TW201040205A - Copolymer for gap filling material composition, preparation method thereof and gap filling material composition for antireflective coating layer - Google Patents

Abstract

A copolymer for a gap filling material, as expressed in Chemical Formula below, wherein R1, R2, R3, R4, R5, R6, and R7 are independent from each other, R1 is hydrogen or a C1-10 alkyl group, each of R2, R3, and R4 indicates hydrogen, the C1-10 alkyl group, or a C1-20 arylalkyl group, each of R5, R6, and R7 indicates hydrogen or a methyl group, and each of a, b, c, and d is a number indicating a repeating unit in a main chain, where a+b+c+d = 1, 0.05 < a/(a+b+c+d) < 0.95, 0.05 < b/(a+b+c+d) < 0.95, 0.05 < c/(a+b+c+d) < 0.95, and 0.05 < d/(a+b+c+d) < 0.95.

Description

201040205

82003524/L901/本本编 ft: I0990002TWI-KR VI. Description of the Invention: [Technical Field] The present invention relates to a copolymer, a method of producing the same, and a composition containing the same (composition), and particularly relates to a copolymer for a gap filling material which can be used as an antireflective coating layer, a method for producing a copolymer for a gap-filling material, and a method for containing A gap filling material composition of a copolymer of a gap filling material. [Prior Art] At present, 'high-integrated 'semiconductor devices' manufacturing of ultra-large integrated circuits scaie integ^ion, ULSI, etc. must be used to be less than or equal to 010 micrometers (Μποη) ) a hyperfme pattern. Also, a lithography process using wavelengths smaller than the wavelengths of conventional rays and 丨-rays has been used. That is, dual damascene is a method of forming a fine line, and is a mainstream method used in the process of a fine semiconductor integrated line device. A damascene process forms a fine line groove (reverse generation) on an insulating layer (sublayer) of a semiconductor substrate, accumulating metal on an insulating layer including a line groove Layer (metaWayer) and using chemical mechanical polishing

Cehemiealmeehankal polishing, CMP) eiiminated the metal layer outside the line groove to form a buried wiring inside the line groove. Moreover, the damascene process can be divided into single layer damascene and double damascene. The dual damascene process forms a via-gated vial for bottom-layered wiring at the bottom of the wire-cut trench formed on the insulating layer, and simultaneously embeds the metal layer into the trench and the via hole to form Lines to reduce the number of processes to be processed. Single-layer metal inspection process in advance in the guide metal grid (she 丨 4 201040205

82003524/L901/This is edited by: I0990002TWI-KR and forms a dark line inside the line groove. The semiconductor device is formed on the semiconductor substrate in accordance with the dual damascene process, and the underlying wiring is formed on the upper portion of the semiconductor skirt. An insulating layer is deposited on top of the underlying wiring, an anti-reflective coating is formed on the insulating layer, and a photoresist layer (phQtoresistlayei) is formed in the anti-reflection layer h photoresist layer by using a photomask formed with a via pattern (photomask) The exposure is performed and continuously developed, and the via pattern of the via hole is transcribed into the observation layer in an open pattern. The anti-reflective coating is axially deflected to prevent the resolution (res-) from decreasing&apos; and is used to prevent the photo-resist layer from being transmitted from the bottom surface of the underlying layer when the photoresist layer is exposed. The anti-reflective coating on the bottom layer of the photoresist layer is called the bottom anti-aliasing layer (bGttom anti r-bar〇. The anti-reflective coating and the insulating layer are subjected to etching) to use the photoresist layer. As a mask, a via hole is formed on the insulating layer. The resist layer and the anti-reflective coating are removed and the inside of the via is filled with the gap fill material. The gap-filling material includes almost complete phase with the anti-reflective coating component. _ dielectric f component. In order to fill in the f-via, the 3⁄4-order transfer material is deposited on the insulating layer including the via hole 3. In the via hole, the material and the filling material are removed by _ (etdiback). When the homing process is performed, the surface of the gap filling material filling the via holes is uniform, and the height of the surface is almost the same as the surface of the insulating layer. The second anti-reflective coating 3 is on the insulating layer, and the second photoresist layer is formed on the second anti-reflective coating. The second photoresist f is exposed by using a wiring to form a mark, and is continuously subjected to display so that a pattern in which the via hole region is opened is transcribed onto the second photoresist layer. For the second subtractive coating, the layer dielectric is formed on the top of the via hole by performing the dielectric layer (5) and the e e middle. The second anti-reflective layer is removed after being turned on. When the second anti-reflective layer is removed, the filled material is also removed, and the surface of the underlying line is at the bottom of the via hole and is inside the via hole and the line trench. ;ir!iSPUtteringSCheme) Cgdd-platingscheme) A copper layer (coppei er) is formed on the insulating layer inside the line groove, and is removed by the 201040205 chemical mechanical grinding method in the channel 导 when the via hole and the dragon (treneh) in the 枓 body When the substrate is processed on the substrate, the sealing cap is closed. The filling material does not have an anti-reflection ship, and only the gap is filled with Wei. In general, the high optical density = inlay process is used to embed the vias and contact windows (_acth()le), = = fill the material for the guide and take over, but the _filler does not (10) )produce. Moreover, when the composition of the material is not in time, 〇 == is required during the trench patterning process: the material must be filled in the gap before the photoresist layer is applied to produce unnecessary high unit manufacturing costs. The material which is opened and can evenly fill the via hole has not been formed.

G filling = ΐΐ problem 'The present invention provides a gap filling material composition which can add a photoresist to the photoresist 郷 ===== S S), thereby increasing the copolymer of the gap filling material as an anti-reflective coating , [Chemical Formula 1] 〇

6 201040205 82003524/L901/Compiled by the Institute: I0990002TWI-KR where 1^, 112, 113, 1^, 115, 1^ and 117 are independent of each other, 111 is a hydrogen or a Cl-ίο alkyl group (alkyl group), each R2, R3 and R4 represents a hydrogen atom, a C1-10 alkyl group or a C1-20 arylalkyl group, and each of R5, 1^ and 7 represents a hydrogen atom or a thiol group. Group), and each a, b, c, and d is the number of repeating units on the main chain, where a+b+c+d = 1,0.05 &lt; a/(a+b+c+ d) &lt; 0.95, 0.05 &lt; b/(a+b+c+d) &lt; 0.95, 0_05 &lt; c/(a+b+c+d) &lt; 0.95 and 0.05 &lt; d/(a+ b+c+d) &lt; 0.95. The present invention further provides a method of preparing a copolymer for a gap filler of Chemical Formula 1 which comprises carrying out polymerization of maleic acid anhydride and acrylate compound. To produce a polymer represented by the following Chemical Formula 2; and reacting the polymer of Chemical Formula 2 with a copolymer and a C1-10 fatty alcohol (Chemical Formula 2)

Rg R3 R4 〇 wherein Ri, R2, &amp;, R4, R5, Re and R7 are independent of each other, R! is a hydrogen atom or a C1-10 alkyl group, and each of R2, R3 and R4 represents a hydrogen atom, C1- a 10 alkyl group or a C1-20 aralkyl group, each of Rs, 1^ and R7 represents a hydrogen atom or a methyl group, and each of a, b, c and d represents the number of repeating units on the main chain, wherein a+b +c+d = 1,0.05 &lt;a/(a+b+c+d;)&lt; 0.95, 0.05 &lt; b/(a+b+c+d) &lt; 0·95, 0.05 &lt; c /(a+b+c+d) &lt; 0.95 spear 0.05 &lt; d/(a+b+c+d) &lt; 0.95. In an embodiment of the invention, the polymerization reaction described above is bulk polymerization, solution polymerization, suspension polymerization, bulk-suspension polymerization, emulsion polymerization. Polymerization) and free radical polymerization 201040205

82003524/L901/Compiled by the Institute: at least one of I0990002TWI-KR (radical polymerization). In an embodiment of the invention, the gap filler material composition described above is applied to the top of the coating for the remainder, and the coated composition is hardened by the baking process (harden' and the gap The filling material is stacked. And, a photoresist is formed on top of the gap filling material, the formed photoresist is exposed and developed to form a photoresist pattern, and the gap filling material is used by using a photoresist pattern as an etching mask. Etching, and the coating is engraved to form a pattern of the coating. The above-described features and advantages of the present invention will become more apparent from the following description. [Embodiment] The following examples will be described in detail with reference to the accompanying drawings. The exemplified embodiments are described below with reference to the following drawings to illustrate the invention. The copolymer used as the gap filler of the antireflection coating will be described below. A copolymer for a gap-filling material having an anti-reflective coating function is represented by the following chemical formula: ^ [Chemical Formula 1]

Here, Ri, R2, R3, m, R·5, R6 and R7 are independent of each other, the heart is a nitrogen atom or a C1-10 alkyl group, and each &amp;, R3 and R4 represents a hydrogen atom, C1-10 alkane a group or a group of Cl 2 〇 炫, each of &amp;, R6 and R/7 represents a hydrogen atom or a methyl group, and each of a, b, c, and d is δ 201040205

82003524/L901/Edited by the Institute « : I0990002TWI-KR indicates the number of repeating units on the main chain, where a+b+c+d =], 〇〇5 &lt;&lt; 0.95, 0.05 &lt; b/(a+ b+c+d) &lt; 0.95, 0.05 &lt; c/(a+b+c+d) &lt; 0.95 and 0.05 &lt; d/(a+b+c+d) &lt; 0.95. The structure of the gap fill material can have different designs. The first design is to lower the average molecular weight to enhance the filling ability, the second design is to provide the absorbance material for the main chain of the polymer, and the third design is used separately. Absorbing material and hardenable polymer (hardening agent polymer) Generally, the light absorbing material is used alone to adjust the amount of the light absorbing chemical. Moreover, the functional group, glycidyl (glycidyl) The functional group or the ethyl acetyl functional group is mainly used as a hardener polymer. The copolymer of the gap-filling material for the anti-reflective coating layer shown in the above Chemical Formula 1 uses a carboxyl group for light. Absorbing and heat hardening (also (C) (4)), and containing maleic anhydride known to have a good silver engraving speed. The copolymer of the gap filler material for antireflective coating according to the embodiment will be described in detail below. The preparation method of the gap filler material for the antireflection coating in Chemical Formula 1 is transmitted through the maleic anhydride and the acrylate compound. The ❹ t δ substance of the chemical formula 2 produced by the polymerization reaction is prepared by reacting a reaction intermediate of the chemical formula 2 with a fatty alcohol. [Chemical Formula 2]

Wherein 'R2, R3, R5, &amp; and R7 are independent of each other, and each of r2, &amp; and ^ represents a hydrogen atom, a C1-10 alkyl group or a C1-20 aralkyl group, each &amp;, & And R? represents hydrogen 201040205 82003524/L901/here edited: I0990002TWI-KR atom or methyl group, and each a, b, c and d is the number of repeating units on the main chain, where a+b+c+ d = 1, 0.05 &lt; a/(a+b+c+d) &lt; 0.95, 0.05 &lt; b/(a+b+c+d) &lt; 0.95, 0.05 &lt; c/(a+b+ c+d) &lt; 0.95 and 0.05 &lt; d/(a+b+c+d) &lt; 0.95. In this case, the 'acrylate compound is at least one selected from the group consisting of: methyl acrylate, ethyl acrylate, isopropyl acrylate. ), n-propyl acrylate, n-butyl acrylate, isobomyl acrylate, 2-ethylhexyl acrylate Acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, mercaptopropionate N-propyl methacrylate, tert-butyl methacrylate, n-butyl methacrylate, is〇butyl methacrylate , cycl〇hexyl methacrylate, isobomyl methacrylate, diethylene glycol monomethyl ether methacrylate, methacrylic acid 2 -ethyl 2-ethylhexyl methacrylate, benzyl methacrylate, i_naphthylmethyl methacrylate, 2-naphthylmethyl G methacrylate , 9-anthrylmethyl methacrylate, 1-anthrylmethyl methacrylate and 2-methyl methacrylate Anthrylme1;hyl methacrylate ). The carboxyl group is reacted with a hardener having a functional group such as acetal to form a crosslinking structure, and the carboxyl group is prepared by ring-opening of a reaction intermediate of Chemical Formula 2 with a fatty alcohol. . The gap-filling material using the copolymer prepared according to the example was coated on the substrate and hardened during the baking treatment, and thus was able to resist dissolution of a solvent. That is, the gap filling material fills the contact window and the via hole, and becomes insoluble in the photoresist after coating the photoresist, and thus has stability. Therefore, the copolymer prepared according to the embodiment of the present invention can be used for 201040205

82003524/L卯 1/Compiled by the Institute: I0990002TWI-KR Hardener copolymer in the gap filler composition. When the polymer of Chemical Formula 2 is prepared, conventional polymerization such as bulk polymerization, solution polymerization, suspension polymerization, bulk-suspension polymerization, emulsion polymerization, or the like can be used, and radical polymerization is preferably used. This is not limited to general radical polymerization initiators such as azobisisobutyronitrile, benzoyl peroxide, laurylperoxide, azobisisoxanenitrile. (azobisiso capronitrile), azobisisovaleronitrile, and t-butyl hydroperoxide are used as initiators for radical polymerization.聚合 The polymerization solvent is derived from benzene, toluene, xylene, halogenated benzene, diethyl ether, and tetrahydrogen. At least one selected from the group consisting of tetrahydrofUran, esters, ethers, lactones, ketones, and amides. The polymerization temperature is appropriately selected depending on the type of the initiator. The molecular weight distribution of the polymer is appropriately adjusted by changing the amount of the polymerization initiator and the reaction time. After the completion of the polymerization reaction, the by-product and the unreacted monomer remaining in the reaction compound need to be removed by extraction or precipitation using a solvent. When the reactive compound contains a ring-opened maleic anhydride, the desired molecular weight is difficult to obtain by conventional gel permission chromatography due to the formation of carboxylic acid. Therefore, the polymer of Chemical Formula 2, which is a polymer before ring opening with a C1-10 alcohol, whose molecular weight is used as a reference when adjusting the molecular weight. That is to say, in the case of polystyrene, the polymer of Chemical Formula 2 obtained by gel permeation chromatography has a weight-averaged molecular weight of about 1,000 to 100,000. Here, the polymer of Chemical Formula 2 is a polymer before ring opening. Further, the weight average molecular weight of the polymer of Chemical Formula 2 is preferably about 5, 〇〇〇 to 1 〇, in view of the solvent solubility, the spreading characteristic, and the sufficient crosslinking. . Moreover, the molecular weight distribution (PDI) of the polymer is preferably from about 1.0 to about 5.0, particularly preferably from about 15 to about 3.5. 11

82003524/L901/Edited by the Institute*: Remuneration Calendar-KR 201040205 The polymer represented by Chemical Formulas 3 to 6 is a chemical formula. However, the examples are not limited thereto. [Chemical Formula 3] Detailed description of the t compound represented by 1

[Chemical Formula 4]

12 201040205 820G3524/L901/Owned No.: I0990002TWI-KR Here, each a, b, c and d is the number of repeating units on the main chain, where a+b+c+d =1, 0.05 &lt; a /(a+b+c+d) &lt; 0.95, 0.05 &lt; b/(a+b+c+d) &lt; 0.95, 0.05 &lt; c/(a+b+c+d) &lt; 0.95 and 0·05 &lt; d / (a + b + c + d) &lt; 0.95. A gap filling material composition for an antireflection coating according to an embodiment of the present invention will be described in detail below. The gap filling material composition according to an embodiment of the present invention may include, in addition to the copolymer of the gap filler material of Chemical Formula 1, an additive for improving the properties and hardenability of the polymer and the light absorbing material, And the additive may include a crosslinking agent and a thermal acid generator. The gap filling material according to an embodiment of the present invention may include a compound containing a light absorbing material or may include a light absorbing material separated from a non-light absorbing poly 5 material. Usually, the light absorbing material is used alone to control the absorbing amount. The wicking material is a polyj′ containing a cross-linking point (cr〇sslin]dng site on one end of the (sulfur-—η) or straight-chain and further including the chemical formulas 7 and 8. Frequency type (dirty (tetra) brown (4) light absorbing material. [Chemical Formula 7]

G

Wherein R« is a 〇 0 -ί II ο CH, ch3 sub, C1-10 alkyl or Cl-ίο alkoxy. Or · 0 1 R9 independently represents hydrogenogen [Chemical Formula 8] 13 201040205

82003524/L901/Editor: I0990002TWI-KR

Ru independently represents a hydrogen atom, a C1-10 alkyl group or a C1-10 alkoxy group. The crosslinking agent is a compound containing at least two crosslinking functional groups, and examples of the crosslinking agent include an aminoplastie compound, a multi-flmctional epoxy resin, and two A dianhydride mixture. Further, the crosslinking agent is derived from oxetanyl, oxazolin, cyclocarbonate, alcohol silyl, aminomethylol, Alkoxymethyl, aziridinyl, methylol, isocyanate, alkoxymethylamino, and multifonctional epoxy At least one of the groups selected. Examples of aminoplasty compounds include dimethoxymethylglycouril, diethoxymethylglycouril, dimethoxymethylglycolil, and diethoxymethylglycine. , diethyldimethylmethylglycouril, tetramethoxymethylglycouril, and hexamethoxymethyl melamine resin. Moreover, MY720, CY179MA, DENACOL, etc. can also be used as the polyfunctional epoxide. It is preferred to use a thermal acid generator as a catalyst to accelerate the hardening reaction. For example, a thermal acid generator is derived from toluenesulfonic acid, an amine salt of a toluene acid, a pyridine salt of a sulfonic acid, a alkyl acid 14 201040205

82003S24/L901/This ff is at least one selected from the group consisting of I0990002TWI-KR (alkylsulfonic acid), an amine salt of an alkylsulfonic acid, and a pyridinium salt of an alkylsulfonic acid. The organic solvent used for the gap filling material composition is from propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), and cyclohexene ( Cyclohexanone), ethyl lactate, propylene glycol n-propyl ether, dimethylformamide (DMF), γ-butyrolactone, ethoxylate Ethyl ethanol, methoxy ethanol, methyl 3-methoxy propionate (C) MMP) and ethyl 3-ethoxtypropionate , EEP) at least one selected from the group consisting of. The gap fill material composition according to an embodiment of the present invention comprises from about 0.1% to about 40% by weight of the total composition of the light absorbing material, and preferably comprises from about 〇1w% to about 15% by weight of the total composition of the light absorbing material. . Moreover, the gap material composition preferably comprises from about 0.1% to about 20% by weight of the total composition of the polymer 'including a crosslinking agent of from about 〇lw〇/〇 to 15w〇/〇 of the total composition' and includes The total composition is from about O.Olw% to 20w% and preferably from about 0.1% to about 15% by weight of the thermal acid generator. According to an embodiment of the present invention, when a gap filling material composition is applied on a wafer, such as a baking heat treatment, the hot acid generator generates acid, a light absorbing material, a polymer, and a bedding. The heat acid generated by the cross-linking reaction is accelerated, thereby producing a gap-filling material which is insoluble in an organic solvent. Gap Filler Fills the vias and contact windows to form a fine line through a dual metal inlay process. A method of forming a semiconductor device pattern using the gap filling material composition according to an embodiment of the present invention will be described in detail below. The method comprises coating a top surface of the coating with an organic gap filler material to be pasted by a baking process to harden the coated composition to form a cross-linking reaction to form a stack of gap filler material on top of the gap-fill material. Coating the photoresist, ^ light and developing to form a silk with, by using a bribe as a mask to the frame 15 201040205 82003524 / L901 / the editor: i0990002TWI-KR gap filling material 'and etching this coating to A pattern of this coating is formed. The baking treatment is preferably carried out at a temperature of about 150 ° C to 25 (TC for about 30 seconds to 5 minutes. Moreover, after the hard mask is coated, the formed spin-coated stone may also be formed. The organic/inorganic gap-filling material composition is additionally laminated on the top of the spin-on carbon hard mask before or after the baking treatment, and the baking treatment is preferably carried out at a temperature of about 7 ° C to 200 ° C. Some examples will be described in detail below. [Synthesis Example] 〇 [Synthesis Example 1: Synthesis of Polymer A for Gap Filler] 20 g of maleic anhydride, 20.42 g of methyl methacrylate, and 34.31 g of methacrylic acid cyclohexane Cyclohexyl metacrylate, 29 g of tert-butyl decyl acrylate and 10.37 g of azodiisobutyronitrile (AIBN) dissolved in 342 g of 1,4-dioxane and at about 80° The polymerization was carried out for 4 hours at C temperature. After the polymerization was completed, the reaction solution was dropped into a metiiyl alcohol to form a precipitate, and the reaction solution was washed with methanol. After being vacuum-dried (vacuum-dried) Sub-amount: 7800, polydispersity index (PDI): 2.84, yield: 60%). 62.23 g of vacuum-dried polymer and 1.03 g of toluenesulfonic acid monohydrate and 34 2 g of methanol is mixed and reacted at a temperature of about 80 ° C for 20 hours. After the reaction is completed, the reaction solution is dropped into distilled water to filter out the formed sinking matter, and the reaction The solution was vacuum dried after washing with distilled water (yield: 58%). [Synthesis Example 2: Synthesis of Polymer B for Gap Filler] 20 g of maleic anhydride, 20.42 g of methyl methacrylate, 34.31 g Cyclohexyl methacrylate, 35.93 g of benzyl methacrylate and 11.06 g of azobisisobutyl hydrazine (AIBN) were dissolved in 365 g of 1,4-dioxane and carried out at a temperature of about 80 ° C. One hour of polymerization. • After the polymerization reaction is completed, the reaction solution is dropped into sterol to filter out the formed precipitate, and 16 201040205 82003524/L卯1/This is the number: I0990002TWI-KR reaction solution Vacuum dried after multiple times (molecular weight: 7 , pDl: 2 79, 产·59%). 65.28 g of vacuum-dried polymer and u g of p-toluene acid monohydrate mixed with 365 g of sterol' and reacted at about machine temperature for 2 hrs . At the end of the reaction, the reaction solution was dropped into steaming water to concentrate the formed precipitate, and the reaction solution was vacuum-dried after washing with distilled water (yield: 59%). [Synthesis Example 3: Synthesis of Polymer C for Gap Filler] 20 g of maleic acid liver, 20.42 g of methyl methacrylate, 35 93 g of mercapto acrylate, 29 g of tert-butyl methacrylate Stirring and 1 〇·53 g of azobisisobutyr (MBN) were dissolved in Q 347 g of hydrazine, 4-dioxane and polymerized at a temperature of about 80 ° C for 4 hours. After the completion of the assembly reaction, the reaction solution was dropped into decyl alcohol to filter out the formed precipitate, and the reaction solution was vacuum dried after washing with methanol several times (molecular weight: 78 〇〇, pDI: 2 82, produced) S : 58%). 60.1 g of the vacuum-dried polymer and 1 g of p-toluenesulfonic acid monohydrate were mixed with 347 g of methanol' and reacted at a temperature of about 80 ° C for 20 hours. After the end of the reaction, the reaction solution was dropped into distilled water to filter out the resulting precipitate, and the reaction solution was vacuum dried after washing with distilled water (yield: 59%). [Synthesis Example 4: Synthesis of Polymer D for Gap Filler] 20 g of maleic anhydride, 20-42 g of decyl methacrylate, 35.93 g of phenyl fluorene acrylate®, 38.38 g of mercaptopropionate Diethyiene giyC〇i methylether methacrylate and 11.47 g of azobisisobutyl hydrazine (ajbn) were dissolved in 378 g of hydrazine, 4-dioxane and at about 8 (TC temperature for 4 hours). Polymerization reaction. After the completion of the polymerization reaction, the reaction solution was dropped into methanol to filter out the resulting precipitate, and the reaction solution was vacuum dried after washing with methanol several times (molecular weight: 7800, PDI: 2.94, yield: 62 %) 71.1 g of vacuum-dried polymer and 1.1 g of p-toluene monohydrate mixed with 378 g of methanol' and reacted at a temperature of about 80 ° C for 20 hours. After the reaction, the reaction solution was dropped. The resulting precipitate was filtered off by steaming, and the reaction solution was vacuum dried after washing with distilled water (yield: 60%) [Example] 17 201040205

82003524/L901/This book is edited: I0990002TWI-KR

[Example 1: Preparation of Gap Filler Composition A] L9 gram of a polymer for gap filler material prepared by Synthesis Example 1, 2.85 g of light absorbing material ' 1.43 g of tetramethoxymethylglycine and 0.10 The gram heat generating agent was dissolved in 93.73 g of propanol-hydrazide-containing acetic acid s (PGMEA) and the solution was filtered through a membrane filter having a diameter of 〇2 to prepare a gap-filling material composition a. [Example 2: Preparation of Gap Filler Composition B] L90 g of a polymer for a gap-filling material prepared by Synthesis Example 2, 2.85 g of a light-absorbing material, 1.43 g of tetradecyloxyguanylurea and 0.10 g The heat generating agent was dissolved in 93.73 g of propylene glycol methyl ether acetate (PGMEA) and the solution was filtered through a filter membrane having a diameter of 0.2 μm to prepare a gap filler composition composition. [Example 3: Preparation of Gap Filler Composition C] L90 g of a polymer for a gap-filling material prepared by Synthesis Example 3, 2,85 g of a light-absorbing material, 1.43 g of tetramethoxyimylglycolil and 0.10 g of the heat generating agent was dissolved in 93.73 g of propylene glycol methyl acetate (PGMEA), and this solution was filtered through a filter membrane having a diameter of 0.2 μm to prepare a gap-filling material composition C. [Example 4: Preparation of Gap Filler Composition D] 〇L90 g of a polymer for a gap-filling material prepared by Synthesis Example 4, 2.85 g of a light-absorbing material '143 g of tetramethoxymethyl guanylurea and 0.10 The gram heat generating agent was dissolved in 93.73 g of propylene glycol methyl ether acetate (PGMEA), and this solution was filtered through a ruthenium having a diameter of 〇.2 ^ to prepare a gap filler material composition D. [Test Example] [Measurement Example 1: stripping test] The gap-filling material composition was spin-spread on a stone wafer and baked on a platform heated to about 230 ° C. 1 minute to form a coating for the gap fill material. In this case, the gap fill material can be prepared by the example of 丨4. Cross-linking 18 201040205

82003524/L901/Edited by the Institute: i〇990002TWI-KR, the thickness of the coating for the gap-filling material was measured, and the wafer coated with the coating for the gap-filling material was immersed in an ethyl lactate solvent for 1 minute. After the ethyl lactate is completely removed, the wafer is heated to about 1 Torr. The crucible platform was baked for a few minutes and the thickness of the coating for the gap fill material was again measured. As a result of the measurement, for all of the gap-fill material compositions prepared by the examples i to 4, there was no difference in the coating thickness of the coating before and after the treatment of ethyl lactate. Therefore, since the gap-filling material composition prepared by the example is completely hardened, the gap-filling material composition is not intermixed with the photoresist during the lithography process. [Test Example 2: Testing the filling characteristics for the gap filling material coating] The gap filling material composition was filled with the contact window and the via hole in the double damascene process and was spin coated on the substrate, and was It was baked to a stage of about 23 (y&gt;c for 1 minute to prepare a coating for the gap-filling material. In this case, the gap-filling material can be prepared by the examples 1 to 4. The coating of the gap-filling material is identified by a scanning electron microscope (SEM). Figure 1 illustrates the scanning of a gap-filling material composition coated on a substrate in Example 1. Electron microscopy image. Please refer to the figure 丨, no voids are generated during the filling process of the double damascene process. Moreover, the gap filling material composition has more than 95% sufficient filling characteristics and good surface uniformity after filling. The present invention has been disclosed in the above embodiments, but it is not intended to limit the invention, and any one of ordinary skill in the art without departing from the invention. The scope of protection of the present invention is subject to the definition of the scope of the appended claims. It can be obtained from the above-described embodiments that A gap fill material composition having good filling characteristics, good adhesive properties and safekeeping properties, and having a fast dry etching rate. According to the embodiment, the filling process in the dual damascene process Will not produce 19 201040205

82003524/L901/Owned No.: I0990002TWI-KR voids, and the gap-filling material composition is sufficiently filled and thus has a uniformity of more than 95%. Moreover, according to the above embodiment, when the gap filling material composition is exposed during the filling lithography process, the gap filling material composition can sufficiently absorb the reflected light which occurs. Moreover, the gap fill material composition is not intermixed with photoresist, anti-reflective coating, dielectric material, etc., and has a gap filler material composition and a photoresist and gap fill material composition and a bottom anti-reflective coating. High etching selectivity. Because of this, the gap fill material mixture simplifies the process and eliminates unnecessary waste by eliminating unnecessary processes. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a scanning electron microscope image of a gap-filling material composition coated on a substrate in Example 1. [Main component symbol description] ❹ No 0 20

Claims (1)

201040205 82003524/L901/本本金:I〇9i»〇〇〇2TWI-KR VII. Patent application scope: - A copolymer for gap filler materials, represented by the following chemical formula ,, [Chemical Formula 1] Wherein R1", 仏^^ and :^ are mutually independent of each other^ are a hydrogen atom or a C1_10 alkyl group, and each R2, &amp; and R4 represents a hydrogen atom, an α10 alkyl group or a C1_20 aralkyl group, each & , 1^ and R? represent a hydrogen atom or a fluorenyl group, and each of a, b, c and d represents the number of repeating units on the main chain, wherein a+b+c+d = 1,0.05 &lt; a/^ +b+e+d^) &lt; 0.95,0_05 &lt; b/(a+b+c+d) &lt; 0_95,0.05 &lt; c/(a+b+c+d) &lt; 0,95 and 0.05 &lt; d / (a + b + c + d) &lt; 0.95 ° 2. A method for preparing a copolymer for a gap filler material, comprising: polymerizing a maleic acid Sf and an acrylic acid vinegar compound, A first polymer represented by the following Chemical Formula 2 is produced; and the first polymer and the C1-10 fatty alcohol are reacted together to form a second polymer represented by the following Chemical Formula 3, [Chemical Formula 2] R6, r R7 , 〇 [Chemical Formula 3] 21 201040205 82003524/L901/Owned No.: I0990002TWI-KR Wherein 'Min, &amp; R3, R4, Rs, 1^ and &amp; are independent of each other, &amp; is a hydrogen atom or a C1-10 sleek group, a parent R2, a stalk 3 and a hydrogen atom, a cl_1 sulphur group Or cl 2 〇 aralkyl 'each Rs, and & represents a hydrogen atom or a methyl group, and each a, b, c and d represents the number of repeating units on the main chain, where a+b+c+d = l 〇〇5 &lt;&lt; 0.95, 0.05 &lt; b / (a + b + c + d) &lt; 0.95, 0.05 &lt; c / (a + b + c + d) &lt; 0.95 and 0.05 &lt; 0 d/(a+b+c+d) &lt; 0.95 ° 3. A method for preparing a copolymer for a gap-filling material as described in claim 2, wherein the acrylate compound is derived from methyl acrylate , ethyl acrylate, isopropyl acrylate, n-propyl acrylate, n-butyl acrylate, isobornyl acrylate, decyl hexyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid Propyl ester, n-propyl methacrylate, tert-butyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, diethylene glycol methacrylate Methyl ether ester, 2-ethylhexyl methacrylate, benzyl methacrylate, 1-naphthylmethyl methacrylate, 2-naphthylmethyl methacrylate, 9-mercapto methacrylate And at least one selected from the group consisting of 11 - fluorenylmethyl methacrylate and 2-mercaptomethyl methacrylate. 4? A method for preparing a copolymer for a gap-filling material as described in claim 2, wherein the polymerization is bulk polymerization, solution polymerization, suspension polymerization, bulk-suspension polymerization, emulsion polymerization, and radical polymerization. At least one of them. 5. The method for preparing a copolymer for a gap-filling material as described in claim 4, wherein the initiator for the radical polymerization is derived from azobisisobutyronitrile, peroxide, stupid, At least one selected from the group consisting of peroxidized laurel, azobisisohexanenitrile, azobisisovaleronitrile, and t-butyl hydroperoxide. 22 201040205 82003S24/L901/This is edited by: The method of preparing a copolymer for a gap-filling material as described in claim 4 of the patent application, wherein the polymerization solvent for radical polymerization is At least one selected from the group consisting of benzene, toluene, diurobenzene, halogenated benzene, diethyl ether, tetrahydrofuran, esters, ethers, lactones, ketones and guanamines. 7. The method for preparing a copolymer for a gap-filling material according to claim 2, wherein in the case of polyethylene, the weight average molecular weight obtained by gel permeation chromatography is about 1,000 100,000. 8. The method of preparing a copolymer of a hard-filling filler material as claimed in claim 2, wherein the first polymer has a molecular weight distribution of from 1 Å to 5 Å. 9. - a Cong filler material composition comprising a light absorbing ruthenium, a thermal acid generator, a crosslinking agent, and a copolymer represented by the following Chemical Formula 4 - filling the composition with the gap, [Chemical Formula 4] Wherein R R 2 , R 3 , R 4 , chemistry, nucleus and R 彼此 are independent of each other, R 1 is a nitrogen atom 疋 C 1 烧 ' 'each heart & and ^ represents a hydrogen atom, a burnt group or an aromatic group each Rs 匕 and Han 7 represents a gas atom or a methyl group, and each represents the number of repeating units on the main chain, and a+b+e+d = i, (10)5 &lt;Caf (4)) &lt; 〇.95, 〇.05 &lt;b/(a+b+C+d)&lt; 0.95, _ &lt; c/(a+b+c+d) &lt; 〇·95 and _ &lt; d/(a+b+c+d) &lt;; 0_95. [Chemical Formula 5] 23 201040205 〇 82003524/L901/This book is compiled: 0 II —-S—II 〇 wherein, private is a hydrazine—, a sub, a C1-10 alkyl group or a Cl-ίο alkoxy group, and [Chemical Formula 6] CH3 or _11 R9 independently represents a hydrogenogen η CH Ch3 or J_ 3 Ru independently represents a hydroquinone atom, a C1-10 alkyl group or a C1-10 alkoxy group. The gap filler material composition according to claim 9, wherein the crosslinking agent is contained At least two compounds having a crosslinking functional group, and at least one selected from the group consisting of aminoplast compounds, polyfunctional epoxy resins, acid anhydrides, and mixtures thereof. The gap filler composition according to claim 9, wherein the crosslinking agent is derived from oxetanyl, phenanthrene, cyclocarbon, ethyl methacrylate, amino group methyl And at least one selected from the group consisting of oxymethyl, 1 propyl, methyl, isocyanate, alkoxyamino and polyfunctional oxide. Apply for the patent application of the Model Fan® Item 11, the towel of the aminoplast 24 201040205 820D3524/L901/Owned No.: I0990002TWI-KR compound is from dimethoxymethyl gland, two Mixture of oxymethylglycine, dimethoxymethylglycoluril and diethoxymethylglycolide, diethyldimethylglycine, tetramethoxymethylglycoluril and hexamethoxyanthryl melamine resin At least one selected from the group consisting of. 14. The gap filling material composition according to claim 9, wherein the thermal acid generator is an amine salt derived from toluene, toluene acid, a caffeine salt of toluene acid, an acid, At least one selected from the group consisting of an alkyl salt of an alkyl acid and a bite salt of a decano acid _, γ-butyl vinegar, pr oxyethanol, methoxyethanol, 3-methoxypropionic acid fs and 3 ethoxy groups = at least one selected from the group. The composition of the crucible filling composition according to the invention of claim 9, wherein the organic solvent of the interstitial filler composition is from the group consisting of propylene glycol, propylene glycol, and cyclamate. , the lactic acid propylene, the propylene glycol propylene propylene, the dimethyl melamine, the _16. The gap filler material composition according to claim 9, the stomach material composition comprises: ^ gap filling 0.1 w % to 30 w% of the copolymer for the gap filling material composition · 0.1 w / 〇 to 50 W% of the light absorbing material; 0.01 w% to 30 w% of the thermal acid generator; and 0.01 The crosslinker is w% to 25 w/〇. 25