain) systems) and organic siloxane polymer KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system) etc.The use level of these surfactants in whole compositions of the composition of formation lower layer reflection preventing film of the present invention, is generally below the 0.2 quality %, is preferably below the 0.1 quality %.These surfactants can add separately, also combination more than 2 kinds can be added.
The composition of formation lower layer reflection preventing film of the present invention in addition, can also contain rheology as required and adjust agent, bonding assistant etc.
Below, the use that antireflection film of the present invention is formed composition is illustrated.
On semiconductor substrate (for example: silicon/silicon dioxide is substrate coated, silicon nitride substrate, silicon wafer, glass substrate and ito substrate etc.), utilize suitable coating processes such as spin coating, coating to be coated with the composition of formation lower layer reflection preventing film of the present invention, then, utilize baking to form lower layer reflection preventing film.As the condition of baking, baking temperature can suitably be selected from 80～300 ℃, and stoving time can suitably be selected from 0.3～60 minute.Preferred baking temperature is 150～250 ℃, and preferred stoving time is 0.5～2 minute.
Dissolution velocity as the alkalies that uses in the development of lower layer reflection preventing film with respect to photoresist that forms is per second 0.1nm～50nm, is preferably per second 0.2nm～40nm, is more preferably 0.3～20nm.Dissolution velocity than the little situation of above-mentioned value under, it is elongated to remove the needed time of lower layer reflection preventing film, causes throughput rate low.Dissolution velocity than the big situation of above-mentioned value under, the lower layer reflection preventing film of photoresist unexposed portion lower floor also dissolves, the result can not form the photoresist pattern sometimes.
Form the lower layer reflection preventing film that the lower layer reflection preventing film composition forms by of the present invention, can be by changing the baking condition when forming, the control lower layer reflection preventing film is with respect to the dissolution velocity of alkaline-based developer.Under the certain situation of stoving time, baking temperature is high more, can form the lower layer reflection preventing film more little with respect to the dissolution velocity of alkaline-based developer.
Then, on lower layer reflection preventing film, form the photoresist layer.Forming the photoresist layer can carry out with general method, i.e. painting photoresist solution on lower layer reflection preventing film, and baking.
As the photoresist of coating on lower layer reflection preventing film of the present invention, formation, as long as the light sensation light that exposure is used just is not particularly limited.In negative type photoresist and the positive light anti-etching agent any one all can use.The phenolic novolac of comprising and diazonium-1 is arranged, the positive light anti-etching agent of 2-naphthoquinone sulfonic acid ester; Comprise to have because of acid and decompose the bonding agent make the group that alkali dissolution speed improves and the chemical amplifying type photoresist of photoacid generator; Comprise the chemical amplifying type photoresist that decomposes low molecular compound, alkali-soluble bonding agent and the photoacid generator of the alkali dissolution speed raising that makes photoresist because of acid; And comprise to have because of acid and decompose the bonding agent make the group that alkali dissolution speed improves, decompose the low molecular compound that the alkali dissolution speed that makes photoresist improves and the chemical amplifying type photoresist of photoacid generator etc. because of acid.For example can list, the commodity etc. of the S-1808 by name of the commodity of iP5200 by name, iP5700, TDMR-AR80 of chemical industry (strain) system and SHIPLEY society system are answered in commodity, the Tokyo of PFi-58 by name, the PFi-88 of Sumitomo Chemical (strain) system.
Then, the mask by regulation exposes.For exposure, can use i line (wavelength 365nm) and g line (wavelength 432nm) etc.After the exposure, back heating (PEB:post exposure bake) as required also can expose.
Then, utilize alkaline-based developer to develop.Thus, using under the situation of positive light anti-etching agent for example, the photoresist of exposed portion and the lower layer reflection preventing film of its underclad portion are removed by development.
As the alkaline-based developer that in the development of photoresist, uses, can list the alkaline aqueous solution of the amine aqueous solution such as aqueous solution, monoethanolamine, propyl group amine, ethylenediamine etc. of the quaternary ammonium hydroxide such as aqueous solution, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline of alkali metal hydroxides such as potassium hydroxide, NaOH as an example.And then, in these developer solutions, can add surfactant etc.As the condition of developing, temperature can suitably be selected from 5～50 ℃, and the time can suitably be selected from 10～300 seconds.
Form the lower layer reflection preventing film that the lower layer reflection preventing film composition forms by of the present invention, the tetramethylammonium hydroxide aqueous solution of 2.38 quality % that uses common usefulness can easily at room temperature develop as alkaline-based developer.
And then, lower layer reflection preventing film of the present invention, also can be used as following layer and use, that is, be used for preventing semiconductor substrate and photoresist interactional layer, have the material that prevents the material that uses at photoresist or generate when photoresist expose substrate is produced the function of bad influence layer, have the material that from substrate, generates when preventing heated baking to the function of the diffusion of upper strata photoresist layer and be used to reduce the restraining barrier of the poisoning effect of the photoresist layer that the semiconductor substrate dielectric layer causes.
Below, further specifically describe the present invention by embodiment, but do not limit the present invention with this.
Embodiment
Embodiment 1
(synthesizing of polyamic acid)
By with 4 of 17.8g, 3 of 4 '-(hexafluoro isopropylidene) two O-phthalic acid dianhydrides, 3.12g, two (4-aminophenyl) sulfone of 5-diaminobenzoic acid, 4.92g reacted 20 hours under 80 ℃ in the propylene glycol monomethyl ether of 145.6g, obtained containing the solution [A] of polyamic acid.The polyamic acid of gained has the structure shown in formula (40) and the formula (41).
(mensuration of the molar absorptivity of light-absorbing compound)
Measure the molar absorptivity of light-absorbing compound by the following method.
Use N, dinethylformamide makes 4 * 10 with light-absorbing compound
-6(g/ml) solution.Use the UV determinator UV2550 of Shimadzu Seisakusho Ltd.'s (strain) system to measure this solution absorbency.Calculate molar absorptivity by [molar absorptivity]=[absorbance]/[molecular weight of the mass concentration/light-absorbing compound of solution].
The benzoic molar absorptivity of 2-(4-diethylamino-2-hydroxy benzoyl) is 20563 (1molcm), and the molar absorptivity of alpha-amido-4-hydroxycinnamic acid is 19827 (1molcm).(forming the modulation of the composition of lower layer reflection preventing film)
In the above-mentioned solution [A] of 14.0g, add 1.04 2-(4-diethylamino-2-hydroxy benzoyl) benzoic acid, 0.35g alpha-amido-4-hydroxycinnamic acid, 2.77g 4; 4 '-methylene, two (N; the N-diglycidylaniline), 3 of 0.16g; the propylene glycol monomethyl ether of 7-dihydroxy naphthlene formic acid, 37.7g and the propylene glycol methyl ether acetate of 51.6g are by at room temperature stirring the solution [1] of modulating the composition that forms lower layer reflection preventing film in 30 minutes.
(forming the evaluation of the composition of lower layer reflection preventing film)
Use spinner that above-mentioned solution [1] is coated on the silicon wafer, on electric hot plate, toasted 60 seconds down at 170 ℃ then, forming thickness is the lower layer reflection preventing film of 70nm.The lower layer reflection preventing film that obtains is insoluble in ethyl lactate and propylene glycol methyl ether acetate.Use the beam split ellipsograph to measure this lower floor side's reflectance coating, the result is 1.74 in the refractive index (n value) at the wavelength place of 365nm, and attenuation coefficient is 0.22 for (k value).
In addition, be to have formed lower layer reflection preventing film with same method under 175 ℃ at baking temperature.And, confirmed that these lower layer reflection preventing films are insoluble to ethyl lactate and propylene glycol methyl ether acetate.
Then, use resist development analyser (リ ソ レ Star Network ジ ヤ パ Application (strain) system) to measure the dissolution velocity of lower layer reflection preventing film with respect to the alkaline-based developer that in the development of photoresist, uses (chemical industry (strain) system, commodity NMD-3 by name are answered in Tokyo).At baking temperature is that 170 ℃, stoving time are that the dissolution velocity of the lower layer reflection preventing film that forms under 60 seconds the condition is per second 4.1nm.In addition, be that 175 ℃, stoving time are that the dissolution velocity of the lower layer reflection preventing film that forms under 60 seconds the condition is per second 3.3nm at baking temperature.
Use spinner that above-mentioned solution [1] is coated on the silicon wafer, on electric hot plate, toasted 60 seconds down at 175 ℃ then, forming thickness is the lower layer reflection preventing film of 70nm.On the lower layer reflection preventing film that obtains, form i line positive light anti-etching agent film.Then, see through the mask of setting and expose, so that form the pattern at row (line)/interval of 600nm with i line (wavelength 365nm).Heat after 90 seconds the exposure carrying out under 110 ℃, use 2.38% tetramethylammonium hydroxide aqueous solution (chemical industry (strain) system, trade name NMD-3 are answered in Tokyo) then, carry out the liquid formula (puddle) of covering in 60 seconds and develop as alkaline-based developer.Also dissolve at the exposed portion lower layer reflection preventing film with photoresist.As mentioned above, the residual film of lower layer reflection preventing film is not found at line/interval of 600nm.
Claims (11)
1. composition that forms lower layer reflection preventing film, said composition is used to form and can it is characterized in that by alkaline-based developer with the lower layer reflection preventing film that photoresist develops, and contains the polyamic acid of the structure shown in (1) and the formula (2) that has formula:
(in the formula, A
1And A
2The organic group of representing 4 valencys, B
1The organic group of representing 3 valencys, B
2The organic group of expression divalent), have the compound of at least two epoxy radicals, be that the molar absorptivity of the light of 365nm is the light-absorbing compound and the solvent of 5000～100000 (1/molcm) to wavelength.
2. the composition of formation lower layer reflection preventing film as claimed in claim 1, it is characterized in that above-mentioned polyamic acid is to have the diamine compound of at least 1 carboxyl and (c) polyamic acid made of diamine compound reaction by (a) tetracarboxylic dianhydride compound, (b).
3. the composition of formation lower layer reflection preventing film as claimed in claim 2 is characterized in that, above-mentioned (a) tetracarboxylic dianhydride compound is the tetracarboxylic dianhydride's compound with at least one benzene ring structure.
4. the composition of formation lower layer reflection preventing film as claimed in claim 2 is characterized in that, the diamine compound that above-mentioned (b) has at least 1 carboxyl is the diamine compound with at least one benzene ring structure.
5. the composition of formation lower layer reflection preventing film as claimed in claim 2 is characterized in that, above-mentioned (c) diamine compound is the diamine compound with 2 benzene ring structures.
6. the composition of formation lower layer reflection preventing film as claimed in claim 1 is characterized in that, above-mentioned compound with at least two epoxy radicals is the compound with 3～5 epoxy radicals.
7. the composition of formation lower layer reflection preventing film as claimed in claim 1; it is characterized in that; above-mentioned light-absorbing compound is to be selected from 2-(4-diethylamino-2-hydroxy benzoyl) benzoic acid; 2-(4-dibutylamino-2-hydroxy benzoyl) benzoic acid; 2; 2 '; 4; 4 '-tetrahydroxybenzophenone; 2; 3; 3 '; 4; 4 ', 5 '-hexahydroxy benzophenone; lichenic acid; phenylfluorone; rosolic acid; 1,8; 9-trihydroxy anthracene; 2-(4-hydroxy phenyl azo) benzoic acid; methyl red; 4; 4 '-diaminobenzophenone; 5,5 '-methylene two (2-hydroxyl-4-methoxy benzophenone); 3, the 4-diaminobenzophenone; compound in curcumin and alpha-amido-4-hydroxycinnamic acid.
8. the composition of formation lower layer reflection preventing film as claimed in claim 1 is characterized in that, further contains the naphthoic acid compound.
9. the composition of formation lower layer reflection preventing film as claimed in claim 1 is characterized in that, further contains the diazo naphthoquinone sulfoacid compound.
10. the formation method of a photoresist pattern that is used for producing the semiconductor devices, comprise following operation: will be coated on the semiconductor substrate at the composition of the formation lower layer reflection preventing film described in each of claim 1～9, toast the operation that forms lower layer reflection preventing film; On above-mentioned lower layer reflection preventing film, form the operation of photoresist layer; The expose operation of the semiconductor substrate that above-mentioned lower layer reflection preventing film and above-mentioned photoresist layer be covered; After exposure, by the operation of alkaline-based developer development.
11. the formation method of photoresist pattern as claimed in claim 10 is characterized in that, above-mentioned exposure is that the light by the wavelength of 365nm or 432nm carries out.
Applications Claiming Priority (2)
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|---|---|---|---|
| JP2004256655 | 2004-09-03 | ||
| JP256655/2004 | 2004-09-03 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201310081190XA Division CN103163736A (en) | 2004-09-03 | 2005-08-23 | Composition including polyamide acid for forming lower layer reflection preventing film |
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| Publication Number | Publication Date |
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| CN101010634A true CN101010634A (en) | 2007-08-01 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA2005800295295A Pending CN101010634A (en) | 2004-09-03 | 2005-08-23 | Composition including polyamide acid for forming lower layer reflection preventing film |
| CN201310081190XA Pending CN103163736A (en) | 2004-09-03 | 2005-08-23 | Composition including polyamide acid for forming lower layer reflection preventing film |
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| CN201310081190XA Pending CN103163736A (en) | 2004-09-03 | 2005-08-23 | Composition including polyamide acid for forming lower layer reflection preventing film |
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| Country | Link |
|---|---|
| JP (1) | JP4466877B2 (en) |
| KR (1) | KR101118697B1 (en) |
| CN (2) | CN101010634A (en) |
| TW (1) | TWI389935B (en) |
| WO (1) | WO2006027950A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110875175A (en) * | 2018-08-31 | 2020-03-10 | 台湾积体电路制造股份有限公司 | Method for manufacturing semiconductor device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7563563B2 (en) * | 2006-04-18 | 2009-07-21 | International Business Machines Corporation | Wet developable bottom antireflective coating composition and method for use thereof |
| US8257901B2 (en) | 2009-03-10 | 2012-09-04 | Lg Chem, Ltd. | Polyimide-based polymers, copolymers thereof and positive type photoresist compositions comprising the same |
| KR101056962B1 (en) * | 2009-03-10 | 2011-08-17 | 주식회사 엘지화학 | Polyimide-based polymer and copolymer mixture thereof, and positive type photoresist composition comprising the same |
| EP2766920B1 (en) * | 2011-10-10 | 2020-12-02 | Brewer Science, Inc. | Spin-on carbon compositions for lithographic processing |
| JP5817939B2 (en) * | 2013-10-18 | 2015-11-18 | 東レ株式会社 | Polyamide resin composition, production method, molded product |
| JP7073845B2 (en) * | 2018-03-28 | 2022-05-24 | 日産化学株式会社 | Polymer and resin composition containing it |
| CN117043678A (en) * | 2021-03-04 | 2023-11-10 | 日产化学株式会社 | Composition for forming protective film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0572736A (en) * | 1991-09-18 | 1993-03-26 | Hitachi Chem Co Ltd | Production of fluorine-contained polyimide resin film pattern |
| US5397684A (en) * | 1993-04-27 | 1995-03-14 | International Business Machines Corporation | Antireflective polyimide dielectric for photolithography |
| JP3031214B2 (en) * | 1995-09-11 | 2000-04-10 | 信越化学工業株式会社 | Anti-reflective coating material |
| JP2000007783A (en) * | 1998-06-23 | 2000-01-11 | Hitachi Chemical Dupont Microsystems Ltd | Polyimide precursor resin composition and preparation thereof |
| US6455416B1 (en) * | 2000-10-24 | 2002-09-24 | Advanced Micro Devices, Inc. | Developer soluble dyed BARC for dual damascene process |
| EP1411088B1 (en) * | 2001-07-26 | 2013-08-21 | Nissan Chemical Industries, Ltd. | Polyamic acid resin composition |
| US7261997B2 (en) * | 2002-01-17 | 2007-08-28 | Brewer Science Inc. | Spin bowl compatible polyamic acids/imides as wet developable polymer binders for anti-reflective coatings |
| JP4525940B2 (en) * | 2004-10-14 | 2010-08-18 | 日産化学工業株式会社 | Underlayer antireflection film-forming composition comprising an aromatic sulfonic acid ester compound and a photoacid generator |
-
2005
- 2005-08-23 CN CNA2005800295295A patent/CN101010634A/en active Pending
- 2005-08-23 CN CN201310081190XA patent/CN103163736A/en active Pending
- 2005-08-23 KR KR1020077005380A patent/KR101118697B1/en active IP Right Grant
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110875175A (en) * | 2018-08-31 | 2020-03-10 | 台湾积体电路制造股份有限公司 | Method for manufacturing semiconductor device |
| CN110875175B (en) * | 2018-08-31 | 2022-06-10 | 台湾积体电路制造股份有限公司 | Method for manufacturing semiconductor device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103163736A (en) | 2013-06-19 |
| KR20070048237A (en) | 2007-05-08 |
| TWI389935B (en) | 2013-03-21 |
| WO2006027950A1 (en) | 2006-03-16 |
| KR101118697B1 (en) | 2012-03-12 |
| TW200619268A (en) | 2006-06-16 |
| JP4466877B2 (en) | 2010-05-26 |
| JPWO2006027950A1 (en) | 2008-05-08 |
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