TW200944546A - Copolymer and composition for organic antireflective layer - Google Patents

Abstract

The present invention provides an organic anti-reflection coating composition comprising a copolymer represented by the following Formula 1, a light absorbent, a thermal acid generating agent, and a curing agent: wherein R1, R2 and R3 are each independent to each; R1 represents hydrogen or an alkyl group having 1 to 10 carbon atoms; R2 represents hydrogen, an alkyl group having 1 to 10 carbon atoms or an arylalkyl group having 1 to 20 carbon atoms; R3 is hydrogen or a methyl group; m and n are repeating units in the main chain, while m+n=1, and they have values of 0.05<m/(m+n)<0.95 and 0.05<n/(m+n)<0.95. The anti-reflection coating using the polymer of the invention has excellent adhesiveness and storage stability, and a very high dry etching rate, and exhibits excellent resolution in both C/H patterns and L/S patterns.

Description

200944546 ·- VI. DESCRIPTION OF THE INVENTION: - Technical Field of the Invention The present invention provides a kind of surface anti-reflection (four) coin which can be used for preventing reflection on the inner coating layer and preventing the fineness of the money. Standing wave, and has a dry side rate. More specifically, the present bribe provides a novel polymer, a light absorbing agent, and an organic antireflective coating composition containing the above novel fluorene and light wei agent, which can be used in the production of organic antireflective coatings. The above organic anti-reflective coating facilitates the ultra-fine patterning of semiconductors using an ArF excimer laser. The present invention also provides a method of patterning a semiconductor device by modulating the organic anti-reaction layer composition. [Prior Art] ❿ Recently, integrated semiconductor devices require ultra-fine patterns with a line width of 〇·10 μm or finer in the production of ultra-LST, etc., and are utilized in existing g-ray or i-ray regions. The wavelength of light used for exposure is smaller at wavelengths

Photolithography of light is needed. Therefore, a microlithography process using a KrF excimer laser or an ArF excimer laser is currently used in the process for producing a semiconductor device. As the size of the semiconductor device remains smaller and smaller, only when the reflectance is maintained at a maximum value less than the generation during the process of the exposure process, the image of the same can be obtained, and the appropriate process benefits can be obtained. The areas that can be acquired and needed can be realized. Therefore, in order to reduce the reflectance and control the reflectance as much as possible to prevent the emission in the undercoat layer to remove the standing wave, it is more and more to arrange an organic anti-reflective coating containing organic molecules capable of absorbing light under the photoresist. important. Therefore, the organic anti-reflective coating composition must satisfy the following conditions. Ό First, the organic anti-reflective coating composition should contain a material that absorbs light in the wavelength region of the exposure source to prevent reflection in the undercoat layer. The first anti-reflective coating is not dissolved by the photoresist during the lamination of the organic anti-reflective coating and the lamination of the photoresist. In this regard, the anti-reflective coating must be designed to have a thermosetting structure, and its curing can be accelerated by performing a baking process after coating in the process of laminating the anti-reflective coating. Third, the anti-reflective coating is on the upper side to reduce photoresist loss due to the undercoat. The fourth &apos;anti-reflective coating compound should not react with the photoresist in the upper portion. Also, compounds such as amines or acids should be able to move into the photoresist layer because these compounds can be deformed in the fine form, such as a footing or a special inner coating. The fifth 'anti-anti-alias compound _ has optical properties suitable for various exposure processes associated with various anti-200944546 substances, ie, appropriate refractive index and absorption coefficient' and should have strong reactivity with various reactants and light Sex. However, in the current situation, an ultra-fine patterned anti-reflective coating capable of satisfying the use of ArF light in the process has not been studied. Therefore, in order to prevent the reflection of standing waves due to exposure and to eliminate the influence of back diffraction and reflected light in the undercoat layer, the development of an organic antireflection material having a strong absorption ability for the side wavelength is considered to be an urgent need. Solve the problem. SUMMARY OF THE INVENTION Accordingly, an exemplary embodiment of the present invention provides an ultra-fine pattern lithography recording using an ArF excimer laser having a wavelength of 193 nm. An organic anti-reflective coating composition that reflects light. Moreover, another exemplary embodiment of the present invention provides a chemical structure capable of designing a basic structure of a reflective coating to accelerate an etching rate of an organic anti-reflective coating, and based on the above structure for manufacturing a polymer, and providing A method for producing an organic anti-reflective coating based on the above polymer, so that the above-described residual process can be simplified. Moreover, another exemplary embodiment of the present invention also provides a method for patterning a semiconductor device using the above organic anti-reflective coating composition, and the method of the invention can eliminate the undercut, the foot, etc., and can reach the pole. Good super-fine graphical effect. An organic anti-reflective coating formed by a novel copolymer and a light absorbing agent that takes care of an organic anti-reflective coating according to the present invention can provide a general resistance to a solvent and can control light interference and high etching rate. . 〇 Therefore, the use of a light source of 193 coffee can provide good process benefits to the ultra-fine patterning process, and thus a good graphic file can be obtained regardless of the type of the lining. Moreover, by promptly engraving the above anti-reflective coating, it is possible to contribute to the more active development of highly integrated semiconductor devices that can achieve industrial profits. [Embodiment] In order to solve the above problems, an object of the present invention is to provide an ultra-fine pattern lithography process which can be used for A# excimer lasers having a wavelength of iggnm. A novel polymer, a light absorber, and an organic anti-reflective coating composition containing the above-mentioned materials, which are capable of absorbing the resulting reflected light from the organic anti-reflective coating according to the exposure. Another object of the present invention is to provide a chemical structure for accelerating the cost of an organic anti-reflective coating based on the basic structure of the reflective coating. Based on the above-mentioned polymer, the anti-reflection (4) financial method of 200944546 can be manufactured, and the above art can be simplified. Moreover, another object of the present invention is to provide a kind of organic anti-reflective coating composition to display the green color of the semi-conducting county, and the upper method can eliminate undercuts, footings, etc. Good super-fine graphical effect. In view of the above, in order to achieve the above object, the organic antireflective coating composition of the present invention comprises a copolymer for an organic antireflective coating, a light absorbing agent, a thermal acid generator, and a curing agent. The above organic anti-reflective coating composition further includes an organic solvent and further includes a surfactant and various additives. The method for patterning a semiconductor device of the present invention comprises applying an organic anti-reflective coating composition to an upper portion of a coating to be etched, curing the above-described coated composition by baking, and forming a crosslinked structure for use. To form an organic anti-reflective coating. The copolymer used for the organic antireflection coating is represented by the following chemical formula i. [Chemical Formula 1] ’

200944546 (hydrogen) or an alkyl group containing 1 to 1 carbon atom (carb〇n atc>m); representing a halogen atom or an alkyl group having 1 to 1 carbon atom or containing 1 to 20 Arylikyi gr〇Up of carbon atom; R3 is a hydrogen atom or a methyl group; m and η are repeating units on the main chain 'm+n=l and satisfy the condition 〇.〇5&lt ;ffl/(m+n)&lt;〇. shame and 0.05&lt;n/(m+n)&lt;0. Generally, organic anti-reflective coatings can be designed in a variety of forms. In one case, a chemical type of light absorbing agent capable of light absorption may be contained in the main chain of the polymer, and in another case, two different chemical species 'that is, a light absorbing agent and a polymerization which cannot perform light absorption. The objects are used separately. In general, the amount of the chemical species that the light absorber is often used alone to use for light absorption can be controlled. As a general polymerization curing agent, a polymer containing a hydrazine Xy 1 functional group, a gyicidyl functional group, an acetal functional group or the like is frequently used. In the present invention, the copolymer represented by the above Chemical Formula 1 has a carb〇xyiic acid functional group capable of undergoing heat curing and a maleic acid needle (maieic 200944546 anhydride) known to have a residual rate. 'And used as a poly-curing agent together with chemicals that can absorb light. The above polymer forms a polymer of the following Chemical Formula 2 by polymerizing maleic anhydride and an alkyl acrylate-based compound, and the reaction intermediate of Chemical Formula 2 obtained from the above polymerization reaction contains 1 It is produced by polymerizing to an alkylene group (alkyl ale〇h〇l) of one carbon atom.

[Chemical Formula 2]

It is characterized in that '沁 and 吣 are independent of each other; R2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms or an arylalkyl group having 1 to 2 carbon atoms, and R3 is a hydrogen atom or a fluorenyl group; And η are repeating units on the main chain, m+n=i and satisfy the condition 〇. 〇5&lt;m/(m+n)&lt;0. 95 and 0. 05&lt;n/(m+n)&lt; 0. 95. The above-mentioned alkyl acrylate-based compound is derived from methyl acrylate, ethyl acrylate, lsopiOpyl acrylate, normal propyl acylate, n-butyl acrylate. (n〇rmai butyl acrylate), acrylic acid 9 200944546 isobutyl acrylate, tert-butyl acrylate, cycloshexyl acrylate, isobornyl acrylate Acrylate), 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, Normal propyl methacrylate, tert-butyl methacrylate, normai butyl methacrylate, is〇butyl methacrylate, Cyclic hexyl methacrylate, isoprene methacrylate, mercapto propylene Group, 2-ethylhexyl acrylate (2-ethyhexyl methacry 1 ate) selected out. The carboxylic acid functional group formed by ring-opening the reaction intermediate compound of Chemical Formula 2 and a fatty alcohol reacts with a curing agent having an acetal functional group or the like to form a crosslinkable structure. The antireflective coating using this polymer is subjected to a coating during the baking process after the coating on the liner and is resistant to impurities in the spray. It can impart stability so that the anti-reflective coating described above is not dissolved in the solvent of the photosensitizer in the stage of the coating of the silk coating after lamination, and the above polymer can be better used as the above organic anti-reflection coating. A polymeric curing agent for a reflective coating composition. The above polymers can be polymerized by an existing method, but a radical-initiated polymerization reaction is more employed. The above radical polymerization initiator is not particularly limited as long as it can be used as a usual radical-initiated polymerization initiator, such as azobisisobutyronitrile or peroxybenzene. Benzoyl peroxide, lauryl peroxide, azobisisocapronitrile, azobisisovaleronitrile or t-butyl hydroperoxide ° The reaction may be carried out by bulk polymerization, solution polymerization, suspension polymerization, su 1 1 suspension polymerization, emulsion polymerization, And for the above polymerization solvent, from benzene, toluene, xylene, halogenated benzene, diethyl ether, tetrahydro sulphur Tetrahydrofuran), esters, mystery 200944546 (ethers), lactones, ketones (ke At least one selected from tones and amides is used. The polymerization temperature of the above polymer is selected and used in accordance with the type of the initiator. The molecular weight distribution of the above polymer can be appropriately controlled by changing the amount of the polymerization initiator and the reaction time. After the completion of the above polymerization, it is preferred to remove any unreacted monomers and by-products remaining in the reaction mixture by precipitation in a solvent. In order to control the above molecular weight, since it is generally difficult to obtain a molecular weight by gel permeation chromatography (GPC: Gel Permeation Chromatography), for example, in the case where a ring-opened maleic anhydride is obtained, the polymer of the above chemical formula 2 should be used. Reference is made to the molecular weight of the above polymer which is a polymer of an alcohol having 1 to 10 carbon atoms in a ring-opening oxime. That is, the reaction intermediate represented by Chemical Formula 2, which is measured by gel permeation chromatography and normalized with polystyrene (p〇lyStyrene), that is, the polymer before ring opening has a weight average molecular weight of 1,000 to 10,000 Å and The solvent solubility (s〇lubiiity in sol vents), coatability (coatabi 1 ty ), and sufficient crosslinkability (sufficient cross-linking bonding) is preferably from 5,000 to 50,000. 5至3. 5。 The polydispersity index of the polymer (pdi: Polydispersity Idex) is the highest in the range of 1. 0 to 5. 0. Specific examples of the polymer represented by Chemical Formula 1 according to the present invention include, but are not limited to, the following polymers containing the structures of the following Chemical Formulas 3 to 7. [Chemical Formula 3]

13 200944546

[Chemical Formula 7] 〇H3

Wherein m and η are repeating units on the main chain, m+n=l and satisfy the condition 〇·05&lt;m/(m+n)&lt;0. 95 and 0. 05&lt;n/(m+n) &lt;0. 95. The light absorbing agent is contained in the above composition to provide an organic antireflection coating having high etching rate, and is represented by the following Chemical Formula 8. [Chemical Formula 8]

R2 200944546 is characterized in that R1 represents a filament containing 1 mG carbon atoms; r2 represents a money atom, minus or contains 1 to H) carbon atoms; m and n are repeating singles on the main chain. +n = 1 and it satisfies the condition Q Q5 &lt; m / (m + n) &lt; 〇 95 and 〇 · 〇 5 &lt; n / (m + n) &lt; The above polymer is produced by polymerizing maleic anhydride and a styrene compound to form a lower oxime type 9 complex, and polymerizing the resulting polymer obtained by the above polymerization reflection with a fatty alcohol having 1 to 10 carbon atoms. . [Chemical Formula 9]

It is characterized in that it represents a hydrogen atom or a hydroxyl group or a burnt group having 1 to 10 carbon atoms; m and η are repeating units on the main chain, m+n=l and satisfy the condition 〇. 05&lt;m/(m +n) &lt;0. 95 and 0. 05 &lt; n / (m + n) &lt; 0. 95. The polymer of Chemical Formula 8 utilizes a fatty alcohol to allow a carboxylic acid functional group formed by ring opening of maleic anhydride to react with a curing agent 15 200944546 having an acetal functional group or the like. Forming a crosslinkable structure. The antireflective coating using this polymer is cured in the baking process after coating on the liner, and maintains resistance to dissolution in a solvent. Therefore, there is no problem in that the above anti-reflective coating layer is in the stage of the photosensitizer coating after lamination, and there is no problem of being dissolved in the photosensitive agent. Further, since the above polymer contains a highly absorptive choromophore to enable the above polymer to absorb light having a wavelength of i93 nm, the polymer of the above chemical formula 1 can be preferably used as a light source with respect to 193 nm. A light absorber for organic anti-reflective coating compositions. Further, since the above polymer has a large amount of oxygen atoms, an organic antireflection coating composition having a high etching rate can be produced. The above light absorbing agent can be polymerized by an existing method, but the radical priming ® polymerization reaction is more advanced. The initiator for the radical-initiated polymerization is not particularly limited as long as it can be used as a usual radical-initiating polymerization initiator, such as azobisisobutyronitrile, benzophenone, and lauric acid peroxide. Azobisisohexanenitrile, azobisisovaleronitrile or tert-butyl peroxide. The above polymerization reaction may be carried out by bulk polymerization, solution polymerization, suspension polymerization, bulk suspension polymerization, emulsion polymerization, etc., and for the above polymerization solvent, from benzene, sulfonate, xylene, benzobenzene, diethyl benzene, tetrahydrofuran, At least one of vinegar, mystery, lactone, and 200944546 remaining and decylamine is used. It is selected and used by riding the county compound (4) and the anti-ship degree (4). The molecular weight distribution of the above polymer is appropriately controlled by changing the amount of polymerization and the reaction enthalpy. After completion of the above polymerization, it is preferred to remove any unreacted monomer and by-products remaining in the reaction mixture by precipitation in the spray. In order to control the above molecular weight, it is difficult to pass the gel permeation under normal circumstances.

Gel Permeation Chromatography), for example, in the case where a ring-opened maleic anhydride is obtained, the molecular weight of the polymer of the above Chemical Formula 2 should be cited, which has 1 to 10 carbon atoms before ring opening. a polymer of alcohol. Gf7, which is measured by gel permeation chromatography and is represented by the chemical formula 2, which is normalized to the polystyrene phase. The weight average molecular weight of the (tetra) compound before the ring opening is 诵 to 10,000. For the light absorber of Chemical Formula 8, one selected from the polymers having the following Chemical Formulas 1 to 13 can be used. [Chemical Formula 10]

200944546 [Chemical Formula 11]

[Chemical Formula 12] ❻

ΟΗ [Chemical Formula 13]

J η ch3 where 'm and η are repeating units on the main chain, m+n=l and satisfy the condition of 0. 05&lt;m&(m+n)&lt;0·95 and 〇. 〇5&lt;n/( m+n) <0. 95. Meanwhile, as the light absorbing agent used in the present invention, a compound having the following chemical gas 18 200944546 14, 19 or 20 can also be used to provide an organic anti-reflective coating having a high residual ratio. [Chemical Formula 14]

〇CHj is characterized in that Ri is selected from one |1 - q ~, 0 , CH3 -11 * 'R2 and R3 represent each independent hydrogen atom, a burnt group containing 丨10 carbon atoms or contains 1~ Alkoxy groups of 10 carbon atoms. Wherein the compound of the above formula 14 has two hydroxyl groups per compound 'and thus can form a curing agent when used together with a curing agent containing a functional group such as an epoxy group (ep〇xy) or an acetal group (acetal) Crosslinkable structure. The antireflective coating using this polymer is cured on the liner after coating on the liner and maintains resistance to dissolution in the solvent. Therefore, there is no problem in that the anti-reflective coating layer described above is in the phase of the photosensitizer coating after lamination, and there is no problem of being dissolved in the solvent of the photosensitizer. Further, since the above polymer contains a highly absorptive chromophore such that the above polymer can absorb light having a wavelength of 193 nm in 200944546, the above-mentioned polymer of the formula 能 can be preferably used as an organic antireflection with respect to a light source of 193 nm. A light absorber for the coating composition. Further, an organic anti-reflective coating composition having a high etching rate can be produced due to a large amount of oxygen atoms of the above polymer. The above compounds can be obtained by using phenyl derivatives with dicarboxyl groups and phenyl glycidol (1,2-epoxy-3-phenoxy-pr〇pane) in a basic catalyst (catalyst) Further, the compound having the following chemical formulas 15 to 18 as the light absorber used in the present invention can also be used to provide an organic antireflection coating having a high yield. 15]

[Chemical Formula 16] H0

0H 200944546

[Chemical Formula 17] HO

OH

Ο—I

[Chemical Formula 18]

[Chemical Formula 19]

〇 OH

The compound of the above formula 19 has four hydroxyl groups per compound, and thus a crosslinkable structure can be formed when used together with a curing agent containing a functional group such as an epoxy group or an acetal group. The use of this polymer 21 200944546, the coating is cured on the liner after the coating, and in the agent to dissolve the dragon resistance. Therefore, the above anti-reflective coating layer does not have a problem of being dissolved in the photosensitive agent at the stage of the photosensitizer coating after lamination. Further, since the above polymer contains a highly absorptive chromophore to enable the above polymer to absorb light having a wavelength of 193 nm, the polymer of the above formula 1 can be better counteracted with respect to a light source of 193 nm. The light of the layered silk is absorbed. Further, since the above polymer has a large amount of oxygen atoms, an organic anti-reflective coating composition having a high etching rate can be produced. The above compound can be produced by reacting bisphenol A diglycidyl and 4-hydroxybenzoic acid under the action of a basic catalyst. [Chemical Formula 20]

The compound of the above formula 20 has three mercapto groups per compound, and thus a crosslinkable structure can be formed when used together with a curing agent containing a functional group such as an epoxy group or an acetal group. The anti-reflective coating using this polymer is cured during baking after coating on the liner, and maintains resistance to dissolution in the solvent. Therefore, there is no problem that the above anti-reflective coating layer is dissolved in the solvent of the photosensitizer at the stage of the photosensitizer coating after lamination. Further, since the above polymer contains a highly absorptive chromophore such that the above polymer can absorb light having a wavelength of 193 nm, the polymer of the above formula i can be preferably used as an organic antireflection coating when it is used with respect to a light source of 193 nm. A light absorbing agent for the layer composition. Moreover, since the above polymer has a large amount of oxygen atoms, an organic anti-reflective coating composition having a high etching rate can be produced. The above compound can be obtained by using tris(2-carboxyethyl)isocyanate

Ctris(2-carboxyethyl)isocyanurate) and 1,2-epoxy-3-phenoxy-propane are formed by a reaction of a basic catalyst. Various compounds can be used as additives to aid in curing and to enhance the properties of the organic antireflective coating and light absorbing agent. The curing agent may be used as the first example of the above-mentioned additive, and a carboxylic acid functional group or hydrogen having at least two or more crosslinkable functional groups per compound and having a carboxylic acid functional group and a light absorbing agent capable of reacting with the antireflective coating compound The compound of the functional group reactive with an oxy group can be used as a curing agent 23 200944546. For example, 'aminoplastic compounds, polyfunctional epoxy resins, anhydrides, mixtures thereof and the like can be referred to. Wherein the above crosslinkable functional group is derived from a methylol group, an alkoxymethyl group, an oxetanyl group, an oxazoline group, a cyclic carbonate group. (cyclocarbonate group), alkoxysilyl group, aziridinyl group, isocyanate group, alkoxymethylamino group, aminomethylol group And a polyfunctional epoxy group, all substituted glycoluril compounds, urea compounds, benzoguanamine compounds, or argon atoms on the amino group of a melamine compound At least one of the groups selected. Specific examples include hexamethoxymethyl melamine, tetramethoxymethyl benzoguanamine, 1'3'4,6-tetrakis(butoxymethyl)glycolil ( Tetrakis(butoxymethyl)glycoluril), 1,3-di-indenyl-4, 5-mono-yl-2-pyristin 24 200944546 · (1, 3-bis(hydroxymethy1)-4, 5-dihydrxy-2 -imidazolinone ... ), 1,3-bis(methoxymethyl)-4, 5-dimethoxy-2-imidazolidinone (1, 3-bis(methoxymethyl)-4, 5-dimethoxy-2-imidazolinon e) Etc. Examples of commercially available products include methoxymethyl tylpe melamine compounds such as melamine resin (Cymel) 300, melamine resin 301 and melamine resin 305; butoxy Butoxymethyl melamine compounds, such as amino resin (Mycoat) 506 and amino resin 508; glycoluril compounds such as Cymel 1170 and glycoluril resin 1Π4; butylated modified urea resin such as URF300, U - VAN10R and U-VAN11HV; urea/formaldehyde-based resin such as Bekamin J-300S,

Bekamin P-955 and Bekamin N and their derivatives. For polyfunctional cyclic oxime compounds, commercial products and derivatives thereof under the trade names MY720, CY179MA and DENAC0L are preferred for use. As a second example of the additive, a thermal acid generator is used as a catalyst for accelerating the above curing reaction. It is preferred to use a compound represented by the following Chemical Formula 21 or 23 as a thermal acid generator. Since the compound represented by the following Chemical Formulas 21 to 23 can exhibit good curing efficiency when used with a curing agent having various functional groups described above, the above compound has an appropriate property of the antireflective coating composition to allow curing of the curing. The time limit is less than 5 minutes. [Chemical Formula 21]

OH

And, as an organic solvent of the organic anti-reflective coating composition which can be used in the present invention, at least one is derived from propylene glycol monomethyl ether (PGME: propylene glycol monomethyl ether). Acetate), cyclohexanone, ethyl lactate, propylene glycol n-propyl ether, dimethyl formamide ' 7-Ti^ Si ( Gamma-butyl ro lac tone) 'ethoxyethanol, methoxyethanol, 26 200944546 3-methoxypropionate (MMP: me1; hyi 3_meth〇xypropionate) and 3- • · B The solvent selected from the group of EEP (ethyl 3-ethoxypropionate) was used. In the organic anti-reflective coating composition according to the present invention, the polymer of Chemical Formula 1 used as the organic anti-reflective coating polymer accounts for 〇. 1% to 40% by weight of the total anti-reflective coating composition, and light The absorbent comprises from 0.1% to 40% by weight of the total antireflective coating composition. 01%至20百分比。 The curing agent is from 0. 01% to 40% by weight of the total anti-reflective coating composition, and the thermal acid generator is from 0.01% to 20% by weight of the total anti-reflective coating composition. When the organic anti-reflective coating composition having the composition ratio of the above components is coated on a wafer and heat-treated, for example, baking, an acid is generated from the above-mentioned hot acid generator, and among the above-mentioned generated acids, The reaction between the hydroxyl group and the light absorbing agent of the chemically resistant organic anti-reflective coating polymer and the curing agent used as an additive is promoted. Therefore, an organic anti-reflection coating which is not dissolved in the photoresist solvent is formed. The above-mentioned organic anti-reaction layer absorption has been transmitted to the anti-reflective coating layer to contact the ultraviolet ray, thereby preventing diffuse reflection in the ridge layer. 27 200944546 In the above process of the organic anti-reflective coating according to the present invention, the above-described feeding process is carried out at a temperature of 251 TC and lasts for 2 sec to 6 。. And the above baking process is preferably 15 〇. 〇 to 25 (the temperature of rc is continued for 5 minutes. In the step, after the acquisition of the organic anti-reflective coating, the red art corresponds to the existing process for the patterned semiconductor device, and thus is not particularly limited. In the above-described patterning method according to the present invention, the second baking process may be additionally performed before or after exposure in the step of forming the photoresist pattern, and the above second baking process is preferably at 7 ° C to 2 The present invention is described in more detail below by combining preferred synthesis examples and specific exemplary embodiments. However, these examples are merely intended to be used as a broad description and the invention is not limited to these. Example: Synthesis Example 1 Synthesis of a polymer for the organic anti-reflective coating A. 2 g of maleic anhydride, 30 g, dissolved in 120 g of 1,4-dioxane. Methyl methacrylate and 2.97 g of AIBN, and the above mixture was subjected to polymerization at 70 ° C for 12 hours at the end of the reaction. After the above reaction was completed, the above reactant was The sinking material obtained by adding to methanol (me thy 1 a 1 coho 1) was dried and vacuum dried (Mw = 17, 200, PDI = 2.95, yield = 58%). 72 g of the above vacuum dried The polymer and 〇.55 g of toluenesulfonic acid monohydrate were mixed with 725 g of methanol, and then the above mixture was subjected to a reaction at 7 (TC for 48 hours). After the above reaction was completed, the above reaction was carried out. The solvent was added to distilled water to obtain a precipitate, which was filtered, and then washed several times with distilled water and vacuum dried (yield = 58%). Synthesis Example 2 Synthesis of a polymer for the organic antireflection coating B at 480 94 g of 1 '4-dioxane dissolved 56.5 g of maleic acid field, 100 g of benzyl methacrylate (benzyl methacrylate) 0 4 67 g of AIBN, and the above mixture was allowed to proceed under it. The polymerization was carried out for 2 hours. After the completion of the above reaction, the precipitate obtained by adding the above reactant to methanol was filtered and dried under vacuum (Mw = 17, 2 〇〇, pDI = 2 95, yield = 53%). 82. 95g of the above vacuum-dried polymer and 4. 23g of the pair Toluene sulfonic acid monohydrate was mixed with 12 〇〇g of methanol, and then the above mixture was subjected to a reaction at 8 〇 29 200944546 ° C for 48 hours. After the above reaction was completed, it was obtained by adding the above reaction solvent to distilled water. The precipitate was filtered, washed several times with distilled water and dried under vacuum (yield = 53%). Synthesis Example 3 Synthesis of Light Absorber A sty 购买 styrene-maleic anhydride polymer purchased from Sigma-Aldrich Company, Inc. (Mn = 1,600, the number of moles of styrene: moles of maleic anhydride = 1.3: 1), and 77 g of p-toluenesulfonic acid monohydrate mixed with 1 g of methanol, and The above mixture was at 7 Torr. The reaction was carried out for 48 hours under the armpit. After completion of the above reaction, a precipitate was obtained by adding the above reaction solvent to distilled water, followed by filtration, and then washed several times with distilled water and vacuum-dried (yield = 1% to 4%). Synthesis Example 4 Synthesis of Light Absorber B 21.80 g of BiSphenol A diglycidyl ether and 17·69 g of 4-hydroxybenzoic acid 200944546 and 〇. 37g of triethyl The triethylamine was dissolved in 78.98 g of Pr〇Pylene glycol monomethyl ether acetate, and the above mixture was subjected to a reaction at 12 ° C for 18 hours. After the completion of the above reaction, the above reaction solution was cooled to ambient temperature and transferred to a vessel. 〇β Synthesis Example 5 Light Absorbent C Synthesis 2 〇〇g Tris(2-carboxyethyl) Isocyanate (tris(2- Carboxyethyl)isocyanurate), 260. 9gl '2-epoxy-3-phenoxy-propane and 3.52g of triethylamine mixed with 928·8gl,4-dioxane' and the above mixture at 12(TC The reaction was carried out for 18 hours. After the completion of the above reaction, the above dissolution was removed in the evaporator, and the residue was dissolved in methylene chloride, followed by repeated aqueous hydrochloric acid solution and distilled water. Washing. The reaction product was obtained by using an evaporator to remove the above solvent. Synthesis Example 6 Synthesis of Light Absorber D 31,044,546 100 g of 4,4'-diphenyl ether dicarboxylic acid, 116.31 g of 1,2-epoxy -3- phenoxypropane and 6.24 g of tetrabutylamm〇nium bromide are mixed with 457·58 g of propylene glycol monomethyl ether acetate, and the above mixture The reaction was carried out at i2 〇 °c for 18 hours. After completion, the reaction solution was cooled to ambient temperature and transferred to a vessel. Synthesis Example 7 Synthesis of Light Absorbent E 50 g of sulfonyldibenzoic acid, 49.03 g of 1,2-epoxy-3-phenyloxy Base propane and 5.26 g of bromotetrabutyl alcohol are mixed with 208.58 g of dimethylformamide and the above mixture is reacted at 12 (TC for 18 hours. After the above reaction is completed, the reaction solution It was cooled to ambient temperature. Distilled water and ethane were used to form a solid and washed with distilled water, and the above-mentioned moisture was removed by a vacuum furnace to obtain a reaction product. Example 1. Production of an organic anti-reflective coating composition A The polymer 7g for the organic antireflection coating manufactured in the above Synthesis Example 1 'the light absorber a 6g manufactured in the above Synthesis Example 3, 2g of the tetramethyl 32 200944546 oxymethylglycolide and having the chemical formula 23 _ The lg thermal acid generator is dissolved in the propylene glycol ketone, and the organic antireflective coating composition A is produced by the lining having a pore size of 0.2 _. Example 2: Organic antireflection coating Fabrication of layer synthesis in the above synthesis example 7 g of a polymer produced in an organic anti-reflective coating layer, a light absorbing agent B 8g manufactured by the above Synthesis Example 3, 2. lg tetradecyloxymethylglycolide, and an ig-touch formation surface having a structure of Chemical Formula 23 The above organic anti-reflective coating composition B was produced by dissolving in 981.9 g of ethyl lactate and then filtering by a membrane filter having a pore size of 0.2 angstrom. Example 3: Production of Organic Anti-Reflection Coating Composition C Polymer 8g for an organic anti-reflective coating layer manufactured in the above Synthesis Example 1 'The light absorber B1〇g, manufactured in the above Synthesis Example 4, 2. 7g of tetradecyloxymethylglycolide and hydrazine having the structure of formula 23. 54g of thermal acid generator is dissolved in 978.76g of propylene glycol oxime ether acetate, and then passed through a membrane filter having pores 33 200944546 with a diameter of 0.2 泖. The above organic anti-reflective coating composition C was produced since the filtration was carried out. Example 2: Manufacture of the organic anti-reflective coating composition D. The polymer for the organic anti-reflective coating layer produced in the above-mentioned Synthesis Example 1 8g of the light absorbing agent C6g produced in the above Synthesis Example 5, 2. 8g Ethoxydimethoxyglycolide and 〇·54g of thermal acid generator having the structure of Chemical Formula 23 were subjected to a solution of 982.66 g of propylene glycol hydrazone acetate, followed by a perforated melon size of 0.2. The above-mentioned organic anti-reflective coating composition D was produced by filtering the film. Example 5: Manufacture of Organic Anti-Reflection Coating Composition E 8 g of a polymer for an organic anti-reflection coating manufactured in the above Synthesis Example 1, a light absorber ton manufactured in the above Synthesis Example 6, 丨々四甲Oxymethylglycine "and the chemical formula 23" _ Mg brewing hydrazine is dissolved in 985 · 9g of propylene glycol A__, and then magnetically made by having a pore size of 〇· 2 Lin H, called the manufacture of the above organic anti-reflection Coating Composition E. 34 200944546 Example 6: Manufacture of organic anti-reflective coating composition F 8 g of the polymer for organic anti-reflective coating produced in the above Synthesis Example 1, the light absorbing agent E4g manufactured in the above Synthesis Example 7, 1. 7 g of tetramethoxyindoline glycol and 〇. 4 g of a thermal acid generator were dissolved in 985. 9 g of propylene glycol methyl ether acetate, and then filtered through a membrane filter having a pore size of 0.2 Å. The above-mentioned organic anti-reflective coating composition F was manufactured. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Tetramethoxyimylglycolide and hydrazine having the structure of Chemical Formula 23 were dissolved in 988·3 g of propylene glycol myristic acetate, and then passed through a membrane filter having a pore size of 0.2 Å. The above organic anti-reflective coating composition G has been manufactured. The synthesis rates of the compositions of Examples 1 to 3 are collectively shown in Table 1. [Table 1] (°/. by weight) Light Absorption Polymerization TMMF* TAG* PGMEA* EL* Recipient 35 200944546 Example 1 A 0.59 0.69 0.19 0.09 98.42 _ Example 2 A 0.80 0.70 0.21 0.10 98.19 Example 3 B 1.00 0.80 0.27 0.054 97.87 - Example 4 C0.60 0.80 0.28 0.054 98.26 - Example 5 D0.40 0.80 0.17 0.04 98.59 Aspect Example 6 E0.40 0.80 0.17 0.04 98.59 - Example 7 E0.50 0.50 0.14 0.03 98.83 - *TMMG(Tetramehoxymethylglycoluril): IV Thermal acid generating agent TAG (Propylene glycol monomethyl ether acetate): Ethyl lactate EL: Ethyl lactate test example: Demembrane test in the example Each of the above-described organic anti-reflective coating compositions manufactured in Example 1 to Example 7 was spin-coated on a wafer and an organic anti-reflective coating was formed by baking on a plate heated to 230 ° C for 1 minute. The thickness of the organic anti-reflective coating was / hr' and the above-mentioned disc laminated with the above organic anti-reflective coating was immersed in an ethyl acetate solvent for 1 minute. Then, ethyl lactate was completely removed, and 36 200944546 and the above-mentioned wafer together with the anti-reflective coating were baked for 10 minutes on a plate heated to 10 (rc. Then 'the thickness of the above organic anti-reflective coating was again As a result of the measurement, no change in the coating thickness before the ethyl lactate treatment and the coating thickness after the ethyl lactate treatment was observed. That is, it can be confirmed that the above organic antireflection coating in the above baking process The layer composition is completely cured, and thus the case of miscible with the photoresist does not occur during lithography. Experimental example: Measurement of refractive index (η) and extinction coefficient (k) values in Examples 1 to 7 Each of the above-described organic anti-reflective coating compositions produced in the present invention was spin-sprayed onto a wafer and formed a crosslinked organic anti-reflective coating after being baked to 23 (rc) for 1 minute. The organic anti-reflective coating used a spectral ellipsometer to measure the refractive index (8) and the extinction coefficient (k) at 193 nm. As a result of the measurement, the refractive index (V) of the above organic anti-reflective coating composition A was 丨.66. And the extinction coefficient (1) is G.%. The refractive index (5) of the above organic anti-reflective coating composition B is 丨.73, and its extinction coefficient (1) 疋〇. The refractive index of the above organic anti-reflective coating composition C (n) Is 1.78, and its extinction coefficient (k) is 〇. 32. 37 200944546 Example 8: Patterning of organic anti-reflective coating and photoresist The above-mentioned organic anti-reflective coating composition manufactured in Example 1 was Rotatingly sprayed on a cerium wafer having cerium oxynitride, and the above composition was crosslinked to form an organic anti-reflective coating after being baked to 23 (TC for 1 minute baking. Then 'produced by JSR Co., Ltd. A photoresist was applied to the upper portion of the above anti-reflective coating and then the above coated wafer was baked at 13 (TC for 90 seconds).

After baking, exposure was performed using an ASML 1400 scanner (〇. 85 M) device and an 80 nm 1:1 L/S mask and the coated wafer was baked for another 9 seconds at 11 (TC). The exposed wafers are made up of tetramethyl hydrazine oxide (TMAH:

Tetra Methyl Ammonium Hydroxide) 2.38% by weight of the developing solution was developed, and thus the final photoresist pattern was obtained. The photoresist pattern obtained using the above-described organic anti-reflective coating composition A is a very good vertical pattern' and has an energy margin of about 25% and a depth of focus margin of about 0.5 qing. The photoresist pattern obtained using the above-described organic anti-reflective coating composition b is a good vertical pattern and has an energy margin of about 23% and a depth of focus margin of about 0.3 Å. The photoresist pattern obtained using the above organic anti-reflective coating composition C is a good vertical pattern and has an energy margin of about 22% and a depth of focus margin of about 0.3 _. 38 200944546 Test example: Measurement of rhyme rate' Each of the above-mentioned organic anti-reflective coating compositions made in the above-mentioned caps were rotatably sprayed on a Shihwa wafer and heated to 23 (rc plate). The organic anti-reflective coating formed by cross-linking has been formed since the minute. According to the organic anti-reflective coating formed above, the wafer is _(3) gas in the dry etching device, and it is 10 亥 hai | J 10 seconds. The side ratio is defined as (thickness before film thickness - film thickness after stenciling) / time. It is converted according to the dry etching selectivity, and as a result of the above, the organic anti-reflective coating compositions AB and C The residual rate of the CF4 gas is 1.25, 2.35, and 2.20, respectively. The above-mentioned dry button selection indicates the photoresist printed on the ArF plate (by Kumho Petrochemical Co., Ltd.: Kumho Petrochemical Co., Ltd. The dry etching rate of the commercial name KUPR-A60) was set to 1·〇〇, and the dry residual rate of the organic anti-reflective coating was obtained. The results of the test examples of Examples 1 to 7 are shown in Table 2. It is shown intensively. [Table 2] De-filming refractive index absorption system Amount of time, a lot of dry money, a few degrees of choice (%) (μιη) degree 39 200944546 Γ----&quot; Example 1 Good 1.77 0.44 25 0.3 2.25 Example 2 ------ Good 1.79 0.47 23 0.3 2.35 Example 3 Good 1.65 0.32 22 0.3 2.20 Example 4 Good 1.72 0.35 22 0.2 2.30 Example 5 Good 1.68 0.30 22 0.3 2.28 Example 6 Good 1.75 0.35 22 0.25 2.25 Example 7 Good 1.78 0.39 21 0.25 2.20 It was confirmed that it was manufactured from Example 1 to Example 7. The film obtained in the organic anti-reflective coating composition of the present invention has a high etching rate as compared with the photoresist. The process of transferring the photoresist pattern formed on the above organic anti-reflective coating onto the liner If the above-mentioned surname is high, the photoresist pattern can be transferred to the liner more accurately and easily. [Schematic Description] Exemplary embodiments of the present invention by combining the following figures The above and other aspects of the features will become more apparent and easy to understand, wherein: Fig. 1 is a W-NMR spectrum of the copolymer formed according to Synthesis Example 1. [Main element symbol description]

Claims (1)

200944546 VII. Scope of the patent application · · A copolymer represented by the following chemical formula 1: [Chemical Formula 1] It is characterized in that 'Rl, 卩2 and R3 are mutually reciprocal; represent a hydrogen atom or a group having 1 to 10 carbon atoms; R2 represents a hydrogen atom or a filament containing 丨 to 1 碳 carbon atom or contains 丨 to 2G hind. An aryl ray of an atom; R3 is an amino atom or a methyl group; m and n are repeating units on the main chain, m(d) and have 〇. 〇5&lt;m/(m+n)&lt;〇. 95 and 〇. 〇 5&lt;n/(m+n)&lt;0·95. An organic anti-reflective coating composition comprising a copolymer represented by the above Chemical Formula 1, a light absorbing agent, a thermal acid generator, and a curing agent. 3. The organic anti-reflective coating composition according to claim 2, wherein the light absorbing agent is a copolymer represented by the following Chemical Formula 8 and has a weight average molecular weight of 1,000 to 100,000, 200944546 [Chemical Formula 8] ] It is characterized in that 'Rl represents a burning group having 1 to 10 carbon atoms; the wire represents a nitrogen atom, weaves or contains 1 to a group of fluorenyl groups; m and η are repeating units on the main chain, m+n=1 and There are values of Q / (m + n) &lt; {).95 and 〇 · 05 &lt; n / (m + n) &lt; 0. 95. The organic anti-reflective coating composition according to claim 2, wherein the light absorbing agent is a compound represented by the following chemical formula 14, 19 or 20, [Chemical Formula 14] R3 OH II 0 11 is characterized in that [^ from .............. selects a table _ cis atom, 42 alkyl group of 200944546 or contains 1 to 10 carbon atoms Alkoxy group. [Chemical Formula 19] The organic anti-reflective coating composition of any one of the above-mentioned items, wherein the above-mentioned two or more crosslinkable functional groups per compound are provided. And selected from the group consisting of an amino plastic compound, a polyfunctional epoxy resin, a sour liver, and a mixture thereof. The organic anti-reflective coating composition as described in claim 5, characterized in that the above-mentioned _ _ _ is from the thiol-containing hydrocarbon 43 200944546 oxymethyl, oxobutyl, oxazole Alkyl, cyclocarbonate, alkoxycarbonyl, aziridine, isocyanate, alkoxyamino, aminoguanidino and polyfunctional epoxy, all substituted glycoluril compounds, urea compounds, At least one selected from the group consisting of a hydrogen atom on the amino group of the benzene melamine compound or the melamine compound. The organic anti-reflective coating composition according to claim 2, wherein the thermal acid generating agent to be used is at least one selected from the group consisting of compounds of the following Chemical Formulas 21 to 23. [Chemical Formula 21] OH Ο II 0-S II Ο [Chemical Formula 22] [Chemical Formula 23] The invention relates to the organic anti-reflective coating composition according to claim 2, wherein the above composition comprises at least one from the group consisting of propylene glycol (PGME), propylene glycol methyl ether acetate (PGMEA), cyclohexanone, and lactate B. Vinegar, propylene glycol n-propyl ether, dimethylformamide (DMF), 7-butyrolactone, ethoxyethanol, methoxyethanol, methyl 3-methoxypropionate (MMP) and 3-ethoxyl The solvent selected from the group of ethyl propionate (EEP). 9. The organic anti-reflective coating composition as described in claim 2, wherein the composition comprises: 1% to 4% by weight of a copolymer for an organic anti-reflective coating 〇. 1% To a 40% by weight of a light absorbing agent, 〇. 〇 1% to 20% by weight of a thermal acid generator and from 0.01% to 40% by weight of a curing agent. 10. The organic anti-reflective coating composition according to claim 1, wherein the copolymer of the above Chemical Formula 1 is an organic anti-reflective coating formed by reacting a reaction intermediate of the following Chemical Formula 2. Copolymer 'The reaction intermediate of the above Chemical Formula 2 is formed by copolymerizing maleic anhydride and an alkyl acrylate base compound with a fatty alcohol having 1 to 10 carbon atoms, [Chemical Formula 2] 45 200944546 characterized in that R 2 and hydrazine are independent of each other; 吣 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms or an arylalkyl group having 1 to 20 carbon atoms; R 3 is a hydrogen atom or a methyl group; m and n are repeating units on the main chain, m+n=1 and have G. G5&lt;m/(m+n)&lt;()· 95 and G·G5&lt;n/(_)&lt;G. The value of 95. 11. The organic anti-reflective coating composition according to claim 10, wherein the alkylacrylic anhydride-based compound is from methyl acrylate, ethyl acrylate, isopropyl acrylate, n-propyl acrylate or acrylic acid. Butane vinegar, isobutyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, N-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methacrylic acid 2 Select from the group of _ethylhexyl ester. 12. The organic anti-reflective coating composition according to claim 3, wherein the compound of the above Chemical Formula 8 is a light absorbing agent produced by reacting the copolymer of the following Chemical Formula 9 'the compound of the above Chemical Formula 8 Formed by copolymerizing maleic anhydride and a styrene compound with a fatty alcohol having from 1 to 1 carbon atom, 46 200944546 [Chemical Formula 9] Ri 〇 〇 沁 沁 沁 沁 沁 沁 沁 沁 沁 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢(m+n) &lt; 0. 95 and 〇· 〇 5 &lt; n / (m + n) &lt; 0. 95 value. 13. A method for patterning a semiconductor device, comprising: applying an organic anti-reflective coating composition according to claim 2 or 4 to an upper portion of a coating to be etched; _ curing by baking to apply the above a composite, and form a crosslinked structure for forming an organic anti-reflective coating; the photoresist is applied to the anti-aliasing layer of the upper surface, and the photoresist is exposed and developed for photolithography A glue pattern; and the above-described organic anti-reflective coating is etched using the above-described photo-pattern as a paste mask and then the above-mentioned coating to be patterned is used to pattern the above-mentioned layer to be surnamed. The method for patterning a semiconductor package 200944546 according to claim 13, wherein the baking process is carried out at a temperature of 15 ° C to 25 (TC for 1 minute to 5 minutes. The method for patterning a semiconductor described in the thirteenth or fourteenth aspect of the patent includes the third baking before or after the exposure wire is patterned into the above photoresist. The method for patterning a semiconductor device according to Item 15, wherein the second baking process is performed at a temperature of 7 (rc to a temperature of C. 17: a petal coffee (four) item Qian Nenyi The semiconductor device manufactured for the semiconductor device. 48