KR100717511B1 - Polymer for Gap-Filling of Semiconductor Device and Coating Compositions using thereof - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor fine gap fill polymer, wherein air voids and the like are commonly used in a spin coating method for semiconductor substrates having a diameter of 100 nm or less and a hole having an aspect ratio of 1 or more in terms of height / diameter. Complete gap fill is possible without defects, and the film can be melted to a desired thickness by an aqueous alkali solution (called developer), and is resistant to isopropyl alcohol (IPA) and plasma etching after curing by baking. It provides a composition that can be removed quickly inside the hole by ashing treatment.

Gap-Fill, Dissolution Rate, Spin Coating, Semiconductor

Description

Polymer for Gap-Filling of Semiconductor Device and Coating Compositions using

The present invention relates to a polymer for semiconductor fine gap fill and a composition using the same. It is important that the coating composition for semiconductor fine gap fill of this invention has the following characteristics. (1) It is possible to completely fill a hole having an aspect ratio of 1 or more and a diameter of 100 nm or less by a general spin coating, and to planarize the substrate to a certain thickness. (2) The film filled in the hole. No voids or gaps in the air, (3) the thickness of the film after coating is constant regardless of the density of holes on the substrate, and (4) the flattening film has a constant dissolution rate in the developer. To be able to dissolve the film to a desired thickness, (5) after thermal curing, the thickness does not change by 60 to 70 ° C. isopropyl alcohol (IPA) cleaning, and (6) after thermal curing to plasma etching. The composition for semiconductor microgap fill, which satisfies the above seven characteristics, is required to have strong resistance, and (7) ashing treatment to leave no residues inside the hole at all and to quickly remove it. need.

Conventionally, silicon oxide is deposited by using a plasma enhanced CVD method for semiconductor fine gap fill, and the oxide layer is removed to a desired thickness by chemical mechanical polishing or an oxide etch-back process. However, in this process, as the diameter of holes or trenches is reduced to 100 nm or less, defects such as air voids and gaps are generated in the holes during oxide deposition. In order to solve such defects during oxide deposition, ALD (Atomic layer Deposition) equipment should be introduced, but there is a problem that the productivity is reduced because the equipment is very expensive and the oxide deposition rate is slow.

    Therefore, the present invention overcomes the problems of the prior art and has a strong resistance to isopropyl alcohol (IPA) and plasma etching after curing by baking, and can be quickly removed from the inside of the hole by ashing. It is a technical problem to provide a fine gap fill polymer and a composition using the same.

The present invention provides a polymer for semiconductor fine gap fill (Gap-Fill) comprising the following general formula (1) and (2) as structural units.

[Formula 1]

 (Wherein Ra represents hydrogen or a methyl group, R 1 is an alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aromatic ring group, a cycloalkyl group or benzyl group having 3 to 10 carbon atoms, X is hydrogen or a vinyl group, m is 0 to 10.)

[Formula 2]

 (Wherein Rb represents hydrogen or a methyl group)

30 to 95 mole% of the structural unit of Formula 1, and 5 to 70 mole% of the structural unit of Formula 2.

In another aspect, the present invention provides a polymer for a semiconductor fine gap fill, characterized in that it further comprises a structural unit of the formula (3).

[Formula 3]

(Wherein Rc represents hydrogen or a methyl group and n is 1 to 10)

It is characterized by containing 1 to 50 mol% of the structural unit of the formula (3).

The semiconductor fine gap fill polymer is characterized by having a weight average molecular weight of 2000 ~ 30000.

The semiconductor fine gap fill polymer is characterized by having a weight average molecular weight of 4000 ~ 15000.

In the present invention, there is provided a composition for semiconductor fine gap fill, comprising the polymer for semiconductor fine gap fill, a crosslinking agent, an acid catalyst, and an organic solvent.

The crosslinking agent is characterized in that the melamine-based, substituted urea-based, the polymer containing an epoxy group and the compound derived from them.

The crosslinking agent in the composition for a semiconductor fine gap fill is characterized in that it contains 0.1 to 30 parts by weight per 100 parts by weight of the polymer for semiconductor fine gap fill.

The acid catalyst is at least one selected from mineral acid, sulfonic acid, sulfonic acid, oxalic acid, maleic acid, hexamic cyclohexylsulfonic acid, and phthalic acid. It is characterized by being an acid.

The acid catalyst in the composition for a semiconductor fine gap fill is characterized in that it comprises 0.01 to 10 parts by weight per 100 parts by weight of the polymer for semiconductor fine gap fill.

The organic solvent is diethylene glycol monomethyl ether, diethylene glycol diethyl ether, ethyl-3-ethoxy propionate, methyl-3-methoxy propionate, cyclopentanone, cyclohexanone, propylene glycol methyl ether Acetate, ethyl lactate, cyclopentanone, hydroxyethyl acetate and the like.

The organic solvent in the composition for semiconductor fine gap fill is characterized in that it comprises 100 to 3000 parts by weight per 100 parts by weight of the polymer for semiconductor fine gap fill.

The present invention also provides a semiconductor fine gap fill composition comprising a surfactant in addition to the composition for semiconductor fine gap fill.

Hereinafter, the present invention will be described in more detail.

    The polymer for semiconductor fine gap fill of the present invention has a dissolution rate (DR) of 0.5 to 500 nm / s, preferably 5 to 50 nm / s, in the developer due to the molar ratio of hydroxyl and carboxyl groups in the repeating unit. As long as it can be adjusted, it can be completely removed without leaving residues inside the hole by ashing.

     The polymer includes the following Chemical Formula 1 and Chemical Formula 2 as a structural unit, preferably 30 to 95 mol% of the structural unit of Formula 1, and 5 to 70 mol% of the structural unit of Formula 2.

[Formula 1]

 (Wherein Ra represents hydrogen or a methyl group, R 1 is an alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aromatic ring group, a cycloalkyl group or benzyl group having 3 to 10 carbon atoms, X is hydrogen or a vinyl group, m is 0 to 10.)

[Formula 2]

 (Wherein Rb represents hydrogen or a methyl group)

     In addition, the polymer may further include a structure of Formula 3 below. The structural unit of the formula (3) preferably contains 1 to 50 mol%.

[Formula 3]

(Wherein Rc represents hydrogen or a methyl group and n is 1 to 10)

     It is preferable to exist in the range of 2000-30000, and, as for the weight average molecular weight (polystyrene conversion) of the said polymer, it is more preferable to exist in the range of 4000-15000. The reason for this is that if the molecular weight is too low, sufficient curability cannot be obtained. If the molecular weight is too high, solvent solubility and coating uniformity are lowered. It is preferable that it is the range of 1-5, and, as for the dispersion degree of molecular weight, it is more preferable that it is 1.2-3.

     On the other hand, the polymer can be synthesized without particular limitation using a conventionally known method, it is preferable to synthesize using a radical polymerization initiator in an organic solvent such as an organic solvent constituting the composition of the present invention. That is, although there is no restriction | limiting in particular in the organic solvent used for the said superposition | polymerization, It is preferable to use the organic solvent like the organic solvent which comprises the composition of this invention mentioned above preferably. On the other hand, the amount of the organic solvent used for the polymerization is preferably adjusted so that the concentration of the polymer in the solution of the organic solvent and the polymer is 5 to 50% by weight. More preferably, it is 15-40 weight%. When the concentration of the polymer in the solution is less than 5% by weight, the polymerization rate is slow, the monomer that remains unreacted may be a problem, and when it exceeds 50% by weight, the viscosity is too high to handle, difficult to control the reaction rate In addition, problems such as difficulty may occur.

     As the polymerization initiator used for the polymerization of the self-curable copolymer, known ones such as thermal polymerization initiators, photopolymerization initiators, and redox initiators can be used, but in terms of ease of handling, reaction rate and molecular weight control can be facilitated. It is preferable to use radical polymerization initiators, such as a peroxide system and an azo system.

 Examples of peroxide-based polymerization initiators usable in the present invention include methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) 3,3, 5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, 1,1-bis (tert-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis ( tert-hexylperoxy) cyclohexane, 1,1-bis (tert-butylperoxy) cyclododecane, isobutyl peroxide, lauroyl peroxide, succinate peroxide, 3,5,5-trimethylhexanoyl peroxide , Benzoyl peroxide octanoyl peroxide, stearoyl peroxide, diisopropyl peroxy dicarbonate, dinormal propyl peroxy dicarbonate, di-2-ethylhexyl peroxy dicarbonate, di-2-ethoxyethyl peroxy dicarbonate, di -2-methoxybutyl peroxydicarbonate, bis- (4-ter t-butylcyclohexyl) peroxydicarbonate, (α, α-bis-neodecanoylperoxy) diisopropylbenzene, peroxy neodecanoic acid cumyl ester, peroxy neodecanoic acid octyl ester, peroxy neodecanoic acid hexyl Ester, peroxy neodecanoic acid-tert-butyl ester, peroxy pivalic acid-tert-hexyl ester, peroxy pivalic acid-tert-butyl ester, 2, 5- dimethyl-2, 5-bis (2-ethylhexanoyl Peroxy) hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, peroxy-2-ethylhexanoic acid-tert-hexylester, peroxy-2-ethylhexanoic acid-tert -Butyl ester, peroxy-2-ethylhexanoic acid-tert-butyl ester, peroxy-3-methylpropionic acid-tert-butyl ester, peroxylauric acid-tert-butyl ester, tert-butylperoxy-3, 5,5-trimethylhexanoate, tert-hexylperoxyisopropylmonocarbonate, tert-butylperoxyisopropylcarbonate, 2,5-dimethyl-2,5-bis (benzoyl Oxy) there may be mentioned hexane, and ethyl -tert- butyl ester, and -tert- acid hexyl ester, and acid -tert- butyl ester and the like. In addition, a reducing agent may be added to the peroxide-based polymerization initiator described above and used as an oxidation-reduction initiator.

 Examples of azo polymerization initiators usable in the present invention include 1,1-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2-methyl-butyronitrile), and 2,2'- Azobisbutyronitrile, 2,2'-azobis (2,4-dimethyl-valeronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 2, 2'-azobis (2-amijino-propane) hydrochloride, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] hydrochloride, 2,2'-azo Bis [2- (2-imidazolin-2-yl) propane] hydrochloride, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane], 2,2 '-Azobis2-methyl-N- (1,1-bis (2-hydroxymethyl) -2-hydroxyethyl] propionamide, 2,2'-azobis [2-methyl-N- (2- Hydroxyethyl) propionamide], 2,2'-azobis (2-methyl-propionamide) dihydrate, 4,4'-azobis (4-cyano-acetic acid), 2,2'-azobis (2-hydroxymethylpropionitrile), 2,2'-azobis (2-methylpropionic acid) dimethyl ester ( There may be mentioned methyl-2,2'-azobis (2-methylpropionate)), cyano-2-propyl-azo-formamide and the like.

 In addition, the above-described peroxide-based polymerization initiator, azo-based polymerization initiator may be used by mixing a variety of species, in addition to the chain transfer agent, chain stop agent, polymerization accelerator, etc. in order to achieve the desired molecular weight range in the polymerization step of the self-curable copolymer The well-known molecular weight regulator of can also be added. Examples thereof include mercaptopropionic acid, mercaptopropionic acid ester, thioglycol, thioglycerine, dodecyl mercaptan, α-methylstyrene dimer and the like.

     In addition, in the preparation of the semiconductor fine gap fill polymer according to the present invention, the reaction temperature is preferably carried out the polymerization reaction at 50 ~ 120 ℃.

     The present invention also provides a semiconductor fine gap fill composition comprising the semiconductor fine gap fill polymer, a crosslinking agent, an acid catalyst, and an organic solvent.

     The crosslinking agent included in the semiconductor fine gap fill composition of the present invention preferably causes a crosslinking reaction with the polymer when the composition of the present invention is heated or calcined. Such crosslinking agents include polymers containing melamine, substituted urea, and epoxy groups. And compounds derived from them. For example, a compound having at least two crosslinking functional groups, for example, divinylbenzene, divinylsulfone, triacylformal, acrylate or methacrylic acid ester of glycerol or polyalcohol or melamine, urea, benzogua It is preferable that at least two of the amino groups of namin and glycoluril are substituted with a methylol group or a lower alkoxymethyl group. Especially, tetramethoxymethylglycoluril or hexamethoxymethylmelamine is preferable.

 The amount of the crosslinking agent added varies depending on the viscosity of the solution or the required film shape, but is 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, more preferably 5 to 15 parts by weight, per 100 parts by weight of the semiconductor fine gap fill polymer. to be.

In the semiconductor fine gap fill composition, as an acid catalyst, mineral acid, sulfonic acid, oxalic acid, maleic acid, hexamic cyclohexylsulfonic acid, phthalic acid Any one or more selected from (phthalic acid) may be used an acid which promotes curing by heat. In particular, it is preferable to use para-toluenesulfonic acid, tripulolomethanesulfonic acid, pyridinium para-toluenesulfonic acid, and compounds having the structure of formula (4). You may use these acid catalysts individually or in combination of 2 or more types.

[Formula 4]

,

,

,

,

,

,

,

,

,

,

The acid catalyst is a catalyst for activating a crosslinking reaction occurring between the polymer and the crosslinking agent. After the composition including the acid catalyst is applied onto a wafer, an acid is generated from the acid catalyst by performing a thermal process such as baking. In the presence of the acid generated in this way, the crosslinking reaction occurs as described above, and thus has strong resistance to isopropyl alcohol (IPA) cleaning and plasma etching process.

    The acid catalyst content is selected in the range of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, per 100 parts by weight of the polymer for semiconductor fine gap fill. If the amount of the acid catalyst is too small, it may be dissolved in isopropyl alcohol even after crosslinking, and if the amount is too large, the storage stability may be lowered.

     In addition, as the organic solvent used in the semiconductor fine gap fill composition, a conventional organic solvent can be used, and diethylene glycol monomethyl ether, diethylene glycol diethyl ether, ethyl-3-ethoxy propionate, methyl-3 Methoxy propionate, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate, propylene glycol dimethyl ether acetate, ethyl lactate, cyclopentanone, hydroxyethyl acetate, etc. desirable. These organic solvents can be used individually or in combination of 2 or more types. The amount of the solvent is preferably 100 to 3000 parts by weight per 100 parts by weight of the polymer for semiconductor gap fill used in the reaction to obtain a coating thickness.

      On the other hand, in the composition for a gap fill for semiconductors of this invention, surfactant can be added in order to improve dispersibility, film thickness uniformity, and semiconductor fine gap fill property in addition to the polymer, crosslinking agent, acid catalyst, and organic solvent which were mentioned above. As surfactant, Polyoxy, such as polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, and polyoxyethylene nonyl phenol ether Ethylene alkyl allyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, polyoxyethylene sorbitan monostearate Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate, F-top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), Mega Pack F171, F173 (manufactured by Dainippon Ink, Inc.), Prorad FC430, FC431 (manufactured by Sumitomo 3M Corporation), Asahi Guard AG710, Sharp Fluorine-based surfactants such as Ron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Can be mentioned. These surfactants are preferably added at a ratio of 0.001 to 5 parts by weight per 100 parts by weight of the total solid fractionation weight of the present invention. These surfactants may be added alone or in combination of two or more kinds.

        Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the following Examples are provided for the purpose of explanation and are not intended to limit the present invention.

Example 1

1. Synthesis of Polymer Compound (A) (MAA 10.5%)

501.4 g of propylene glycol monomethyl ether acetate was added to a 1000 ml flask equipped with a reflux condenser and a stirrer, and then the reaction temperature was raised to 80 ° C while stirring. The reaction temperature was maintained at 80 ° C. and 152 g of benzyl methacrylate, 43.7 g of 2-hydroxyethyl methacrylate, 22.96 g of methacrylic acid and dimethyl-2,2′-azobis (2- A mixture of 40.5 g of methyl propionate) was added dropwise, and after dropping all the mixtures, the reaction temperature was maintained at 120 ° C. or lower, and reacted within 10 hours while stirring to obtain a transparent polymer solution (A). The solution was measured by Gel Permeation Chromatography (hereinafter referred to as "GPC") method. As a result, the polystyrene reduced weight average molecular weight was 7,100 and the number average molecular weight was 2,900.

2. Preparation of Composition for Semiconductor Fine Gap Fill

To 83 g of the obtained polymer solution (A), 2.88 g of melamine-based resin (Cymel 303LF, manufactured by Cytec, USA), 0.04 g of para-toluenesulfonic acid pyridine salt, 0.28 g of a surfactant (manufactured by Sumitomo 3M; frorard FC-430), and propylene 10.05 g of glycol monomethyl ether acetate was added, sufficiently stirred and dissolved, followed by filtration to obtain the desired composition for semiconductor fine gap fill (D).

Example 2

1. Synthesis of Polymer Compound (B) (MAA 11%)

150.9 g of benzyl methacrylate, 43.7 g of 2-hydroxyethyl methacrylate, 24.1 g of methacrylic acid and dimethyl-2,2'-azobis (2- 40.5 g of methyl propionate) was synthesized After the synthesis, the solution was measured by Gel Permeation Chromatography ("GPC") method. As a result, the polystyrene reduced weight average molecular weight was 7,000 and the number average molecular weight 2,900.

2. Synthesis of Polymer Compound (C) (MAA 11.5%)

149.8 g of benzyl methacrylate, 43.7 g of 2-hydroxyethyl methacrylate, 25.1 g of methacrylic acid, and dimethyl-2,2'-azobis (2- in the same manner as in the polymer compound (A) of Example 1; 40.5 g of methyl propionate) was synthesized After the synthesis, the solution was measured by Gel Permeation Chromatography (GPC) method. The weight average molecular weight was 7,000 and the number average molecular weight was 2,900.

3. Preparation of Semiconductor Fine Gap Fill Composition

42 g of the obtained polymer compound (A) and 42 g of the polymer compound (B), 2.88 g of melamine-based resin (Cymel 303LF, manufactured by Cytec, USA), 0.04 g of para-toluenesulfonic acid pyridine salt (Aldrich, USA), and a surfactant (Sumitomo 3M) 0.28 g of frorard FC-430) and 10.05 g of propylene glycol monomethyl ether acetate were added, sufficiently stirred and dissolved, followed by filtration to obtain the desired composition for semiconductor fine gap fill (E).

Example 3

1. Preparation of the composition for semiconductor fine gap fill

83 g of the polymer compound (B), 2.88 g of melamine-based resin (Cymel 303LF, manufactured by Cytec Co., Ltd.), 0.04 g of para-toluene sulfonic acid pyridine salt (Aldrich Co., Ltd.), surfactant (manufactured by Sumitomo 3M; frorard FC-430) 0.28 g and 10.05 g of propylene glycol monomethyl ether acetate were added, sufficiently stirred and dissolved, followed by filtration to obtain the desired composition for semiconductor fine gap fill (F).

Example 4

1. Preparation of the composition for semiconductor fine gap fill

42 g of the polymer compound (B), 42 g of the polymer solution (C), 2.88 g of melamine-based resin (Cymel 303LF, manufactured by Cytec, USA), 0.04 g of para-toluene sulfonic acid pyridine salt (Aldrich, USA), and a surfactant (Sumitomo 3M Co., Ltd.) Product; frorard FC-430) 0.28 g and 10.05 g of propylene glycol monomethyl ether acetate were added, sufficiently stirred and dissolved, followed by filtration to obtain the desired composition for semiconductor fine gap fill (G).

Example 5

1. Preparation of the composition for semiconductor fine gap fill

83 g of the polymer compound (C), 2.88 g of melamine-based resin (Cymel 303LF, manufactured by Cytec, USA), 0.04 g of para-toluenesulfonic acid pyridine salt (Aldrich, USA), surfactant (manufactured by Sumitomo 3M; frorard FC-430) 0.28 g and 10.05 g of propylene glycol monomethyl ether acetate were added, sufficiently stirred and dissolved, followed by filtration to obtain the desired composition for semiconductor fine gap fill (H).

Comparative Example 1

1. Preparation of the composition for semiconductor fine gap fill

Phenol novolak resin PSM-4326 (Japan Gunei Chemical) 25g, melamine resin (Cymel 303LF, Cytec Co., Ltd.) 2.88g, para-toluenesulfonic acid pyridine salt (Aldrich Co., Ltd.) 0.04g, surfactant (Sumitomo 3M Co., Ltd.) 0.28 g of frorard FC-430 and 68.05 g of propylene glycol monomethyl ether acetate were added, sufficiently stirred and dissolved, followed by filtration to obtain the desired comparative composition (I).

     Regarding the fine gap fill composition for semiconductors in each of the above-described examples, the gap fill characteristics, the dissoluton rate (DR) caused by the developer, the IPA resistance, and the plasma etching resistance were obtained by the following method. The removal performance by ashing was tested and the results are shown in Table 1.

(1) gap fill characteristics

  After spin-coating a silicon pattern wafer having a hole having a diameter of 80 nm and a height of 1700 nm under the same coating conditions, soft baking at 90 ° C. for 1 minute to volatilize only the solvent, the cross section of the wafer was observed with a scanning electron microscope. It was confirmed that the composition filled in the hole was completely filled without voids or the like.

(2) dissolution rate (DR)

 The compositions were each spin-coated on 8 inch silicon wafer under the same coating conditions, soft baked at 90 ° C. for 1 minute, and the coating thickness was about 500 nm. The wafer thus coated was obtained with an average dissolution rate using a resist development system (RDA-760 system, Litho Tech Japan Co., Ltd.). At this time, the developer concentration was 2.38% and the developer temperature was 23.0 占 폚.

(3) IPA immunity

 The compositions were each spin-coated on 8-inch silicon wafer under the same coating conditions, hard baked at 220 ° C. for 1 minute, and then immersed in isopropyl alcohol (IPA) at 70 ° C. for 5 minutes to measure the change in thickness. If the thickness difference before and after dipping in isopropyl alcohol is within 1%, it was good, and if it was 1% or more, it evaluated as bad.

(4) oxygen plasma etching resistance

 Each of the compositions was spin-coated on an 8-inch silicon wafer under the same coating conditions, and after 1 minute hard bake at 220 ° C., the coating film was checked for tear by oxygen plasma etching.

(5) Remaining residue after oxygen ashing treatment

  Each of the compositions was spin-coated on a pattern wafer having holes having an aspect ratio of 20 and a width of 80 nm, and soft baked at 90 ° C., and then the developer was applied to remove the coating layer except for the inside of the hole. After curing at 220 ° C., the presence or absence of residues in the holes was confirmed by oxygen ashing.

Gap Fill Characteristics  DR (nm / s) IPA immunity Plasma etching resistance Presence of residues by ashing Example 1 Good 20.1 Good Good none Example 2 Good 23.6 Good Good none Example 3 Good 27.4 Good Good none Example 4 Good 31.9 Good Good none Example 5 Good 36.9 Good Good none Comparative Example 1 Good 28.8 Bad Good existence

 When the coating composition of the present invention is used, a complete gap fill (Gap) is performed on a semiconductor substrate having a diameter of 100 nm or less and a hole having an aspect ratio of 1 or more, without defects such as air voids by spin coating. -Fill), the film can be melted to the desired thickness by aqueous alkali solution (called developer), and after curing by baking, it has strong resistance to isopropyl alcohol (IPA) and plasma etching, and ashing treatment. It can be quickly removed from inside the hole.

Claims (14)

 A semiconductor fine gap fill polymer comprising the following general formula (1) and (2) as structural units. [Formula 1]

 (Wherein Ra represents hydrogen or a methyl group, R 1 is an alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aromatic ring group, a cycloalkyl group or benzyl group having 3 to 10 carbon atoms, X is hydrogen or a vinyl group, m is 0 to 10.) [Formula 2]

 (Wherein Rb represents hydrogen or a methyl group) According to claim 1, wherein 30 to 95 mol% of the structural unit of the formula (1), 5 to 70 mol% of the structural unit of the formula (2) characterized in that the semiconductor fine gap fill polymer. According to claim 1, wherein the semiconductor fine gap fill polymer characterized in that it further comprises a structural unit of the formula (3). [Formula 3]

(Wherein Rc represents hydrogen or a methyl group and n is 1 to 10) The semiconductor fine gap fill polymer according to claim 3, wherein the polymer unit comprises 1 to 50 mol% of the structural units of the above Chemical Formula 3 with respect to 100 mol% of the total structural units of the Chemical Formulas 1 and 2. The semiconductor fine gap fill polymer according to any one of claims 1 to 4, which has a weight average molecular weight of 2000 to 30000. The semiconductor fine gap fill polymer according to claim 5, which has a weight average molecular weight of 4000 to 15000. A composition for semiconductor fine gap fill, comprising a polymer for semiconductor fine gap fill according to any one of claims 1 to 4, a crosslinking agent, an acid catalyst, and an organic solvent. 8. The composition for semiconductor fine gap fill according to claim 7, wherein the crosslinking agent is a melamine-based, substituted urea-based, polymer-containing epoxy group, or a compound derived therefrom. The composition of claim 7, wherein the crosslinking agent is included in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the polymer for semiconductor fine gap fill. 8. The acid catalyst of claim 7, wherein the acid catalyst is a mineral acid, sulfonic acid, oxalic acid, maleic acid, hexamic cyclohexylsulfonic acid, or phthalic acid. The composition for a semiconductor fine gap fill characterized by the above-mentioned. The composition of claim 7, wherein the acid catalyst is included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the polymer for semiconductor fine gap fill. The method of claim 7, wherein the organic solvent is diethylene glycol monomethyl ether, diethylene glycol diethyl ether, ethyl-3-ethoxy propionate, methyl-3-methoxy propionate, cyclopentanone, cyclohexanone A composition for semiconductor fine gap fill comprising at least one solvent selected from the group consisting of paddy, propylene glycol methyl ether acetate, ethyl lactate, cyclopentanone, ethyl hydroxyacetate, and the like. The composition of claim 7, wherein the organic solvent comprises 100 to 3000 parts by weight per 100 parts by weight of the polymer for semiconductor fine gap fill. 8. The composition for semiconductor fine gap fill according to claim 7, further comprising a surfactant in the composition for semiconductor fine gap fill.