TW201009503A - Underlayer film composition - Google Patents

Abstract

Provided is a underlayer film composition which could be used for forming a underlayer film that has excellent embedability, few sublimation amount; besides, also has excellent etching resistance, great values of refraction coefficient and decay coefficient. An underlayer film composition comprises (A) polymer having desired structure unit, (B) cross-linking agent having butyl ether group, and (C) solvent.

Description

201009503 6. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to an underlayer film forming composition. More specifically, in addition to the excellent embedding property and the small amount of sublimation, the composition of the underlayer film formation is excellent in that the urethane resistance is excellent, the refractive index and the coefficient of decay are good. [Prior Art] A manufacturing process of a semiconductor device often includes a plurality of substances deposited on a germanium wafer as a film to be processed, and a desired pattern (patterning) is formed on the film to be processed. Specifically, the patterning first deposits a photoresist (photosensitive substance) on the film to be processed to form a photoresist film, and exposes a predetermined region of the photoresist film. Next, the exposed portion or the unexposed portion of the photoresist film is removed by a developing process to form a photoresist pattern. Subsequently, the film to be processed is dry etched using the photoresist pattern as an etch mask. In this process, ultraviolet light such as an ArF excimer laser is used as an exposure light source for applying π to the photoresist film. Nowadays, the demand for miniaturization of large-scale integrated circuits (LSI) is increasing, and the necessary resolution is set to be equal to or lower than the wavelength of exposure light. When the resolution is equal to or lower than the wavelength of the exposure light, the exposure process tolerance such as the exposure amount tolerance and the focus tolerance becomes insufficient. In order to compensate for the shortage of the exposure process tolerance, it is effective to reduce the film thickness of the photoresist film to improve the resolution, but on the other hand, it is difficult to ensure the thickness of the photoresist film necessary for etching the film to be processed. In view of this, a photoresist underlayer film (hereinafter, simply referred to as "lower film") is formed on the film to be processed, and after the photoresist pattern is temporarily transferred to the underlayer film 201009503 to form an underlayer film pattern, the lower layer is used. The review of the film pattern as a process for transferring an etch mask to a film to be processed (also referred to as a multilayer process) is prevailing. In the process, it is preferred that the underlayer film is composed of a material having etching resistance. For example, a composition of a polymer having a terpene skeleton which absorbs energy during etching and has etching resistance is proposed as a material for forming the underlayer film (see, for example, Patent Documents 1 to 5). However, when the LSI pattern rule of 0.13 m or less is formed, the influence of the wiring delay on the speed of the LSI is increased, and it is difficult to improve the performance of the LSI in accordance with the current LSI process technology. Therefore, one of the materials (wiring materials) currently used to reduce the wiring delay is known as Cu. Moreover, the technique for introducing the wiring material from A1 to Cu is a dual damascene process (for example, refer to the patent). In the case of the double damascene process, the lower layer film is formed on the substrate having a finer aspect ratio (concavity and convexity) than the substrate of the conventional wiring material A1. Here, Patent Documents 1 to 4 describe The underlayer film forming composition has excellent etching resistance and anti-reflection function unique to the terpene skeleton, but cannot sufficiently embed a substrate having a large aspect ratio and a large aspect ratio. Therefore, a method of embedding a substrate having a large aspect ratio, In the method of improving the embedding property, there is a report that the molecular weight of the polymer (polymer having a terpene skeleton) in the underlayer film forming composition is 2000 or less (see Patent Document 5). Further, in Patent Document 7, there is The molecular weight of the polymer in the underlayer film-forming composition is 3,000 or less. Patent Document 1 JP-A-2000-143937, 201009503 Patent Document 2 Patent Document 3 Patent Document 4 Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. OBJECTS OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION However, when a polymer of a lower film formation composition, particularly a polymer having a terpene skeleton, has a small molecular weight, a composition is formed by using the underlayer film. When the underlayer film is formed, the low molecular component in the polymer and the decomposition product thereof are sublimed. Such a sublimation low molecular component or its decomposition product {that is, a sublimate is produced), and the device for forming the underlayer film is subject to The problem of pollution. As a result, when the molecular weight of the polymer is lowered for the purpose of improving the embedding property of the underlayer film forming composition, there arises a problem that the amount of the sublimated substance increases. Therefore, in addition to the excellent embedding property for a substrate having a large aspect ratio, the development of the film formation composition under the amount of the sublimate generated at the time of forming the underlayer film is eagerly expected. In the present invention, it is possible to provide an underlayer film which is excellent in etch resistance and has a good number of refractive index and decay coefficient, in addition to excellent embedding property and small amount of sublimation material. The underlying film forms a composition. Means for Solving the Problem 201009503 According to the present invention, the following underlayer film forming composition can be provided. [1] A lower layer film-forming composition comprising the structural unit represented by the following formula (1) and the structural unit represented by the following general formula (1), and the following structural formula: a structural unit represented by the above, a polymer of the structural unit represented by the above formula (4), (B) a crosslinking agent having a butyl ether group, and a solvent of cerium (C).

(1) A carbon number group of 6 (in the above formula (1), R1 represents a hydrogen atom, an alkyl group which may be substituted by a carbon number, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a carboxyl group, 1~ Alkoxycarbonyl group of 6, alkoxycarbonyloxy group having 1 to 6 carbon atoms, alkoxymethylol group of hydroxymethyl group or carbon number 6, and R2 and R3 each represent hydrogen n or carbon number 1 to 6 Also substituted for alkyl) R4 —{~CH2—C—)— c=o 〇/ (2) \5

I

OH 201009503 (However, in the above formula (2), R4 represents a hydrogen atom or a methyl group, and R5 represents an alkyl group 1 R7 of a carbon number of 4;

(But, in the above formula (3), R6 represents a hydrogen atom, an alkyl group which may be substituted with 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having a carbon number, a carboxyl group, or an alkoxycarbonyl group having 1 to 6 carbon atoms. , alkoxycarbonyloxy group of carbon number 6, hydroxymethyl group, or alkoxymethylol of carbon number 6, r7 represents a hydrogen atom or a carbon number of 6 can also be substituted for the yard, η represents ι An integer from ~3) R9

Rio—〇—c-C- (4)

© II Ο R8 (However, in the above formula (4), R8, R9 and R10 each independently represent a hydrogen atom and an alkyl group which may have a carbon number of 1 to 6). [2] The underlayer film forming composition according to the above [1], wherein the (Α) polymer has a polystyrene-equivalent weight average molecular weight (Mw) of 500 to 10000 ° [3] as described above [1] or The underlayer film forming composition according to [2], wherein the (B) crosslinking agent is a compound represented by the following formula (5) or (6). 201009503

(5) (However, in the above formula (5), R11 each independently represents a hydrogen atom, a methyl group, a n-butyl group or an isobutyl group; however, two of the four R11 groups are positively on the ruthenium. Base or isobutyl) OR12 OR12

(6) (However, in the above formula (6), R12 each independently represents a hydrogen atom, a methyl group, a n-butyl group or an isobutyl group; however, two of the six R12 groups are positive on ❹ W Butyl or isobutyl). [4] The film formation composition according to any one of the above items (1) to (3), wherein the ratio of the structural unit represented by the above formula (1) contained in the polymer (A), The % structural unit % of the total structural unit of the polymer (A) is 5 to 80% by mole; the structural unit represented by the above formula (2) contained in the above (A) polymer The ratio of the total structural unit relative to the above (A) polymer is 1 to 8 mol. /. 201009503 The ratio of the structural unit represented by the above formula (3) contained in the above (A) polymer is 0.1 to 5 with respect to the total structural unit of the above (A) polymer. [0] The film formation composition of any one of the above [1] to [4], which further contains (D) an acid generator. EFFECTS OF THE INVENTION The underlayer film forming composition of the present invention exhibits an effect of forming an underlayer film which is excellent in embedding property, small in etch resistance, and excellent in the number of refractive indices and fading coefficients. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the best mode for carrying out the invention will be described, but the present invention is not necessarily limited to the following embodiments. In other words, it is also possible to make appropriate changes, improvements, and the like in the following embodiments based on the general knowledge of the present invention within the scope of the present invention, and it is also understood to be within the scope of the present invention. [1] Lower film formation composition: The embodiment of the lower film formation composition of the present invention contains (A) a structural unit represented by the following general formula (1) and represented by the following general formula (2). a structural unit, a structural unit represented by the following formula (3), and a polymer of a structural unit represented by the following formula (4), (B) a crosslinking agent having a butyl ether group, and (C) Solvent. The underlayer film forming composition system can form an underlayer film which is excellent in etch resistance and has a good refractive index and a coefficient of decay, in addition to excellent embedding property and a small amount of sublimation. 201009503 R2 R3

(1) R1 (However, in the above formula (1), R1 represents a hydrogen atom, an alkyl group which may be substituted, a hydroxyl group, an alkoxycarbonyl group having an alkoxy group having 1 to 6 carbon atoms, or an alkoxy group having a carbon number of 6 Carbonyloxy or alkoxymethylol having 1 to 6 carbon atoms, R2 and R3 each or a substituted alkyl group having 1 to 6 carbon atoms, a carboxyl group having 1 to 6 carbon atoms, a carbon number S, and a hydroxyl group Base, representing a hydrogen atom,

(However, in the above formula (2), R4 represents a hydrogen atom or a methyl group, and R5 represents an alkyl group of a carbon number of 4) R7

-10- (3) 201009503 (However, in the above formula (3), R6 represents a hydrogen atom, an alkyl group which may be substituted with 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having a carbon number, and a carboxyl group of 1 carbon number; ~6 alkoxycarbonyl group, carbon number 6 alkoxycarbonyloxy group, hydroxymethyl group, or carbon number alkoxy hydroxymethyl group, and r7 represents a hydrogen atom or a carbon number which can also be substituted. η. represents an integer of ι~3) R9 Plant-cIR 1 CMHNO ο I ο R1 (However, in the above formula (4), R8, R9 and R10 each independently represent a hydrogen atom and a carbon number of 1 to 6 (A) polymer: The polymer (A) containing the layer film-forming composition of the present embodiment has a structural unit represented by the formula (1) (hereinafter, it is described) In the case of "structural unit (1)", the structural unit represented by general formula (2) (hereinafter referred to as "structural unit (2)"), and the structural unit represented by general formula (3) ( Hereinafter, it is described as "the structural unit (3)") and the structural unit represented by the general formula (4) (hereinafter, referred to as "structural unit (4)"). In addition, since it contains a lot of aliphatic main chain, an aliphatic group in a structural unit, and a terminal ester group can improve the softness of the whole resin, it has the advantage that the penetration of a through-hole and a ditch which is small in diameter is favorable. [1-1-1] The structural unit represented by the formula (1): -II- 201009503 Since the (A) polymer contains the structural unit represented by the general formula (1), the layer film forming composition under the present embodiment A layer film having excellent uranium resistance can be formed. In the formula (1), Ri is an alkoxy group having 1 to 6 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a n-propoxy group, and an isopropoxy group. , n-butoxy, b-propylpropoxy, 2-methylpropoxy, tert-butoxy, n-pentyloxy, n-hexyloxy, etc. The alkoxycarbonyl group having 1 to 6 carbon atoms may, for example, be a Oxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, decyl 1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl, tert-butoxy a carbonyl group, a n-pentyloxycarbonyl group, a n-hexyloxycarbonyl group, etc. The alkoxycarbonyloxy group having 1 to 6 carbon atoms may, for example, be a methoxycarbonyloxy group or a Oxycarbonyloxy, n-propoxycarbonyloxy, isopropoxycarbonyloxy, n-butoxycarbonyloxy, 1-methylpropoxycarbonyloxy, 2-methylpropoxycarbonyloxy Examples of the alkoxymethylol group having 1 to 6 carbon atoms, such as a methoxymethylol group, may be mentioned, for example, a methoxymethylol group, or a hexyloxycarbonyloxy group, a n-pentyloxycarbonyloxy group, a n-hexyloxycarbonyloxy group or the like. 0 ethoxymethylol, n-propoxymethylol, isopropoxyhydroxymethyl, n-butoxyhydroxymethyl, 1-methylpropoxyhydroxymethyl, 2-methylpropoxy Hydroxymethyl, tert-butoxymethylol, n-pentyloxymethylol, n-hexyloxymethylol, etc. In the formula (1), R2 and R3 may be substituted by a carbon number of 1 to 6. The alkyl group may, for example, be a methyl group, a butyl group or a hexyl group. Among these, methyl is preferred. The monomer which provides the structural unit represented by the general formula (1) is, for example, terpene, 3-hydroxymethyl decene, 4-hydroxymethyl decene, 5-hydroxymethyl oxime, 1-methyl 3-hydroxymethyl decene, 1-methyl-4-hydroxymethyl decene, 1-methyl-5-hydroxymethyl decene methyl -6-hydroxymethyl decene, methyl-12- .201009503 -7-Hydroxymethyl decene, 1-methyl-8-hydroxymethyl decene 4,2-dimethyl- 3 hydroxymethyl decene, 1, 2-dimethyl-4-hydroxyl Base olefin, 1, 2-dimethyl-5-hydroxymethyl decene, 1-phenyl-3-hydroxymethyl decene decene, phenyl-4-hydroxymethyl decene decene, 1 _Phenyl-5-hydroxymethyldecene decene, phenylphenyl-6-hydroxymethyl decene decene, 1-phenyl-7-hydroxymethyl decene, 1-phenyl-8-hydroxyl Terpene terpene, iota, 2-diphenyl-3-hydroxymethyldecene, 1,2-diphenyl-4-hydroxymethylnonene, 1,2-diphenyl-5-hydroxyl Hydroxymethyl decenes such as decenes; 3-methoxymethyl decene, 4-methoxy fluorene methyl decene, 5-methoxymethyl decene, 1-methyl-3- Methoxymethyl decene, 1-methyl-4-methoxymethyl dilute, 1- 5--5-methoxymethyl critical, 1-methyl-6-methoxymethyl critical, 1-methyl-7-methoxymethyl critical, 1-methyl-8-A Oxymethyl decene, 1, 2-dimethyl-3-methoxymethyl decene, 1, 2-dimethyl-4-methoxymethyl decene, 1, 2-dimethyl 5-5-methoxymethyl decene, 1-phenyl-3-methoxymethyl decene, 1-phenyl-4-methoxymethyl decene, 1-phenyl-5-methoxy Methyl decene, 1-phenyl-6-methoxy & methyl decene, 1-phenyl-7-methoxymethyl decene, 1-phenyl-8-methoxyformamidine Base olefin, 1, 2-diphenyl-3-methoxymethyl decene, 1, 2-diphenyl-4-methoxymethyl decene, 1, 2-diphenyl-5- a methoxymethyl decene such as methoxymethyl decene; 3-phenoxymethyl decene, 4-phenoxymethyl decene, 5-phenoxymethyl decene, 3- Vinyloxymethyl decene, 4-vinyloxymethyl decene, 5-vinyloxymethyl decene, 3-ethoxymethoxymethyl decene, 4-ethyl methoxymethyl decene, 5-Ethyloxymethyl decene and the like. Further, these single systems may be used alone or in combination of two or more. -13- 201009503 Among these, especially terpenes, 3-hydroxymethyl decene, 4-cyanomethyl decene, 5-hydroxymethyl decene, 3-methoxymethyl decene, 4 Preferably, methoxymethyl decene or 5-methoxymethyl decene is preferred. The proportion of the structural unit represented by the formula (1) contained in the polymer (A) is preferably 5 to 8 mol% based on 100% of the total structural unit of the (A) polymer, 30 ~80% of the mole is better, 50% to 70% of the mole is particularly good. When the above ratio is less than 5 mol%, the pattern resistance is lowered at the time of etching because the hung resistance is lowered. On the other hand, more than 80 moles. /. , because the anti-reflection function can be reduced, there will be a problem that the pattern forming ability of the lithography technique cannot be sufficiently obtained. [1-1-2] The structural unit represented by the formula (2): Since the (A) polymer contains the structural unit represented by the formula (2), the glass transition temperature of the polymer (A) is lowered and the energy is lowered. The embedding property of the substrate which imparts flexibility and has a large aspect ratio is a favorable composition. Further, by heating or exposure, the crosslinking reaction occurs between the molecular chains, and the degree of crosslinking (intermixing) of the polymer (A) can be controlled, and the hybrid formula (2) can be prevented. In the above, R5 is an alkylene group having 2 to 4 carbon atoms, and examples thereof include an exoethyl group, a propyl group, an exo-propyl group, a butyl group, an isobutylene group, etc., which are represented by the formula (2). The single system of the structural unit may, for example, be 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate or 2-hydroxy acrylate. Further, these single systems may be separately 1 It is also possible to use two or more types in combination. -14- 201009503 (A) The ratio of the structural unit represented by the formula (2) contained in the polymer is based on the total structural unit of the (A) polymer. 1〇〇% of the ear is 5~8〇%, preferably 5~60mol./ is better, 5~50% is especially good. Since the above ratio is less than 5m%, It is difficult to fully form the cross-linking structure, so there is a possibility that the intermediate layer is mixed with the intermediate layer and the etching selectivity is lowered. On the other hand' When the etching resistance is more than 80%, the etching resistance is lowered. Therefore, there is a problem that the pattern cannot be transferred by etching. [1-1-3] Structural unit represented by the general formula (3): Since (A) Since the polymer contains the structural unit represented by the general formula (3), the reflectance of the underlying film can be controlled. Specifically, increasing the content ratio of the structural unit (3) can increase the extinction at the ArF wavelength. In the formula (3), R6 is the same as in the formula (i). In the formula (3), R7 is an alkyl group which may have a carbon number of 1 to 6 and may be substituted. The same as the alkyl group which may be substituted with R2 or R3 in the formula (1) and having a carbon number of 1 to 6. The single system to which the structural unit represented by the above formula (3) is supplied may, for example, be benzene. Ethylene, hydroxystyrene, tert-butoxystyrene, tert-butoxycarbonyloxystyrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methyl Styrene, 4-methoxystyrene, 4-hydroxymethylstyrene, 3-hydroxymethylstyrene, 4-ethylstyrene, 4-ethoxystyrene, 3,4-dimethylbenzene Ethylene, 3,4-diethyl Ethylene, 2-chlorostyrene, 3-chlorostyrene, 4-chloro-3-methylstyrene, 4-tert-butylstyrene, 2,4-dichlorostyrene, 2,6 - Dichlorostyrene, etc. Further, these single systems may be used alone or in combination of two or more. -15- 201009503 Among these, especially styrene, 4-hydroxymethyl Styrene, 3-hydroxymethylstyrene, tert-butoxystyrene, and tert-butoxycarbonyloxystyrene are represented by the formula (3) contained in the (A) polymer. The proportion of the structural unit is preferably 1 to 50 mol%, more preferably 1 to 30 mol%, more preferably 3 to 20 mol%, relative to the total structural unit of the (A) polymer. . /. It is especially good. Since the above ratio is less than 0.1% by mole, the antireflection function is lowered, so that the pattern forming ability of the lithography technique cannot be sufficiently obtained. Further, since the antireflection function is also lowered in the case of more than 50 mol%, there is a possibility that the pattern forming ability of the lithography technique cannot be sufficiently obtained. [I-4] The structural unit represented by the general formula (4): Since the (A) polymer contains the structural unit represented by the general formula (4), that is, since the structural unit (4) is located at (A) In addition to the flexibility of the resin ((A) polymer), it is difficult to decompose the (A) polymer, so that it is possible to obtain a film forming composition which is excellent in embedding property and low sublimation property. . In the formula (4), R8, R9 and 1 are an alkyl group which may be substituted with a carbon number of 6 and may be substituted with R2 or R3 in the formula (1) as a carbon number of 1 to 6. The alkyl group is the same. The structural unit represented by the formula (4) is derived from a structural unit of a radical polymerization initiator used in the production of the polymer (A). The commercially available product of the radical polymerization initiator may be, for example, "V-60 1", "VE-057", "V-501", or "VA-057" (above, Wako Pure Chemical Co., Ltd.) -16- 201009503 system) and so on. Among these, 'V_601' is preferred because it can be protected by an ester group and from the viewpoint that the end of the resin ((oc)polymer) is a soft skeleton. (A) The ratio of the structural unit represented by the formula (4) contained in the polymer is relative to the total structural unit of the (A) polymer. /. It is preferably 0.01 to 50 mol%, more preferably 1 to 30 mol%, and 1 to 20 mol% is particularly good. Since the above ratio is less than 0.01 mol%, the flexibility of the resin is lowered, so that the embedding property is lowered. On the other hand, since the etching resistance is lowered by more than 50% by mole, there is a problem in that the pattern transfer ability is lowered. ❹ [1-1-5] Other structural units: (A) The polymer system may be in addition to the above-mentioned structural unit (1), structural unit (2), structural unit (3), and structural unit (4). Contains other structural units. The single system providing other structural units may, for example, be glycidyl methacrylate, vinyl hydrazine, vinyl carbazole, vinyl acetate, vinyl propionate, vinyl hexanoate, (meth) acrylonitrile, chloro group. Acrylonitrile, divinyl cyanoethylene, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate , (meth) butyl butyl acrylate, n-hexyl (meth) acrylate, glycidyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, ( Methyl)vinyl acrylate, dimethyl vinyl (meth) propylene oxymethyl decane, chloroethyl vinyl ether, vinyl chloroacetate, allyl chloroacetate, (methyl ) acrylamide, decyl decanoate, and the like. Among them, glycidyl methacrylate is preferred. The proportion of other structural units contained in the (Α) polymer is from 1 to 50 moles per 100% of the total structural unit of the (Α) polymer. /. It is better. -17- 201009503 (A) The polymer is preferably a polystyrene-equivalent weight average molecular weight (Mw > 500 to 10,000, more preferably 1,500 to 5,000. The above weight average molecular weight (Mw) is less than 500, When the underlayer film is formed, the amount of sublimation material from the underlayer film is increased, and the film formation device is contaminated. On the other hand, when it exceeds 10,000, the embedding property of the substrate having a large aspect ratio is changed. In the present specification, the "weight-average molecular weight (Mw) in terms of polystyrene" is based on the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography. When the weight average molecular weight (Mw) is 1500 to 5,000, it is possible to obtain an underlayer film which can sufficiently suppress the amount of the sublimate from the underlayer film when the underlayer film is formed, and which can be well embedded even for a substrate having a large aspect ratio. In order to manufacture the (A) polymer, for example, the monomer providing the structural unit (1), the monomer providing the structural unit (2), the monomer providing the structural unit (3), and other structural units are provided. The monomer component composed of the monomer is dissolved in a solvent (for example, methyl ethyl ketone or methyl isobutyl ketone) which can dissolve the monomer component, and is dissolved to obtain a solution. Then, the solution is dissolved. In the liquid, a monomer which provides the structural unit (4) (that is, a radical polymerization initiator) is added. Next, the temperature is raised to a predetermined temperature (for example, 50 to 90 ° C) to carry out polymerization for 4 to 8 hours. The polymerization reaction liquid is obtained. Then, the polymerization reaction liquid is reprecipitated by an organic solvent such as n-heptane and methanol to obtain (A) a polymer. Further, the radical polymerization initiator is used in an amount according to the desired weight. The (A) polymer having an average molecular weight is suitably selected, but in the case of obtaining the (A) polymer having a weight average molecular weight of 500 to 10,000, the amount of the total monomer used in the polymerization is compared with -18 to 201009503 (provided The monomer of the structural unit (1), the monomer providing the structural unit (2), the monomer providing the structural unit (3), the monomer providing the structural unit (4), and the total of the monomers providing the other structural unit Quantity) 1〇〇 part by mass, 〇.5~30 mass The component is preferably 1 to 20 parts by mass, more preferably 3 to 15 parts by mass. The content ratio of the (A) polymer contained in the underlayer film-forming composition of the present embodiment may be in accordance with the lower layer formed. The film thickness of the film is suitably selected, and the solid content of the composition of the underlayer film is preferably 5 to 30% by mass, more preferably 8 to 15% by mass, and the content of the (A) polymer is low. At 5% by mass, the film having a sufficient film thickness is not obtained. On the other hand, when it exceeds 30% by mass, the viscosity of the underlying film forming composition becomes too high, and the substrate is buried. In addition, the (A} polymer system contained in the underlayer film forming composition of the present embodiment may contain only one type or two or more types. [1-2] (B) Crosslinking agent: The (B) crosslinking agent contained in the underlayer film forming composition of the present embodiment has a butyl ether group. The (B) crosslinking agent is generally a component having a halo preventing effect. By containing the (B) crosslinking agent, since the film density of the underlayer film can be increased, there is a so-called difficulty in mixing with the intermediate layer and the etching resistance can be improved. (B) The crosslinking agent is not particularly limited. It is preferably a compound represented by the following formula (5) or (6). When the compound represented by the formula (5) or (6) is used, since the volatility can be lowered, there is an advantage that it is difficult to sublimate. -19- 201009503

R11C R11C

OR11 OR11 (However, in the above formula (5), R1i each independently represents a hydrogen atom, a methyl group, a n-butyl group, or an isobutyl group; however, two of the four R11 groups are positively on the ruthenium Butyl or isobutyl) OR12 〇R12

V

(In the above formula (6), R12 each independently represents a hydrogen atom, 0 methyl group, n-butyl group or isobutyl group; however, two or more of the six R12 groups are n-butyl groups or Isobutyl} The compound represented by the formula (5) is more resistant to the sublimation of the (B) crosslinking agent by making two or more of the four Rii groups be n-butyl or isobutyl. Further, by the sublimate from the underlayer film forming composition, contamination of the coating device can be suppressed. Further, since the number of n-butyl groups is more, the sublimation of the (B) crosslinking agent can be suppressed, so that it is preferably four. All of Rii is an n-butyl group. The compound represented by the formula (6) is more resistant to (B) a crosslinking agent by making two or more of the six Ri2s be n-butyl or isobutyl. Sublimation -20-201009503 Sex' and by the sublimate from the underlying film forming composition, the coating device can be inhibited from contamination. Furthermore, since the number of n-butyl groups is increased, the (B) crosslinking agent can be inhibited. Sublimation 'so 6 series of r 1 2 are all n-butyl groups. (B) The amount of the crosslinking agent is 1 part by mass relative to the (A) polymer. It is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass, and if the amount is less than 1 part by mass, the crosslinking property is deteriorated and halo is generated in the underlayer film. When the amount is more than 50 parts by mass, the unreacted (B) crosslinking agent (that is, the 'reactive to (A) polymer) is mostly left in the underlayer film ◎, so the etching resistance of the underlayer film is deteriorated. In the underlayer film forming composition of the present embodiment, other crosslinking agent components may be contained in addition to the (B) crosslinking agent. Examples of the other crosslinking agent component include polynuclear phenols and curing agents. Examples of the polynuclear phenols include 2-nuclear phenols such as 4,4′-biphenyl diol, 4,4′-methylene bisphenol, 4,4′-ethylene bisphenol, and bisphenol A; 4,4',4"-methinetriol, 4,4'-[ 1-{4-(1-[4-hydroxyphenyl]-1-methylethyl)phenyl} fluorene ethylene a trinuclear phenol such as bisphenol or a polyphenol such as a novolac. The hydrazine curing agent may, for example, be a toluene 2,3-diisocyanate or a toluene 2,4-diisocyanate or the like. 4-Diisocyanate toluene, 3,5-diisocyanate toluene, 4,4'- A diisocyanate such as phenylmethane diisocyanate, hexamethylene diisocyanate or 1,4-cyclohexyl diisocyanate. The commercially available product of the curing agent may, for example, be the following: EPICOAT 812, 815, Same as 826, same as 828, same as 834, same as 836' with 871, same as 1001, same as 1〇〇4, same as 1007, same as 1009, same as 1〇31 (above 'oily shell epoxy company'), Araldite 6600, Same as 6700, same as -21-201009503 6800, same as 502, same as 6071, same as 6084, same as 6097, same as 6099 (above, Ciba Geigy company), DER331, same 332, same 333, same 661, same 644, same 667 ( The epoxy compound of the above, manufactured by Dow Chemical Co., Ltd.; CYMEL 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, 701, 272, Melamine-based hardeners such as 202, MYCOAT 506, and 508 (above, Mitsui Cyan amid); CYMEL 1 123, same as 1123-10, same as 1128, MYCOAT 102, same 105, same 106, same 13 0 (above) , benzoguanamine-based hardeners such as Mitsui Cyanamid Co., Ltd.; CYMEL 1170 With 1172 (the above, manufactured by Mitsui-Cyanamid Ltd.), .Nicarack N-2702 (Sanwa Chemical Co., Ltd.) glycoluril-based hardener. [1-3] {C) Solvent: The (C) solvent contained in the underlayer film forming composition of the present embodiment is soluble in (A) polymer, (B) crosslinking agent, and (D) acid generator. There is no particular limitation on the basis of the above, and those well known in the past can be used as appropriate. The Q (C) solvent may, for example, be an ethylene glycol monomethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether or ethylene glycol mono-n-butyl ether. Alkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether Ethylene glycol monoalkyl ether acetates such as acid esters; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether Diethylene glycol dialkyl ethers; triethylene glycol dialkyl ethers such as triethylene glycol dimethyl ether and triethylene glycol diethyl ether; -22- 201009503 propylene glycol monomethyl ether, a propylene glycol monoalkyl ether such as propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether or propylene glycol mono-n-butyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-n-propyl ether, Propylene glycol dialkyl ethers such as propylene glycol di-n-butyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl C, ethyl acetate, etc. Glycol monoalkyl ether acetates; lactate esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate; methyl formate, formic acid@@ Ester, n-propyl formate, isopropyl formate, n-butyl formate, isobutyl formate, n-amyl formate, isoamyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, N-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-propionate An aliphatic carboxylic acid ester of an ester, isobutyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate; Ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropanoate, methyl 3-methoxy-2-methylpropanoate, methyl 2-hydroxy-3-methylbutanoate, methoxyacetic acid Ethyl ester, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropyl acetate , 3-methoxybutyl acetate, 3- 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetate Other esters such as methyl pyruvate and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, 2 Ketones such as heptanone, 3-heptanone, 4-heptanone, cyclohexanone, etc.; N-methyl-23- 201009503 formamide, N,N-dimethylformamide, N-methyl b An amide such as guanamine, N,N-dimethylacetamide or N-methylpyrrolidone; or an internal vinegar such as r-butyrolactone. Further, these (C) solvents may be used singly or in combination of two or more. In particular, ethylene glycol monoethyl ether acetate, ethyl lactate, and n-butyl acetate are used. The ester, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, 2-heptanone or cyclohexanone is preferred. (C) The amount of the solvent to be added may be appropriately selected depending on the film thickness of the underlayer film to be formed, and the solid content concentration of the obtained underlayer film forming composition is preferably in the range of 0·0 Bu 70% by mass. 〇.〇5~60% by mass is better in the range of 0.1~50% by mass. When the concentration of the solid component is less than 0 - 01% by mass, it is difficult to form a film having a film thickness under a sufficient film thickness. On the other hand, when it exceeds 70% by mass, the viscosity becomes too high, so that formation of a film becomes difficult. [1-4] (D) Acid generator: The underlayer film forming composition of the present embodiment may further contain (D) acid in addition to the (A) polymer, (B) crosslinking agent, and (C) solvent. Incidence agent. The (D) acid generator is a component which generates an acid by exposure or heating. When the (D) acid generator is further contained, since the hardenability of the underlayer film can be enhanced, there is an advantage that it is more efficient and easier to form a film. Further, by increasing the acid concentration in the underlayer film, there is an advantage that the amine component such as ammonia is blocked. The (D) acid generator (hereinafter also referred to as "photoacid generator") which generates an acid by exposure may, for example, be diphenyliodonium trifluoromethanesulfonate or diphenyliodide pentafluorofluorene-positive Butane sulfonate, diphenyl iodonium sulfonate, diphenyl iodine-24- 201009503 gun n-dodecylbenzene sulfonate, diphenyl iodine gun ίο-camphor sulfonate, diphenyl Base iodine naphthalene sulfonate, diphenyl iodine hexafluoroantimonate, bis(4-tert-butylphenyl) iodine trifluoromethane sulfonate, bis(4-tert-butylphenyl) Iodine-free nonafluoro-n-butane sulfonate, bis(4-t-butylphenyl) iodine-n-dodecylbenzenesulfonate, bis(4-t-butylphenyl) iodine gun 10 - camphorsulfonate, bis(4-t-butylphenyl) iodine gun naphthalenesulfonate, bis(4-t-butylphenyl) iodine hexafluoroantimonate, triphenylsulfonium trifluoromethane Sulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium n-dodecylbenzenesulfonate, triphenylsulfonium naphthalenesulfonate, triphenylsulfonium 10-quinone Sulfonic acid ester, triphenyl mirror hexafluoroantimonate, 4-hydroxyphenyl phenyl methyl hydrazine p-toluene sulfonate 4-hydroxyphenyl·benzyl·methylhydrazine P-tosylate, cyclohexyl·methyl·2-oxycyclohexylfluorene trifluoromethanesulfonate, 2-oxycyclohexyldicyclohexylfluorene Fluoromethanesulfonate, 2-oxycyclohexyldimethylsulfonium trifluoromethanesulfonate, 1-naphthyldimethyltrifluoromethanesulfonate, naphthyldiethyltrifluoromethanesulfonate, 4-cyano-p-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyldiethyl & fluorene trifluoromethanesulfonate, 4-nitro-p-naphthyldimethylhydrazine Fluoromethanesulfonate, 4-nitro-1-naphthyldiethyltrifluoromethanesulfonate, 4-methyl-1-naphthyldimethyltrifluoromethanesulfonate, 4-methyl 1-naphthyldiethylphosphonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethyltrifluoromethanesulfonate, 4-hydroxy-1-naphthyldiethylphosphonium trifluoromethane Sulfonate, 1-(4-hydroxynaphthalen-1-yl}tetrahydrothiophene trifluoromethanesulfonate, 1-(4-methoxynaphthalen-1-yl)tetrahydrothiophene trifluoromethanesulfonic acid Ester, 1-(4-ethoxynaphthalenyl-bu)tetrahydrothiophene trifluoromethanesulfonate, 1-(4-methoxymethoxynaphthalene-bu)tetrahydrothiophene Trifluoromethanesulfonate, 1-(4-ethoxymethoxynaphthalen-1-yl)tetrahydrothiophene gun-25- 201009503 trifluoromethanesulfonate, 1-[4-(1-methoxy) Ethoxy)naphthalen-1-yl]tetrahydrothiophene trifluoromethanesulfonate, 1-[4-(2-methoxyethoxy)naphthalen-1-yl]tetrahydrothiophene trifluoromethanesulfonate Acid ester, 1-(4-methoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophene trifluoromethanesulfonate, 1-(4-ethoxymethoxynaphthalen-1-yl)tetra Hydrothiophene trifluoromethanesulfonate, 1-(4-n-propoxycarbonyloxynaphthalen-1-yl)tetrahydrothiophene trifluoromethanesulfonate, 1-(4-isopropoxycarbonyloxyl) Naphthyl-1-yl)tetrahydrothiophene trifluoromethanesulfonate, 1-(4-n-butoxycarbonyloxynaphthalene)-tetrahydrothiophene trifluoromethanesulfonate, 1-(4 _T-butoxycarbonyloxynaphthalen-1-yl)tetrahydrothiophene gun trifluoromethanesulfonate, i-[4-(2-tetrahydrofuranyloxy)naphthalen-1-yl]tetrahydrothiophene gun trifluoride Methanesulfonate, i-[4-(2-tetrahydropyranyloxy)naphthalen-1-yl]tetrahydrothiophene iron trifluoromethanesulfonate, 1-(4-benzyloxy)tetrahydrothiophene Key trifluoromethanesulfonate, 1_(naphthylacetamidine a gun salt-based photoacid generator such as tetrahydrothiophene trifluoromethanesulfonate; phenylbis(trichloromethyl)-s-three tillage, 4-methoxyphenylbis(trichloromethyl) )-s- tri-crop, 1-naphthylbis(trichloromethyl)-s-three-till, etc., halogen-containing compound-based photoacid generators; 1,2-naphthoquinonediazide-4-sulfonate 1,2-naphthoquinonediazide-4-, chloro, 1,2-naphthoquinone diazide, azide-5-sulfonyl chloride, 2,3,4,4'-tetrahydrodiphenyl ketone A diazoketone compound such as a sulfonate or a 1,2-naphthoquinonediazide-5-sulfonate is a photoacid generator: 4-triphenylsulfonium methylhydrazine, benzyl quinone methyl maple, Anthracene compounds such as bis(phenylsulfonyl)methane are photoacid generators; benzoin tosylate, tris(trifluoromethanesulfonate) of pyrogallol, nitrobenzyl-9,10- Diethoxyanthracene-2-sulfonate, trifluoromethanesulfonylbicyclo[2,2,1]hept-5-ene-2,3-dicarbodiimide, N-hydroxysuccinimide Fluoromethanesulfon-26-201009503 acid-generating agent such as acid ester or octadecyl trifluoromethanesulfonate of 1,8-naphthalene dicarboxylate. Among these photoacid generators, preferred are diphenyl iodine trifluoromethanesulfonate, diphenyl iodine gun nonafluoro-n-butane sulfonate, diphenyl iodonium sulfonate, Diphenyl iodine gun n-dodecylbenzene sulfonate, diphenyl iodine 1 〇 樟 磺酸 sulfonate, diphenyl iodine naphthalene sulfonate, bis (4-tert-butylphenyl) Iodine gun trifluoromethanesulfonate, bis(4-tert-butylphenyl) iodine gun nonafluoro-n-butane sulfonate, bis(4-tert-butylphenyl) iodine-n-dodecane Benzobenzenesulfonic acid ◎ ester, bis(4-t-butylphenyl) iodine 10-camphorsulfonate, bis(4-t-butylphenyl) iodine naphthalenesulfonate. In addition, these photoacid generators may be used alone or in combination of two or more. (D) acid generator (hereinafter also referred to as "thermal acid generator j") which generates an acid by heating. For example, 2,4,4,6-tetrabromocyclohexadienone, benzoisotosylate, 2-nitrobenzyl tosylate, alkylsulfonate, etc. These thermal acid generators may be used singly or in combination of two or more kinds. Alternatively, a photoacid generator and a thermal acid generator may be used. ❹ (D) The amount of the acid generator It is preferably 100 parts by mass or less, more preferably 0.1 to 30 parts by mass, more preferably 〇·ι~ι〇 parts by mass, and 0.5 to 10 parts by mass, based on 1 part by mass of the (A) polymer. When the amount of the above-mentioned compounding amount is less than 1 part by mass, the acid may not be sufficiently generated in the underlayer film, and the hardenability of the film may be impaired. Further, there may be a composition which hinders the formation of the photoresist. The amine component such as ammonia in the chemical reaction does not sufficiently prevent the amine component from diffusing in the photoresist film. On the other hand, if it exceeds 30 parts by mass, it will be present in the underlayer film. The excess acid that is generated is diffused in the photoresist film, which causes the shape of the photoresist film to deteriorate. In addition, when the underlayer film is formed, the decomposition product of the (D) acid generator becomes sublimation. (1) Other additives: The underlayer film forming composition of the present embodiment is in addition to (A) polymer, (B) crosslinking agent, (C) Other additives may be contained in addition to the solvent and the (D) acid generator. Examples of the other additives include a thermosetting resin, a radiation absorber, a surfactant, a storage stabilizer, an antifoaming agent, and a bonding aid. The thermosetting resin has a component which is insoluble in a solvent enthalpy by heat curing, and can prevent mixing between the obtained underlayer film and the photoresist film formed thereon. The thermosetting resin is a thermosetting resin. Various thermosetting resins can be used, and examples thereof include acrylic resins (thermosetting acrylic resins), phenol resins, urea resins, melamine resins, amine resins, aromatic hydrocarbon resins, and rings. Oxygen resin Among them, urea resin, melamine resin, and aromatic hydrocarbon resin are preferred. _ The amount of thermosetting resin is based on the mass of (A) polymer 100.

The Q portion is preferably 20 parts by mass or less, and more preferably 1 to 10 parts by mass. When the amount exceeds 20 parts by mass, the mixing between the obtained underlayer film and the photoresist film formed thereon cannot be satisfactorily prevented.

Examples of the radiation absorbing agent include dyes such as oil-soluble dyes, disperse dyes, salt-based dyes, methine dyes, pyrazole dyes, imidazole dyes, and hydroxy azo dyes; Fluorescent whitening agents such as saponin, hydrazine, 4,4'-diamino hydrazine derivatives, coumarin derivatives, pyrazoline derivatives, etc.; hydroxy azo dyes, trade name "TINUVIN - 28-201009503 2 34", ultraviolet absorbers such as "TINUVIN 1 130" (above, manufactured by Ciba Geigy Co., Ltd.); aromatic compounds such as anthracene derivatives and anthracene derivatives. In addition, these radiation absorbers may be used alone or in combination of two or more. The blending amount of the radiation absorber is 100 parts by mass or less based on 1 part by mass of the (A) polymer. Good, 1~50 parts by mass is better. The surfactant has a component which can improve the applicability, the striation, the wettability, the developing property and the like. The surfactant may, for example, be polyoxyethylene ethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene-n-octylphenyl ether, polyoxyethylene-n-decylbenzene. A nonionic surfactant such as a base ether, polyethylene glycol dilaurate or polyethylene glycol distearate, and all of the following product names: "DYNAFLOW" (manufactured by JSR Corporation), "SURFYNOL" ( Air-Products, Inc., "SURFYNOL Derivatives" (made by Air-Products), "DYNOL" (made by Air-Products), "DYNOL Derivatives" (made by Air-Products), "OLFINE" (Air- Products company), "OLFINE derivative" (made by Air-Products), "KP341" (manufactured by Shin-Etsu Chemical Co., Ltd.), "POLYFLOW Νο·75", "同Νο·95" (above, Kyoeisha oleochemicals) Industrial Company), "FDOPE EF101", "Same EF204", "Same EF303", "Same EF352" (above, Tohchem Products), "MEGAFAC F171", "Same F172", "Same F173" (above, Dainippon Ink Chemical Industry Co., Ltd.) FLUORIDFC430", "with FC431", "same FC135", "same as FC93" (above, Sumitomo 3M), "AsahiGuard AG710", "SURFLON S382", "Same -29-201009503 SC101", "Same SC102", "Same as SC103", "same as SC104", "same as SC105", "same as SC106" (above, manufactured by Asahi Glass Co., Ltd.), etc. In addition, these surfactants may be used alone or in combination of two or more. The amount of the surfactant to be added is preferably 15 parts by mass or less, more preferably 0. 00 1 to 1 part by mass, based on 100 parts by mass of the (A) polymer. [2] Lower film forming composition Modulation method: The preparation method of the underlayer film forming composition of the present embodiment is not particularly limited. For example, first, (A) a polymer, (B) a crosslinking agent, and (D) an acid generator are mixed in the mixture. The (C) solvent is added and adjusted to a predetermined solid component concentration. Subsequently, filtration is carried out using a filter having a pore diameter. Thus, an underlayer film forming composition can be obtained. [3] A double damascene structure using the underlayer film to form a composition Forming method: The underlayer film forming composition of the present embodiment is suitably used for a multilayer photo-resistance process. That is, when a composition is formed using an underlayer film, in addition to obtaining a good photoresist pattern, the underlayer film forming composition is buried. Since the intrinsic property is excellent, a double damascene structure in which the inorganic film (low dielectric insulating film) is less damaged can be formed satisfactorily. The method of forming the dual damascene structure includes, for example, embedding a conductive material in the first recessed portion of the first low dielectric insulating film formed in the first recessed portion of the predetermined pattern shape to form a predetermined first wiring. a step of forming a first wiring layer (first wiring forming step); embedding a conductive material in the second recess -30-201009503 of the second low dielectric insulating film formed in the second recess of the predetermined pattern shape, a step of forming a second wiring layer of a predetermined second wiring (second wiring forming step); and embedding in the third recess portion via a third low dielectric insulating film formed in a third recess portion of a predetermined pattern shape A method of forming a third wiring layer (third wiring forming step) by forming a conductive material. 5 shows that an etch stop layer 8 is formed between the second low dielectric insulating film 7 and the third low dielectric insulating film 9, and uranium engraving is formed between the third low dielectric insulating film 9 and the underlying film 11. An example of the state of the stop layer 10 is stopped. ❹ [3-1] First wiring forming step: The lower film forming composition of the present embodiment is a user who forms the concave portion in order to form the concave portion, and the method of forming the concave portion in the first wiring forming step is specifically, for example And a step of forming a lower layer film by forming a composition on the first low dielectric insulating film of the wafer formed of the first low dielectric insulating film (the lower film forming step): formed a step of forming a photoresist film on the underlayer film (resist film formation step); a step of forming a photoresist pattern on the photoresist film @ (resist pattern formation step); using a photoresist film formed with a photoresist pattern as a mask, a transfer step of transferring the photoresist pattern of the photoresist film to the underlayer film by etching (first transfer step); using a lower layer film with a photoresist pattern transferred as a mask, and a photoresist pattern of the underlying film a transfer step (second transfer step) transferred to the first low dielectric insulating film disposed under the lower film; and after the transfer of the photoresist pattern to the first low dielectric insulating film, via plasma ashing To remove the photoresist film A method of removing step underlayer film (film-removing step) is. [3-1-1] Lower film formation step: -31-201009503 First, a composition is formed through the underlayer film of the present embodiment on the first low dielectric insulating film forming the wafer of the first low dielectric insulating film The step of forming an underlayer film (underlayer film forming step) is performed. When the composition of the underlayer film of the present embodiment is used, the embedding property of the underlayer film forming composition is good, so that the low dielectric insulating film can be prevented from being exposed to the plasma during etching. For this reason, damage to the low dielectric insulating film is not caused and the dual damascene structure can be favorably formed. The first low dielectric insulating film (Low-k film) is not particularly limited as long as it can be disposed under the lower film ,. For example, an inorganic film can be used. The inorganic film system can be formed by, for example, ruthenium oxide, ruthenium nitride, ruthenium oxynitride, polysiloxane or the like. In particular, it can be formed by using commercially available products such as "Black Diamond" (manufactured by AMAT Corporation), "SYLK" (manufactured by Dow Chemical Co., Ltd.), and "LKD5109" (manufactured by JSR Corporation). The first low dielectric insulating film is, for example, a film formed by coating a substrate such as a wafer. The method of forming the first low dielectric insulating film is not particularly limited, and a well-known method can be used. For example, a coating method (SOD: Spin On Dielectric) and a chemical vapor deposition method (CVD: Chemical Vapor Deposition) can be used. The method of forming the composition by the underlayer film of the present embodiment to form the underlayer film is not particularly limited, and examples thereof include a spin coating method, a spray coating method, and a dip coating method. The film thickness of the underlayer film is not particularly limited, and is preferably 100 to 2000 nm, more preferably 200 to 100 nm, and particularly preferably 200 to 500 nm. When the film thickness of the underlayer film is less than 100 nm, a sufficient amount of the cover can not be formed on the processed substrate, and there is a possibility that the substrate cannot be processed. On the other hand, when it exceeds 2000 nm, for example, when a line and space resist pattern is formed, the vertical/horizontal ratio (aspect ratio) of the line portion becomes too large, and the line portion eventually collapses. . [3-1-2] Photoresist film forming step: Next, a step of forming a photoresist film on the formed underlayer film is performed. A photoresist film can be formed using the photoresist composition. As the photoresist composition, a conventionally known composition can be used, for example, a positive or negative type chemically amplified photoresist composition containing a photoacid generator, and an alkali-soluble resin and a quinone diazide-based photosensitive layer. A positive-type photoresist composition composed of an agent, a negative-type photoresist composition composed of an alkali-soluble resin and a crosslinking agent, and the like. The method of forming the photoresist film on the underlayer film is not particularly limited, and examples thereof include a spin coating method and the like. Specifically, the photoresist composition is applied onto the underlayer film by a spin coating method, followed by prebaking, and a photoresist film is formed by volatilizing the solvent in the coating film. In addition, the prebaking temperature can be appropriately adjusted according to the type of the photoresist composition used in the π photolithography, preferably 30 to 200 ° C, and 50 to 150 ° C is better. The film thickness of the photoresist film. The system is not particularly limited, and l〇〇~20000 nm is preferred, and 100 to 200 nm is more preferable. [3- 1-3] Resistive Pattern Forming Step: Next, a step of forming a photoresist pattern on the photoresist film is performed. The formation of the photoresist pattern can be formed by irradiating (exposing) the photoresist film with light such as radiation through a mask (intermediate mask) designed to describe the device. -33- 201009503 The radiation system for irradiating the photoresist film can be appropriately selected according to the type of (D) acid generator contained in the photoresist film, and examples thereof include visible light, ultraviolet light, far ultraviolet light, X-ray, electron beam, and 7 • Lines, molecular rays, ion beams, etc. Among them, especially ultraviolet light is preferred, especially KrF excimer laser (248nm), ArF excimer laser (I93nm>, F2 excimer laser (wavelength 17 7nm), Kr2 excimer laser (wavelength) 147nm), ArKr excimer laser (wavelength 134nm), far ultraviolet (wavelength I3nm, etc.). The imaging liquid used for imaging can be selected according to the type of photoresist composition. It contains positive chemical amplification light. The developing liquid used in the positive resist composition of the resist composition and the cerium soluble resin may, for example, be sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia or ethylamine. , n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, hydroxylated tetramethylammonium, hydroxylated tetraethylidene Base ammonium, pyrrole, piperidine, choline, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-decene An alkaline water-soluble q solution, etc. Further, in such an alkaline aqueous solution, a water-soluble organic solvent such as an alcohol such as methanol or ethanol or a surfactant may be appropriately added. Further, after the development of the photoresist film, it is preferable to wash and dry the photoresist film. Further, in order to improve the resolution, pattern outline, and developability, post-baking may be performed after exposure and before development. [3-1-4] First Transfer Step: Next, a step of using a photoresist film forming a photoresist pattern as a mask and transferring the photoresist pattern of the photoresist film to the underlayer film by etching is performed. As shown in FIG. 1 , the first low dielectric insulating film 2 , the lower film 3 , and the photoresist film 20 are sequentially disposed on the substrate 1 from the side of the substrate 1 in the order of -34-201009503, and are formed in this step. The photoresist film 20 of the photoresist pattern 14 serves as a mask, and the photoresist pattern 14 of the photoresist film 20 is transferred to the underlayer film 3 by etching. Further, FIGS. 1 to 10 illustrate one of the formation methods of the dual damascene structure. A schematic diagram of the step. The etching method is not particularly limited and can be carried out by a well-known method, that is, dry etching or wet etching. In the case of dry etching, the source gas system can be used, for example. 〇2, CO, co2 〇, etc., gas containing oxygen atoms, He, N2 Inert gas such as Ar, chlorine gas such as Cl2 or BCI2, and other H2, NH2, etc. These source gas systems may be used alone or in combination of two or more. -5] second transfer step: next, using a lower layer film of the transfer resist pattern as a mask, and transferring a photoresist pattern of the underlying film on the first low dielectric insulating film disposed under the lower layer film The method of transferring the photoresist pattern of the underlayer film to the first low dielectric barrier film is not particularly limited, and examples thereof include a method such as etching described above. Further, this step can be performed by using the above A transfer step is performed after the photoresist pattern is transferred (that is, formed) to the underlying film and etching is continued. For example, as shown in FIG. 2, in this step, the underlying film 3 of the transfer resist pattern is used as a mask, and the underlying film 3 is transferred onto the first low dielectric insulating film 2 disposed under the underlying film 3. The photoresist pattern is formed on the first low dielectric insulating film 2 to form the first recess 4. [3-1-6] Film removal step: -35 - 201009503 Next, a step of removing the photoresist film and the underlayer film by plasma ashing after transferring the photoresist pattern to the first low dielectric insulating film is performed. Here, the term "plasma ashing" means that a plasma of a reaction gas such as oxygen is generated in a gas phase, and an organic substance such as a photoresist film or a lower layer film is decomposed and removed into cox and h2o by the plasma. Wait. The condition of the plasma ashing is not particularly limited as long as the photoresist film and the underlayer film can be removed. For example, the high frequency power applied to the heating stage is preferably 100 to 1000 W, and more preferably 100 to 500 W. Further, the temperature of the heating stage is preferably 20 to 100 ° C, and more preferably 20 to 60 ° C. Further, the pressure in the processing container is preferably from 1 to 300 mtorr, and more preferably from 30 to 100 mtorr. The gas used for the plasma ashing is not particularly limited as long as the photoresist film and the underlayer film can be removed, and the viewpoint of suppressing the increase in the specific dielectric constant of the first low dielectric insulating film from the viewpoint of plasma ashing can be suppressed. In view of the above, it is preferred to contain at least one selected from the group consisting of nitrogen, hydrogen, ammonia, and argon. It is a mixed gas of nitrogen and hydrogen, a mixed gas of ammonia and argon, and a mixed gas of ammonia, nitrogen and hydrogen. Further, in the case of using a mixed gas of nitrogen and hydrogen, hydrogen is preferably 20 or less and hydrogen is preferably 1 to 10 in terms of a capacity ratio with respect to nitrogen 100. Further, in the case of using a mixed gas of ammonia and argon, argon is preferably 10 or less with respect to ammonia 100 in terms of a capacity ratio. 3 is a view showing that the photoresist film 20 and the underlayer film 3 shown in FIG. 2 are removed by plasma ashing, and the substrate 1 is left and disposed on the substrate 1 and the photoresist pattern is transferred (the first recess 4 is formed). The state of the first low dielectric insulating film 2. -36- 201009503 Next, the conductive material buried in the concave portion of the first low dielectric insulating film may be, for example, copper, aluminum or the like. The method of embedding the conductive material may, for example, be an electrolytic copper plating method. Thus, the desired wiring structure can be formed by embedding the conductive material in the photoresist pattern'. Fig. 5 shows an example in which copper is buried in the photoresist pattern (first recess 4) in which the first low dielectric insulating film 2 is formed, and the first wiring 6 is formed. [3-Bu 7] Other Steps: The above-described method of forming the dual damascene structure may be a step of forming an intermediate layer between the photoresist film and the underlayer film in addition to the above steps (intermediate layer forming step), in the film The step of forming a barrier metal layer on the surface of the first low dielectric insulating film and a portion of the substrate after the removing step (the barrier metal layer forming step). [3-l-7a] Intermediate layer forming step: In the intermediate layer forming step, the intermediate layer is formed in the resist pattern to fill the underlayer film, the photoresist film, and the layers which are insufficient for both functions. Can also form an intermediate layer. That is, for example, in the case where the anti-reflection function of the underlayer film is insufficient, the material of the intermediate layer in which the antireflection function can be applied to the intermediate layer can appropriately select the organic compound and the inorganic oxide in accordance with the necessary functions. Further, in the case where the photoresist film is an organic compound, an inorganic oxide may be applied to the intermediate layer. Commercially available products of the organic compound for forming the intermediate layer are all trade names, and examples thereof include "DUV-42", "DUV-44", "ARC-28", and "ARC-29" (above, Brewer Science, Inc.) "), "AR-3", "AR-19" (above, R〇hn and Hass), etc., forming -37-201009503 The inorganic oxide used for the intermediate layer is, for example, polyoxyalkylene. Titanium oxide, aluminum oxide, tungsten oxide, and the like. For example, "NFC SOG01" or "NFC SOG04" (manufactured by JSR Corporation), etc., may be used, and a method of forming an intermediate layer may be, for example, a coating method or a CVD method. Among these, a coating method for continuously forming an intermediate layer after forming an underlayer film is preferably used. The film thickness of the intermediate layer can be selected according to the function of the intermediate layer to select an appropriate film thickness to 10 ~3000nm is preferable, and 20~300nm is more preferable. The film thickness of the intermediate layer is lower than l〇nm, and the intermediate layer is cut in the middle of etching the underlayer film. On the other hand, if it exceeds 3000 nm, there is When the photoresist pattern of the photoresist film is transferred to the intermediate layer, the difference in processing change is remarkably caused. [3-l-7b] barrier metal layer forming step: in the barrier metal layer forming step, the barrier metal layer is formed Enhancing the adhesion of the conductive material and the low dielectric insulating film in the embedded light q-resist pattern (that is, the recess formed in the first low dielectric insulating film). Further, preventing the conductive material from diffusing (transfer) at a low level In the dielectric insulating film, the material of the barrier metal layer can be For example, tantalum, tantalum nitride, titanium, tantalum nitride, nails, etc. The method of forming the barrier metal layer can be performed, for example, according to a CVD method or the like. -38 - 201009503 Fig. 4 shows the first low dielectric insulating film 2 a surface, and a surface of the first recess 4 of the first low dielectric insulating film 2, a state in which the barrier metal layer 5 is formed. Further, after the lamination step, the conductive material and the barrier metal layer adhered to the surface of the low dielectric insulating film Preferably, the surface of the low dielectric insulating film is planarized by chemical honing (CMP) removal. [3-2] Second wiring forming step and third wiring forming step: in the second wiring forming step and In the three-wiring forming step, the method of forming the concave portion may be the same as the method of forming the concave portion in the first wiring forming step, and it is preferable to form the concave portion by the method described below. A second wiring layer and a third wiring layer are simultaneously formed. First, a third low dielectric insulating film is formed on the first wiring layer formed in accordance with the first wiring forming step. Subsequently, in the third low dielectric insulating film Upper shape A second low-dielectric insulating film. Further, a second low-dielectric insulating film and the third low-dielectric insulating film can be used with the system of the above-described first low-dielectric insulating film the same

The method of forming the second low dielectric insulating film and the third low dielectric insulating film of the G can be the same as the first low dielectric insulating film described above. Next, a third recess is formed in the second low dielectric insulating film and the third low dielectric insulating film. The method of forming the third recess may be the same as the method of forming the first recess described above. FIG. 6 shows an example of a state in which the third low dielectric insulating film 9 and the third low dielectric insulating film 7 form the third concave portion 12. -39- 201009503 Next, a second recess is formed in the second low dielectric insulating film. The method of forming the second recess may be the same as the method of forming the first recess described above. Specifically, it can be carried out as follows. First, in addition to coating the underlayer film forming composition of the present embodiment on the second low dielectric insulating film, the second low dielectric insulating film and the third low dielectric insulating film are buried in the third recess formed, A film (lower film) is formed on the surface of the second low dielectric insulating film. Further, the method of forming the underlayer film forming composition is not particularly limited, and examples thereof include a spin coating method, a spray coating method, and a dip coating method. Next, after a photoresist film is formed on the formed underlayer film, a photoresist pattern is formed on the photoresist film. Next, a photoresist film formed using a photoresist pattern is used as a mask, and the photoresist pattern of the photoresist film is transferred to the underlayer film by etching. Fig. 7 shows a state in which the photoresist film 22 formed using the photoresist pattern is used as a mask, and the photoresist pattern of the photoresist film 22 is transferred to the underlayer film 13 by etching. Next, the underlying film was transferred as a mask using a photoresist pattern, and the photoresist pattern of the lower β layer film was transferred onto the second low dielectric insulating film disposed under the underlying film. 8 is a view showing that the underlayer film 13 is transferred as a mask using a photoresist pattern, and the photoresist pattern of the underlayer film 13 is transferred onto the second low dielectric insulating film 9 disposed under the underlayer film 13 (forming a second The state of the recess 14). Next, the photoresist film and the underlayer film are removed by plasma ashing. At this time, the plasma ashing is used, and the underlayer film forming composition buried in the third recess formed in the third low dielectric insulating film is also removed. FIG. 9 is a view showing that the photoresist film 22 and the underlying film 13 shown in FIG. 8 are removed by plasma ashing, and -40-201009503 on the second low dielectric insulating film 9 and the third low dielectric insulating film 7, respectively. A state in which the second recess 14 and the third recess 12 are formed. Then, by embedding the conductive material in the second recess and the third recess, the second wiring and the third wiring connecting the first wiring and the second wiring can be simultaneously formed. Further, the barrier metal layer described above may be formed before the conductive material is buried in the second recess and the third recess. 1 shows that the barrier metal layer 15 is formed before the conductive material is buried in the second recess 14 and the third recess 12 shown in FIG. 9, and then the conductive material is buried in the second recess 14 and the third recess 12, The second wiring 31 and the third wiring 16 connecting the first wiring 6 and the second wiring 31 can be simultaneously formed. Thus, the second wiring layer 29 having the first wiring layer 25' forming the first wiring 6 and the second wiring layer 29 forming the second wiring 31, and the third wiring 16 connecting the first wiring 6 and the second wiring 31 can be manufactured. The dual damascene structure 100 of the wiring layer 27. Further, after the conductive material is buried in the second recess and the third recess, chemical honing (CMP) can be performed. (Examples) Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited to the Examples and Comparative Examples. Further, "parts" and "%" in the "Examples" are quality standards unless otherwise specified. (Synthesis Example 1) In a separation flask equipped with a thermometer, 'in a gas nitrogen atmosphere' was fed as a monomer for providing a structural unit represented by the general formula (1) (in Tables i and 2, 'represented as "monomer (1) 70% of the sputum (indicated as "M_1_1" in Table 1 < 2], as a monomer providing the structural unit represented by the general formula (2) (in Tables i and 2, 'represented as -41-201009503' 20 parts of hydroxyethyl methacrylate (indicated as "M-2-l" in Table 1) of the monomer (2)"), and a monomer which provides a structural unit represented by the general formula (3) (Table 1, In 2, 10 parts of styrene (indicated as "M-3-1" in Tables 1 and 2), which is represented by "monomer (3)"), is represented as a radical polymerization initiator (expressed by the formula (4)). Provided as 2,2'-azobis(2-methylbutyrate dimethyl ester) of the monomer of the structural unit (manufactured by Wako Pure Chemical Industries, Ltd., trade name "V-60 1"), which is indicated in Table 1 as " 10 parts of a polymerization initiator [V-6011" and 400 parts of methyl isobutyl ketone were polymerized at 90 ° C for 4 hours while stirring. After the end of the polymerization, the solution was water-cooled and cooled to below 30 °C. After cooling, the polymerization solution was poured into a large amount of methanol to precipitate a white solid. Subsequently, the precipitated white solid was separated by decantation, and the separated white solid was washed with a large amount of methanol. After washing, it was dried at 50 ° C for 17 hours to obtain a polymer (A-1). The weight average molecular weight (Mw) of the obtained polymer (A-1) was measured by the conditions shown below. [Measurement of weight average molecular weight (Mw)]: GPC column (G2000HXL: 2, G3000HXL: 1) manufactured by TOSO Co., Ltd., flow rate: 1.0 mL/min, solvent: tetrahydrofuran, column temperature: 40 Under the analysis conditions of °C, the monodisperse polyphenylene was used as a standard gel permeation chromatograph (detector/differential thermal analyzer). In addition, in Table 1 and Table 2, it shows the "molecular weight." The weight average molecular weight (Mw) of the polymer (A-1) obtained in the present synthesis example was 2,800. (Synthesis Example 2 to 26) -42-201009503 The monomer and the radical polymerization initiator shown in Table 1 were synthesized in the same manner as in Synthesis Example 1 except that the compounding amount shown in Table 1 was used. 2) ~ Polymer (A-26), and the weight average molecular weight (Mw) of each polymer was measured. The results are shown in Table 1. In addition, in Tables 1 to 4, "parts" means parts by mass.

-43- 201009503

Table 1 Polymer monomer (1) (type/part) Monomer (2) (type/part) Monomer (3) (type/part) Polymerization initiator [V-601] (part) Molecular weight (Mw) Synthesis Example 1 Α-1 Μ-1-1/70 Μ- 2-1/20 Μ-3-1/10 10 2800 Synthesis Example 2 Α-2 Μ-1-1/70 Μ-2-1/20 Μ-3- 1/10 15 2000 Synthesis Example 3 Α-3 Μ-1-1/70 Μ-2-1/20 Μ-3-2/10 20 1600 Synthesis Example 4 Α-4 Μ-1-1/70 Μ-2 -1/20 Μ-3-3/10 10 2500 Synthesis Example 5 Α-5 Μ-1-1/60 Μ-2-1/20 Μ-3-1/20 10 2400 Synthesis Example β Α-6 Μ- 1-1/60 Μ-2-1/20 Μ-3-2/20 10 2800 Synthesis Example 7 Α-7 Μ-1-1/60 Μ-2-1/20 Μ-3-3/20 10 2900 Synthesis Example 8 Α-8 Μ-1-1/60 Μ-2-2/20 Μ-3-1/20 10 2900 Synthesis Example 9 Α-9 Μ-1-1/60 Μ-2-1/10 Μ -3-1/20 Μ-3-2/10 10 2200 Synthesis Example 10 Α-10 Ml-1/50 Μ-2-1/20 Μ-3-1/30 10 2700 Synthesis Example 11 Α-11 Μ- 1-1/50 Μ-2-1/10 Μ-3-1/20 Μ-3-2/20 10 2400 Synthesis Example 12 Α-12 Μ-1-1/50 Μ-2-1/10 Μ- 3-1/20 Μ-3-2/20 20 1800 Synthesis Example 13 Α-13 Κ4-1-1/50 Μ-2-1/30 Μ-3-1/20 10 2800 Synthesis Example 14 Α-14 Μ -1-1/55 Μ-2-1/20 Μ-3-1/25 10 2700 Synthesis Example 15 Α-15 Μ-1-1/30 Μ-1-2/20 Μ-2-2/ 20 Μ-3-1/30 10 2700 Synthesis Example 16 Α-16 Μ-1-1/4 Μ-2-1/48 Μ-3-1/48 10 2500 Synthesis Example 17 Α-17 Μ-1-1 /6 Μ-2-1/47 Μ-3-1/47 10 2800 Synthesis Example 18 Α-18 Μ-1-1/85 Μ-2-1/10 Μ-3-1/5 10 2700 Synthesis Example 19 Α-19 Μ-1-1/48 Μ-1-1/4 Μ-3-1/48 10 2700 Synthesis Example 20 Α-20 Μ-3-1/47 Μ-1-1/6 Μ-3- 1/47 10 2800 Synthesis Example 21 Α-21 Μ-1-1/5 Μ-1-1/85 Μ-3-1/10 10 2800 Synthesis Example 22 Α-22 Μ-1-1/74 Μ-2 -1/25 Μ-3-1/1 10 2700 Synthesis Example 23 Α-23 Μ-1-1/30 Μ-2-1/25 Μ-3-1/45 10 2700 Synthesis Example 24 Α-24 Μ- 1-1/20 Μ-2-1/25 Μ-3-1/55 10 2500 Synthesis Example 25 Α-25 Μ-1-1/55 Μ-2-1/20 Μ-3-1/25 25 400 Synthesis Example 26 Α-26 Μ-1-1/55 Μ-2-1/20 Μ-3-1/25 20 600 -44- 201009503 (Synthesis Example 27) In a separation flask equipped with a thermometer, in a nitrogen atmosphere Xenon T, 50 parts of decene, hydroxymethyl decene (in Tables 1 and 2, it is expressed as "m_12 parts, azo-isobutyronitrile as a radical polymerization initiator (Table 2 φ, _ "Polymerization Initiator [AIBN] 】") 25 parts and methyl isobutyl _ 4 聚合 were stirred at 60 ° C for 15 hours while stirring. After the end of the polymerization, the solution was polymerized and cooled to below 30 °C. After cooling, the polymerization solution was a large amount of n-heptane to precipitate a white solid. Subsequently, the white solid was separated by decantation and washed with a large amount of n-heptane. After washing, it was dried at 50 ° C for 17 hours to obtain a polymer (CA-1). The weight average molecular weight (Mw) of the polymer (CA-1) obtained in the present synthesis example was 1,300. (Synthesis Example 28 to 3 1 In the same manner as in Synthesis Example 30 except that the monomer and the base polymerization initiator shown in Table 2 were used in the amounts shown in Table 2, polyfluorene (CA-2) to polymer (CA-5) was synthesized. The polymer was measured for the weight average fraction (Mw). The results are shown in Table 2. Feed j) 5 parts, water-cooled, isolated, in the amount of free compound -45-201009503 Table 2 Polymer monomer (1) (type /part) Monomer (2) (type/part) Monomer (3) (type/part) Polymerization initiator [AIBN] (part) Molecular (Mw) Synthesis Example 27 CA-1 M-1-1/50 M-1-2/50 - — AIBN/25 1300 Synthesis Example 28 CA-2 M-1-1/50 M-1-2/50 — — AIBN/10 2800 Synthesis Example 29 CA-3 M-1-1 /55 M-2-1/20 M-3-1/25 AIBN/10 2500 Synthesis Example 30 CA-4 M-1-1/70 One M-3-1/30 AIBN/10 2500 Synthesis Example 31 CA- 5 M-1-1/50 M-3-1/20 M-3-2/30 AIBN/10 2600 In addition, in Tables 1 and 2, 'M-2-2' means hydroxyethyl acrylate, "M -3-2" means hydroxymethylstyrene "M-3-3" represents a third butoxystyrene. (Example 1) The polymer (Al) obtained in Synthesis Example 1 was mixed in an amount of 1.0 part by weight as the (B)-crosslinking agent. (7) The compound (tetrabutoxymethyl glycoluril (manufactured by CAR本CARBIDE), Tables 3 and 4, expressed as "Bl") 3. 〇, propylene glycol monomethyl as (C) solvent Ethyl ether acetate (expressed as "C-1" in Tables 3 and 4) 86_5 parts, and bis(4-t-butylphenyl) iodonium nonafluoro-n-butyl as (D) acid generator The alkane sulfonate (manufactured by Green Chemical Co., Ltd., trade name "BBI-109", and Tables 3 and 4, expressed as "D-1"} 0.5 parts, and dissolved to obtain a mixed solution. The resulting mixed solution was filtered to prepare an underlayer film-forming composition. -46- 201009503 /7-〇4, Hg A7-C4H9

N N

N, .N (7)

Sn-C4Hg / T-C4Hg The properties shown below were evaluated for the film formation composition under preparation. (1) Etch resistance: The underlayer film was coated by a spin coating method to form a composition on a ruthenium substrate, and after calcination at 220 ° C for 60 seconds, an underlayer film having a film thickness of 300 nm was formed. Subsequently, an underlayer film was etched (pressure: 〇.〇3 Torr, high-frequency power: 300 W, Ar/CF4 = 40/lOOsccm, substrate temperature: 20 °C), and the film thickness of the underlayer film after the etching treatment was measured. Further, the etching rate (nm/min) was calculated from the relationship between the amount of decrease in film thickness and the treatment time, and was used as an evaluation criterion for etching resistance (indicated as "etching rate (nm/min)" in Tables 5 and 6). Further, the smaller the number of etching rates, the more excellent the etching resistance. (2) Buried property: The underlayer film forming composition was well immersed in the via hole, and the following evaluation was performed as to whether or not the film was buried well. First, after forming a composition by spin coating a lower layer film on a substrate having a via hole size of 70 nm, a via pitch of 1 H/1.2 S, and a depth of 40 Å. Heat on a hot plate at 200 °C for 60 seconds. Thus, a lower layer of -47-201009503 film was formed on the surface of the TEOS in the via hole. Further, the film thickness of the underlayer film was 300 nm. Next, the state of the underlying film buried in the via hole was observed by a scanning type electron micromirror, and the embedding property was evaluated. The evaluation criteria are the case where the underlayer film is formed in the via hole, that is, the case where the underlayer film is buried in the via hole, and the case where the underlayer film is not buried in the via hole is "X". (3) Hardening temperature: The underlayer film was coated by a spin coating method to form a composition on a ruthenium substrate, and calcined at 140 to 400 ° C for 60 seconds to obtain an underlayer film. The underlying film was immersed in propyl glycol monomethyl ether acetate for 1 minute at room temperature. Further, the film thickness change of the underlayer film before and after the immersion was measured using a spectroscopic ellipsometer "UV1280E" (manufactured by KLA-TENCOR Co., Ltd.) and evaluated. In the evaluation, the lowest temperature at which the film thickness is not changed is referred to as the "hardening temperature" (in Tables 5 and 6, it is expressed as "hardening temperature (°C)"). Further, in the case of calcination at a temperature of 250 ° C, when the film thickness was observed to change, it was also set to "X". q (4) Sublimation amount: The underlayer film was spin-coated on a ruthenium substrate having a diameter of 8 Å to form a composition. Subsequently, it was heated on a hot plate at 140 to 400 ° C for 60 seconds to obtain an underlayer film having a film thickness of 300 nm. The amount of the sublimate produced from the underlayer at this time was measured (in Tables 5 and 6, it is expressed as "sublimation amount (mg)"). Further, the capture of the sublimate is carried out as follows. First, prepare a heating plate. Next, the 8 吋 矽 wafer of the previously measured weight was attached to the cover of the heating plate. Next, after heating the heating plate, the lower layer film is spin-coated to form a composition on the crucible substrate, and a heating plate is used to apply heat of -48 to 201009503. Next, on the underlayer film of the substrate on which the underlayer film was formed by spin coating, the underlayer film was spin-coated to form a composition, which was heated by a hot plate. Moreover, these steps are performed 100 times. Subsequently, the weight of the 8 吋矽 wafer attached to the cover was measured. Next, the difference in weight of the 8 吋矽 wafer was calculated as the amount of sublimation, and the amount of sublimation was confirmed. (5) Refractive index: The composition film was applied onto a ruthenium substrate by a spin coating method, and calcined at 200 ° C for 60 seconds to obtain an underlayer film having a film thickness of 300 nm. Then, using a spectroscopic ellipsometer "VUV-VASE" (manufactured by J.A. Woollam Co., Ltd.), an optical constant (refractive index) at a wavelength of 193 nm was calculated (in Tables 5 and 6, "refractive index (?)"). Further, when the refractive index (??) is in the range of 1.40 to 1.60, it can be judged that it has sufficient function as an antireflection film in the ArF exposure resist step. (6) Extinction coefficient: The underlayer film is coated by a spin coating method to form a composition on the ruthenium substrate,

After calcination at 200 ° C for 60 seconds, an underlayer film having a film thickness of 300 nm was obtained. Then, using a spectroscopic ellipsometer "VUV-VASE" (manufactured by J.A. Woollam Co., Ltd.), an optical constant (extinction coefficient) at a wavelength of 193 nm (indicated as "extinction coefficient (k値)" in Tables 5 and 6) was calculated. Further, when the extinction coefficient (k値) is in the range of 0.25 to 0.40, it can be judged that it has sufficient function as an antireflection film in the ArF exposure photoresist step. In the present embodiment, the results of the respective performance evaluations were 67 in etching resistance, the embedding property was "〇", the hardening temperature was 180 ° C, the sublimation amount was 1.8 mg, the refractive index was 1.55, and the extinction coefficient was 0.28. » -49- 201009503 (Examples 2 to 36, Comparative Examples 1 to 10) In addition to the various components and blending amounts shown in Tables 3 and 4, the lower layer film forming composition was prepared in the same manner as in Example 1, and the lower layer was formed. The film-forming composition was subjected to the above various performance evaluations. The evaluation results are shown in Tables 5 and 6. ❹

-50- 201009503

Polymer (A) Solvent (B) Crosslinking agent (C) | Acid generator (D) I Type compounding amount (part) Type compounding amount (part) Type compounding amount (part) Type compounding amount (part) Example 1 A-1 10.0 B-1 86.5 C-1 3.0 D-1 0.5 Example 2 A-1 10.0 B-1 87.5 C-1 2.0 D-1 0.5 Example 3 A-1 10.0 B-1 87.5 C-2 2.0 D-1 0.5 Example 4 A-2 10.0 B-1 86.5 C-1 3.0 D-1 0.5 Example 5 A-2 10.0 B-1 87.5 C-1 2.0 D-1 0.5 Example 6 A-2 10.0 B -1 87.5 C-2 2.0 D-1 0.5 Example 7 A- 3 10.0 B-1 86.5 C-1 3.0 D-1 0.5 Example 8 A-3 10.0 B-1 87.5 C-1 2.0 D-1 0.5 Implementation Example 9 A-4 10.0 B-1 86.5 C-1 3.0 D-1 0.5 Example 10 A-5 10.0 B-1 86.5 C-1 3.0 D-1 0.5 Example 11 A-6 10.0 B-1 86.5 C- 1 3.0 D-1 0.5 Example 12 A-7 10.0 B-1 86.5 C-1 3.0 D-1 0.5 Example 13 A-8 10.0 B-1 86.5 C-1 3.0 D-1 0.5 Example 14 A-9 10.0 B-1 86.5 C-1 3.0 D-1 0.5 Example 15 A-10 10.0 B-1 86.5 C-1 3.0 D-1 0.5 Example 16 A-11 10.0 B-1 86.5 C-1 3.0 D-1 0.5 Example 17 A-11 10.0 B-1 88.0 C-1 1.5 D-1 0.5 Example 18 A-12 10.0 B-1 86.5 C-1 3.0 D-1 0.5 Example 19 A-12 10.0 B-1 87.5 C-1 2.0 D-1 0.5 Example 20 A-13 10.0 B-1 86.5 C-1 3.0 D-1 0.5 Example 21 A-13 10.0 B -1 87.5 C-1 2.0 D-1 0.5 Example 22 A-14 10.0 B-1 87.5 C-1 2.0 D-1 0.5 Example 23 A-14 10.0 B-1 88.5 C-1 1.0 D-1 0.5 Implementation Example 24 A-14 10.0 B-1 88.5 C-2 3.0 D-1 0.5 Example 25 A-15 10.0 B-1 87.5 C-1 2.0 D-1 0.5 Example 26 A-16 10.0 B-1 87.5 C- 1 3.0 D-1 0.5 Example 27 A-17 10.0 B-1 87.5 C-1 3.0 D-1 0.5 Example 28 A-18 10.0 B-1 87.5 C-1 3.0 D-1 0.5 Example 29 A-19 10.0 B-1 87.5 C-1 3.0 D-1 0.5 Example 30 A-20 10.0 B-1 87.5 C-1 3.0 D-1 0.5 A-21 10.0 B-1 87.5 C-1 3.0 D-1 0.5 A- 22 10.0 B-1 87.5 C-1 3.0 D-1 0.5 A-23 10.0 B-1 87.5 C-1 3.0 D-1 0.5 A-24 10.0 B-1 87.5 C-1 3.0 D-1 0.5 A-25 10.0 B-1 87.5 C-1 3.0 D-1 0.5 A-26 10.0 B-1 87.5 C-1 3.0 D-1 0.5 -51- 201009503 Table 4 Polymer (A) Solvent (B) Crosslinker Busy) Acid generation (D) Type of compound (parts) Type of compound (parts) Type of compound (parts) Type of compound (parts) Comparative example 1 C A-1 10.0 B-1 89.0 C-1 0.5 D-1 0.5 Comparative Example 2 CA-1 10.0 B-1 89.0 C-2 0.5 D-1 0.5 Comparative Example 3 CA-1 10.0 B-1 89.0 C-3 0.5 D-1 0.5 Comparative Example 4 CA-2 10.0 B-1 86.5 C-1 1.0 D-1 0.5 Comparative Example 5 CA-3 10.0 B-1 86.5 C-1 3.0 D-1 0.5 Comparative Example 6 CA-3 10.0 B -1 89.0 C-3 3.0 D-1 0.5 Comparative Example 7 CA-4 10.0 B-1 86.5 C-1 3.0 D-1 0.5 Comparative Example 8 CA-4 10.0 B-1 89.1 C-3 3.0 D-1 0.5 Comparison Example 9 CA-5 10.0 B-1 86.6 C-1 3.0 D-1 0.5 Comparative Example 10 CA-5 10.0 B-1 86.5 C-3 3.0 D-1 0.5 In addition, in Tables 3 and 4, "B-2" The compound represented by the following formula (8) (n-butyl etherified hexamethylol melamine) and "B-3" represent a compound represented by the following formula (9) (tetramethoxymethyl glycoluril) n-C4Hg

/7-C4H9 /7-C4Hg -52- 201009503 h3c

(9)

H3c

ο

-53- 201009503

Table 5 Etching rate (nm/min) Buried hardening temperature CC) Sublimation amount (mg) Refractive index [n値] (193 nm) Recession coefficient [kffi] (I93 nm) Example 1 67 〇 180 1.8 1.55 0.28 Example 2 67 〇 190 1.6 1.45 0.29 Example 3 65 〇 180 2.0 1.54 0.29 Example 4 69 〇 200 3.3 1.55 0.28 Example 5 69 〇 210 3.5 1.54 0.29 Example 6 69 〇 200 3.2 1.54 0.29 Example 7 72 〇 200 4.5 1.56 0.27 Example 8 72 〇 210 4.2 1.55 0.28 Example 9 71 〇 180 1.3 1.57 0.26 Example 10 76 〇 180 1.7 1.53 0.30 Example 11 77 〇 180 1.7 1.53 0.29 Example 12 76 〇 180 1.9 1.54 0.29 Example 13 75 〇 180 1.6 1.54 0.29 Example 14 72 〇 180 1.5 1.48 0.33 Example 15 78 〇 180 1.8 1.49 0.32 Example 16 72 〇 180 1.5 1.44 0.36 Example 17 71 〇 200 1.8 1.41 0.38 Example 18 73 〇 180 3.0 1.44 0.36 Example 19 73 〇200 3.6 1.43 0.37 Example 20 79 〇180 2.2 1.56 0.26 Example 21 80 〇190 1.8 1.55 0.27 Example 22 75 〇180 1.6 1.54 0.28 Example 23 77 〇200 1.9 1.53 0.30 Example 24 78 〇190 2.1 1.55 0.28 Example 25 76 〇190 1.9 1.56 0.28 Example 26 96 〇180 1.9 1.56 0.56 Example 27 93 〇180 1.8 1.55 0.54 Example 28 60 〇210 2.1 1.54 0.18 Example 29 65 〇230 1.9 1.53 0.55 Example 30 68 〇 230 2.0 1.55 0.55 Example 31 78 〇 180 1.8 1.56 0.20 Example 32 76 〇 180 2.1 1.55 0.16 Example 33 82 〇 180 1.9 1.56 0.50 Example 34 85 〇190 2.0 1.55 0.53 Example 35 75 〇220 9.8 1.54 0.30 Example 36 73 〇220 8.5 1.53 0.30 -54- 201009503 Table 6 Etching rate (nm/min) Buried hardening temperature (V) Sublimation halo (mg) Refraction coefficient [η値] ( I93nm) Decay coefficient [k値] (193nm) Comparative Example 1 70 〇200 8.2 1.46 0.28 Comparative Example 2 70 〇200 8.8 1.45 0.23⁄4 Comparative Example 3 69 〇200 12.5 1.46 0.28 Comparative Example 4 73 X 200 6.2 1.46 0.28 Comparative Example 5 78 〇180 2.1 1.50 0.23 Comparative Example 6 80 〇180 6.2 1.49 0.24 Comparative Example 7 74 XX 1.9 1.46 0.27 Comparative Example 8 72 XX 6.6 1.45 0.28 Comparative Example 9 72 X 190 1.8 1.41 0.42 Comparative Example 10 80 X 190 6.3 1.40 0.43

As is apparent from Tables 5 and 6, the underlayer film formed by the film formation compositions of Examples 1 to 36 can be compared with the underlayer film formed by the film formation composition of Comparative Example 1 to 1〇. It was confirmed that the etching resistance and the embedding property were excellent, and the amount of sublimation was small. Further, since the underlayer film formed of the underlayer film forming compositions of Examples 1 to 36 is set to have an optimum function as an antireflection film in the ArF exposure resist step, η値 and k値 are set to be in an optimum range of sufficient function as an antireflection film in the ArF exposure resist step. It was confirmed that it has sufficient function as an antireflection film. On the other hand, the underlayer film formed of the underlayer film forming compositions of Comparative Examples 1 to 10 was an underlayer film which was inferior in etching resistance, embedding property, sublimation amount, and function as an antireflection film. Specifically, since the layer-forming composition of Comparative Examples 1 to 3 contains the (A) polymer having a small weight average molecular weight, the amount of the sublimate is increased even if the embedding property is excellent. On the other hand, the underlayer film of Comparative Example 4 was formed to have a composition of -55 to 201009503. Since the (A) polymer having a large weight average molecular weight was contained, even if the amount of the sublimate was decreased, good embedding property was not obtained. Further, since the underlayer film-forming compositions of Comparative Examples 7 and 8 have an appropriate crosslinking group in the structure containing the (A) polymer, film hardening can be formed at a low temperature of 250 °C or lower. Further, the film formation composition k 之下 under the comparative examples 5 to 10 was not in the most appropriate range. Further, in the lower film forming compositions of Comparative Examples 7 to 10, since the (A) polymer contained did not have the structural unit (2), it was confirmed that the embedding property was poor. INDUSTRIAL APPLICABILITY The underlayer film forming composition of the present invention is in a manufacturing process of a semiconductor device, and specifically, a plurality of substances as a film to be processed are deposited on a germanium wafer, and processed therein. In the step of forming the desired pattern by the film, it is suitable as a composition for forming the underlying film to be used. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a step of a method of forming a dual damascene π structure for forming a composition using the underlayer film of the present invention. Fig. 2 is a schematic view showing a step of a method of forming a dual damascene structure using the underlayer film forming composition of the present invention. Fig. 3 is a schematic view showing a step of a method of forming a dual damascene structure using the underlayer film forming composition of the present invention. Fig. 4 is a schematic view showing a step of a method of forming a dual damascene structure using the underlayer film forming composition of the present invention. Fig. 5 is a schematic view showing a step of a method of forming a dual damascene structure using the underlayer film forming composition of the present invention. -56- 201009503 Fig. 6 is a schematic view showing a step of a method of forming a dual damascene structure using the underlayer film forming composition of the present invention. Fig. 7 is a schematic view showing a step of a method of forming a dual damascene structure using the underlayer film forming composition of the present invention. Fig. 8 is a schematic view showing a step of a method of forming a dual damascene structure using the underlayer film forming composition of the present invention. Fig. 9 is a schematic view showing a step of a method of forming a dual damascene structure using the underlayer film forming composition of the present invention. Fig. 1 is a schematic view showing a double damascene structure obtained by forming a composition using the underlayer film of the present invention. [Description of main component symbols] 1 : Substrate 2: First low dielectric insulating film 3, 11, 13: Lower film 4: First recess 0 5, 15: Barrier metal layer 6: First wiring 7: Third low dielectric Electrical insulating film 8, 10: etching stop layer 9: second low dielectric insulating film 12: third recess 14: second recess 16: third wiring 20, 21, 22: photoresist film - 57 - 201009503 25 : 27 : 29 : 3 1: First wiring layer Third wiring layer Second wiring layer Second wiring 100 : a barrier metal layer.

Claims (1)

201009503 / VII. Patent application scope: 1 . An underlayer film forming composition comprising: (A) a structural unit represented by the following general formula (1) and a structural unit 13 represented by the following general formula (2), a structural unit represented by the following formula (3) and a polymer of a structural unit represented by the following formula (4), (B) a crosslinking agent having a butyl ether group, and (C) a solvent, R2 R3 (However, in the above formula (1), R1 represents a hydrogen atom, an alkyl group which may be substituted with 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having a carbon number of 6, a carboxyl group, and an alkoxy group having 1 to 6 carbon atoms. a carbonyl group, an alkoxycarbonyloxy group having 1 to 6 carbon atoms, a hydroxymethyl group, or an alkoxymethylol group having a carbon number of 6, wherein R 2 and R 3 each represent a hydrogen atom or a carbon number of 6 Substitutable alkyl) R4 —(-ch2—— .C=0 〇/ (2) \s I OH (However, in the above formula (2), R4 represents a hydrogen atom or a methyl group, and R5 represents a carbon number of 1 ~4 alkylene group) -59- 201009503 (However, in the above formula (3), R6 represents a hydrogen atom, an alkyl group which may be substituted with 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a carboxyl group, and a carbon number of 1 to 60; Alkoxycarbonyl group, alkoxycarbonyloxy group having 1 to 6 carbon atoms, hydroxymethyl group, or alkoxymethylol group having 1 to 6 carbon atoms, and R7 represents a hydrogen atom or a carbon number of 6 Alkyl group, η represents an integer of 1 to 3 > R10 - 〇-CC-- Ο R8 (However, in the above formula (4), R8, R9 and R1Q each independently represent a hydrogen atom and have a carbon number of 1 to 6 2. The film forming composition under the first aspect of the patent application, wherein the (A) polymer has a polystyrene-equivalent weight average molecular weight (Mw) of 500 to 10,000. 3. The film forming composition under the first or second aspect of the patent application, wherein the (B) crosslinking agent is a compound represented by the following formula (5) or (6), Ο 60-201009503 (However, in the above formula (5), R11 each independently represents a hydrogen atom, a methyl group, an n-butyl group or an isobutyl group; however, two or more of the four R11 groups are positive. Butyl or isobutyl OR12 OR12 (6) (However, in the above formula (6), R12 each independently represents a hydrogen atom, a methyl group, a n-butyl group or an isobutyl group; but two or more of the six R12 groups are n-butyl or different Butyl). 4. The film-forming composition of any one of the above-mentioned items (1), wherein the ratio of the structural unit represented by the above formula (1) contained in the polymer (A) is relative to The total structural unit 100 of the above (A) polymer has a molar % Q of 5 to 80 mol%; the ratio of the structural unit represented by the above formula (2) contained in the above (A) polymer is relative to The total structural unit of the above (A) polymer has a molar percentage of 5 to 80 mol%; the ratio of the structural unit represented by the above formula (3) contained in the above (A) polymer is relative to The total structural unit 100 of the above (A) polymer has a molar percentage of 0.1 to 50% by mole. 5. The film forming composition under any one of claims 1 to 4, which further contains (D) an acid generator. -61-