TWI295295B - Organic anti-reflective coating polymers, anti-reflective coating composition comprising the same and preparation methods thereof - Google Patents

Description

1295295 Case No. 90127504__年月曰_Amendment_ V. INSTRUCTION DESCRIPTION (1) Technical Aspect The present invention relates to an organic anti-reflective polymer which can prevent the lower film layer from being reflected and eliminated due to the thickness of the photoresist The standing wave caused by the change of light and the process of manufacturing ultra-fine pattern by using the photoresist of 193 nm argon fluoride (ArF) lithography and its preparation method. More particularly, the present invention is also directed to an organic antireflective polymer for ultrafine patterns of 64 Μ, 256 Μ, 1 G, and 4 G DRAM semiconductor devices. There is also a composition comprising the organic antireflective polymer, an antireflective coating made thereof, and a method of preparing the same. BACKGROUND OF THE INVENTION The CD produced by the optically specific standing wave and the reflective concave in the preparation of the semiconducting low film layer (critically introduced can be introduced into the organic material, coated with a 4/L reflective coating, or as it is used for the use of The anti-reflective coating is used as an absorption system, and in the process of using ultra-fine patterns of fluorination using argon oxynitride as a film, it will be inevitable due to changes in wafer properties and thickness of the film. The mouth of the ground; in addition, 'the size of the diffracted light and the reflected light from the lower film layer' will have other problems. Therefore, an anti-reflective coating having high absorbance in the wavelength region of light as a light source to avoid back reflection at a lower film layer has been proposed. y Depending on the materials used, it is divided into inorganic and organic anti-back-action mechanisms and is divided into absorption and interference anti-reflection coatings. For (365 nm wavelength) radiation, it can be clearly used, because titanium nitride can be used. ) with amorphous carbon when using yttrium oxynitride (Si〇N) as an interference system. In the process of making ultra-fine patterns of gas (KrF) laser, it has been made of inorganic anti-reflection film; however, it can control interference when using inorganic anti-reverse 1295295 __ case number 90127504 _ _ _ 5, invention description -- . Therefore, there are many efforts to utilize organic compounds as anti-reflective coatings. In order to be a good organic anti-reflective coating, the following conditions must be met: (1) The photoresist layer peeling due to dissolution in a solvent must not occur in the lithography process. A mold coating must be designed to achieve this goal. (molded coating) joins the structure without producing any by-product chemicals. (2) Chemicals such as acids or amines must not migrate into or escape from the antireflective coating because, as the acid migrates from the antireflective coating, amine migration occurs at the substrate, And undercut occurs in the lower part of the pattern. The θ (3) anti-reflective coating must be etched at a faster rate than the upper photosensitive film to perform an etching process using the photosensitive film as a mask. (4) Therefore, the anti-reflective coating must be as thin as possible to reflect the extent of the coating. Anti-anti

The existing organic anti-reflective coatings are mainly classified into two types, in particular, (1) polymerization comprising a chromophore, a crosslinking agent (single molecule) of a crosslinked polymer, and an additive (thermally variable oxidizing agent). And (2) a polymer which is self-crosslinkable and which includes a chromophoric group and an additive (thermally variable oxidizing agent). However, there is a problem with the two antireflective materials: the k value can hardly be controlled because of the chromophore content defined by the ratio of the original design at the time of polymerization. Therefore, if you want to change the k value, you must re-synthesize. Summary of invention

5i42.4459PFl.ptc Page 6

Fix 曰

Jf;_η The present invention also provides a method for preparing a white. The anti-reflective coating composition of the polymer is formed into a rd; for: forming a pattern on the semiconductor device by using an anti-reflective coating of sub-micron lithography. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The coatings are respectively provided with the following compounds having the formulas 1 and 2 for an anti-reflection type 1 in the above formula 1:

Ra ' Rb is an individual independent gas or thiol · R, R is an individual -H, -oh..., -CH2〇H ' or a substituent or an unsubstituted group, or a straight or branched An alkyl group or an alkoxy group having 1 to 6 carbon atoms; η represents an integer selected from 1, 2, 3, 4, and 5; X, y each represents a molar fraction from 0·01 to 〇·99 .

1295295

Further, in the above formula 2, riq and Rii are each independently a linear or a substituted alkoxy group; and further, r12 is hydrogen or a methyl group. The compound of the formula 2 is prepared by polymerizing (fluorenyl) acrolein so that the obtained polymerization product is reacted with a branched or linear substituted alkoxy group having 1 to 1 carbon atom to give a polydecyl acrolein. In more detail, (meth)acrolein is first dissolved in an organic solvent, a polymerization initiator is added thereto, and polymerization is carried out for 4 to 6 hours under a vacuum of 6 to 7 art. Next, the obtained polymerization product is reacted with a branched or linear substituted alkoxy group having 1 to 1 carbon atom at room temperature with trifluoromethylsulfonic acid as a catalyst. In the above process, it includes tetrahydrofuran (THF), CyCi〇hexanone, dimethylformamide, dimethylsulfoxide, dioxane. An appropriate organic solvent is selected from the group consisting of methylethylketone, benzene, toluene, xylene, and mixtures thereof. As the polymerization initiator, it can be 2, 2-azobis catalyst (2, 2~azobisisobutyronitrile) (AIBN), peroxydibenzoic acid

1295295 -- Case number, 诵 _ bunch 曰 s correction _ 5, invention description (5) (benzoylperoxide), acetyiperoxide (acetyiperoxide), laurylperoxide, tertiary butyl peracetate (t -buty lperacetate), butyl hydroperoxide or di-t-butylperoxide, etc., and having 1 to 1 carbon atom of the alkyl group A preferred embodiment of the alcohol is ethanol or decyl alcohol. Preferred compounds of formula 2 may be compounded by the following formulas 3 to 6 A3

5142-4459PFl.ptc 1295295 No. 1 90127504 V. Description of invention (6)

〇ch2ch3

The compound of the above formula 3 to formula 6 of the h3ch2co alcohol-based polymer can be cured under acid and other conditions. The polymer of Formula 1 can be prepared by reacting an acetoxy styrene monomer with a hydroxyalkyl acrylate monomer in an organic solvent, followed by polymerization of the resulting compound. The reaction initiator is polymerized. In this process, any conventional organic solvent can be used, but a preferred solvent is from the group of tetraphenyl, benzene, butyl hydrazine, dioxane and a mixture thereof to the polymerization initiator. A conventional radical polymerization initiator is used, but it is preferably used from a group including 2, 2,-azo catalyst, peroxydiethyl ether, lauryl peroxide, and tertiary butyl hydroperoxide. The selected compounds of the group. The above polymerization is preferably carried out at a temperature ranging from about 50 to 90, and the molar fraction of each monomer is in the range of 〇·〇卜〇. The invention is also a composition comprising an anti-reflective coating of a monoterpene polymer and a polymer component of formula 2. A method for preparing an organic anti-reflective coating according to the present invention comprises the steps of: dissolving a polymer of formula 1 and a compound of formula 2 in an organic solvent, filtering the resulting solution, coating the filtrate on a lower layer, and baking the coating. Cloth layer. In this process, any conventional organic solvent may be used, but it is preferred to include ethyl 3-ethoxypropyl g, decyl 3-ethoxypropyl g, cyclohexanone.

Jg5295 when 90_ year month aw 5, invention description (7) (cyclohexanone) and propylene glycol methyl ether acetate (propyleneglycol methyl ether acetate) selected in the group, and depending on the total weight of the anti-reflective coating resin used, The preferred solvents described above are preferably employed in amounts ranging from about 200 to about 5000% by weight, with the preferred hard roasting temperatures ranging from about 100 to about 300 °C. The present invention also provides a semiconductor device from any of the anti-reflective coating compositions of the present invention.

First, two kinds of monomers having large chromophores (ethoxylated styrene monomer, hydroxyloxy acrylate monomer) are synthesized, so that the polymer obtained from the two monomers can be high at 193 nm. Absorption rate; in addition, in order to produce an organic anti-reflective coating with improved properties such as good moldability, air-tightness and resistance to dissolution, an epoxy resin base can be introduced to allow for the coating step. The hard baking step increases the crosslinking reaction, and the resulting polymer can be regarded as the first polymer (the compound of the formula). Further, the second polymer (the compound of the formula 2) may also synthesize a compound which can form a crosslink upon reaction with the alcohol group in the resin to form a crosslinked product having the first polymer by thermal reaction, in particular, The form of the crosslinking agent is to design a polymer having the maximum crosslinking reaction efficiency, and in particular, the k value of the antireflection film can be freely adjusted by controlling the fraction of the first polymer. Further, the antireflective coating resin has a good bismuth in all hydrocarbon solvents. The bismuth 5 has resistance to solubility in any solvent in the hard baking step. In addition, there will be no undercut or pedestal in the patterning process.

5142.4459PFl.ptc Page 11 Gan special. It is an anti-reflective coating made of 1 acrylic vinegar resin, which can have a higher etching rate relative to the photosensitive film in 1^295. Case No. 90127504 V. Invention Explain the (8) rate, thus improving the etching selectivity. The embodiments of the present invention will be more apparent from the following description of the preferred embodiments of the invention. ^N-oxyethyl methacrylate 2-hydroxyethyl ester) 1 copolymerization example Example 1 Composition - a 50 0 ml round bottom container filled with 〇·1 mol acetoxy group while stirring Benzene oxide / 0. 1 molar 2-hydroxyethyl acrylate, and 30 0 g of the individually prepared tetrazo 11 pentane was added to the complete mixture, after which 0, 1 to 3 · 0 g of 2 was added. 2'-Azo catalyst was polymerized for 5 to 20 hours under a nitrogen atmosphere at 60 to 75 °C. After the completion of the reaction, the resulting solution is washed with diethyl ether or fresh hexane, and then filtered and dried to obtain a poly[acetoxy phenethyl acetonate (2-hydroxyethyl acrylate)] Resin (yield: 82%). Equation 7

Example 2 A gas-based stupid---(3-acrylic acid urethane-I-gold composition)

I II

5142-4459PFl.ptc Page 12 1295295 90127504 _Μ, 曰Revision 5, invention description (9) A 500 ml round bottom bottle container is filled with 〇·1 mol acetoxy styrene/0·1 while stirring Mohr 3-hydroxypropyl acrylate, and 300 g of the individually prepared tetrahydrofuran is added to the complete mixture, after which the bismuth 2, 2'-azo catalyst is added at 60 to 75 The polymerization was carried out under a nitrogen atmosphere at ° C for 5 to 20 hours. After the completion of the reaction, the resulting solution was precipitated with diethyl ether or a neohexyl solution. Then, the mixture was subsequently subjected to a transition and dried to obtain a poly [ethylene styrene styrene (3-hydroxypropyl acrylate)] resin of the following formula 8 (yield: 80%). Equation 8

#乙f例例3—Composition of a mixture of acetamidine bases The bottom-bottomed bottle container is filled with 0.1 mole of B-oxygen in the mixing: dip-tomox acrylic 4_ butyl ester, and 300 g Individual pseudo-purines are added to the complete mixture and then added. · Bu 3. 〇 m Nitro ί catalyst was polymerized in a nitrogen atmosphere at 60 to 75 t for an hour. After the completion of the reaction, the resulting solution was filtered and dried with diethyl ether or fresh hexane:: 淀: 淀 ΐ to obtain a poly [ethylene ethoxylated ethylene-(4-hydroxybutyl acrylate)] resin of the following formula 9 ( Yield: 79%). 5142.4459PFl.ptc Page 13 1295295 Case No. 90127504 修正 Amendment V. Invention Description (10) Μ

Example 4 - Composition of Poly(Ethylene Oxide-Based Styrene-(2-Hydroxyethyl Methacrylate) 1 Copolymer - A 500 ml round bottom bottle container was filled with 0.1 molar acetoxybenzene when stirred Ethylene/0·1 molar 2-hydroxyethyl methacrylate, and 303 g of the individually prepared tetrahydrofuran was added to the complete mixture, after which 0.; 1 to 3.0 g of 2, 2'-azo group was added. The catalyst is polymerized for 5 to 20 hours under a nitrogen atmosphere at 60 to 75 ° C. After completion of the reaction, the resulting solution is precipitated with diethyl ether or a new hexane solution, followed by filtration and drying to obtain a polycondensation of the following formula [10] Ethyloxystyrene-(2-hydroxyethyl methacrylate) resin (yield: 83%).

5142-4459PFl.ptc Page 14 1295295 _ Case No. 90127504 V. Invention Description (Π) Year Month 修正 Correction Η

c=o 1 (CH2): 0 1 0=0 ! ch3 OH Example 5 - Composition of a mixture of "Ethylene gas-based stupid ethylene_(3-hydroxypropyl methacrylate) 1 total φ polymer-500 The ml round bottom bottle container was filled with 0.1 mol of ethoxylated styrene / 0.1 mol of 3-hydroxypropyl methacrylate while stirring, and 300 g of the individually prepared tetrahydrofuran was added to the complete mixture. Thereafter, 3.0 g of a 2,2'-azo catalyst was added to carry out polymerization for 5 to 20 hours under a nitrogen atmosphere at 60 to 75 ° C. After the reaction was completed, the resulting solution was mixed with diethyl ether or new one. The alkane solution was precipitated, followed by filtration and drying to obtain a poly([ethoxy styrene-(3-hydroxypropyl methacrylate))] resin of the following formula 11 (yield: 84%).

5142-4459PFl.ptc Page 15

1295295 Case No. 90127SfU Jade, invention description (12)

〇—The 500 ml round bottom bottle container is filled with 〇·t molar ethoxylated styrene/〇·1 molar 4-hydroxybutyl methacrylate while stirring, and 30 〇g of the individually prepared tetrahydrofuran is added. To the completion of the mixture, a 2,2'-azo catalyst was added to the mixture under a nitrogen atmosphere at 60 to 75 ° C for 5 to 20 hours. After completion of the reaction, the resulting solution is precipitated with diethyl ether or a fresh hexane solution, followed by filtration and drying to obtain a poly(ethyleneoxystyrene-(methylpropionic acid 4-butylide) of the following formula 1] Resin (yield · · 78%). Equation 12

5142-4459PFl.ptc Page 16 1295295 Case No. 90127504 ±_η 修正 Correction V. Description of invention (13)

Example 7 - Anti-Reflection Coating 湓* 66 The polymer of Formula 如 as in one of Examples 1 to 6 and the polymer of Formula 2 were dissolved in propyleneglycolmethylether acetate (PMMEA) Filtration of the resulting solution, coating it on a wafer, baking it at 100 to 300 f 3 for 1 J 1 sec., then applying a photosensitive film on the coating, followed by an ultra-fine pattern process . The cross-linking agent used in the polymer of the scorpion is designed to have the largest cross-linking right 嫱h ^ 2 , which can be freely adjusted by controlling the ratio of the first polymer _ monomer. This is included by the anti-reflective coating resin. Two chromophores having a large size chromophore have a protective undercut effect, and the undercut is caused by an acid imbalance of the weakly alkaline film, and this The polymer made of chromophore 3 has high absorbency at 193 (10) wavelength. Anti-reflective coating resin is soluble in all hydrocarbon solvents

V. INSTRUCTIONS (14) — _ , very good, but not dissolved in the hard-bake step. There is no undercut or bottom in the looping process. : In the two solvents, and the shot coating is composed of acrylate polymer, the 疋 of j, due to the button-etching rate of the anti-reflective film, i can improve the etching selection: the engraving rate is higher than the feeling here has been implemented The present invention is intended to be illustrative of the present invention and not to limit the invention, and it is intended that various modifications and changes can be made to the present invention after the use of the invention. In the material, 'as long as the invention is present.疋 迷 迷 迷 , , , , , , , , ,

Claims (1)

1295295 VI. Application for Patent __ Structure: Organic anti-reflective coating polymerization I Ra Rb c=o (R··-c-R"J] CH3 r , K heart is independent chlorine or methyl; -COOH, and only "for each Independent, and includes from _H, -011, _0C0Cil3, Shishan; § /~CH2〇H, an alkyl group having 1 to 6 carbon atoms, and a group having 1 to 6 ',, and a decyloxy group n is an integer from 1 to 5; X and 7 represent the molar fraction from 〇 01 to 0·99. ^ The organic anti-reflective coating polymer 'system as described in claim 1 a compound of poly(ethoxylated styrene-(2-hydroxyethyl acrylate)] wherein Ra and Rb are each independently hydrogen, R' and R" are each independently hydrogen, η is 2, and x ' y are each有机·5. 3 _ The organic anti-reflective coating polymer according to claim 1 is a compound of [ethoxylated styrene-(3-hydroxypropyl acrylate)], wherein Ra and Rb is independently hydrogen, and 1^ is independently hydrogen 'η is 3, and X and y are each 〇·5. 5142-4459-PF2.ptc Page 19 1295295 ----- Case No.----^ Amendment VI. Patent Application Range 4. The organic anti-reflective coating polymer 'system as described in claim 1 a combination of poly[acetoxystyrene-(hydroxybutyrate)] wherein Ra and Rb are each independently hydrogen 'R and Rn are independent gases 'η4, and X and y are each 〇 · 5. 5. The organic antireflective coating polymer according to claim 1 of the invention is a compound of poly [acetoxystyrene methacrylate 2-hydroxyethyl ester]], wherein Ra is hydrogen and Rb It is a mercapto hydrogen, R' and R" are independent gases, η is 2, and X and y are each 〇·5. 6. The organic antireflective coating polymer according to claim 1, wherein the compound is a compound of [ethoxylated styrene-(3-hydroxypropyl methacrylate)], wherein Ra is hydrogen and Rb It is a fluorenyl group, R, and R" are independent hydrogens, η is 3, and X and y are each 〇·5. 7. The compound of the organic anti-reflective coating polymer according to claim 1, wherein the compound is a compound of [ethoxyphenylidene 4-(4 butyl methacrylate)], wherein Ra is hydrogen. And Rb is a methyl group, R, and R" are each independently hydrogen, η is 4, and X and y are each 〇·5. 8. A method of preparing an organic anti-reflective coating polymer for preparing a polymer according to claim 1, wherein the method comprises: The ethoxylated styrene monomer is reacted with a hydroxyalkyl propylene monomer in a solvent to obtain a product; and the product is polymerized using a polymerization initiator. 9. The method for preparing an organic anti-reflective coating layer according to claim 8, wherein the solvent is selected from the group consisting of tetrahydrofuran, toluene, benzene, methyl ethyl ketone, hexaoxane and mixtures thereof . 1295295 _ Case No. 90127504_Year ι Day Amendment _____ VI. Application Patent Range I 0 · A method for preparing an organic anti-reflective coating polymer as described in claim 8 of the patent application, which includes 2, 2'-even The polymerization initiator is selected from the group consisting of a nitrogen-based catalyst, acetonitrile peroxide, a lauryl peroxide, a tertiary butyl peroxide, and a mixture thereof. A method for producing an organic anti-reflective coating polymer according to claim 8, wherein the polymerization is carried out at a temperature ranging from 50 to 90 °C. 1 2. An antireflective coating composition comprising a compound of the formula 1 as described in the first aspect of the patent application and a compound of the following formula 2 Rio R" wherein R1Q and Ru are each independently Cwg methoxy or ^(1) 炫' and Rl2 is hydrogen or methyl. 1-3 · Anti-reflective coating, group as described in claim 12 The compound of the formula 1 is a poly[acetoxy styrene-(propylene® hydroxyethyl 2-hydroxyethyl ester)] 〇- 14. The anti-reflective coating group according to claim 12 &', wherein the compound of the formula 1 is poly[acetoxy styrene-(propyl, hydrazine 3 hydroxypropyl)]. 1 5 · Anti-reflective honey as described in claim 1 a group of compounds wherein the compound of formula 1 is poly[6-methoxy styrene-(C,-- 5142-4459-PF2.ptc 21st tribute 1295295 _ case number 901275fU__ raw shell j_ six, the scope of patent application hydroxybutyl ester)]. The anti-reflective coating composition according to claim 12, wherein the compound of the formula 1 is poly[acetoxystyrene-(2-hydroxyethyl methacrylate)]. The anti-reflective coating composition of claim 1, wherein the compound of the formula 1 is poly[acetoxystyrene-(3-hydroxypropyl methacrylate)]. The antireflective coating composition of claim 1, wherein the compound of the formula 1 is poly[acetoxystyrene-(4-hydroxybutyl methacrylate)]. 1 9 · A method for preparing an anti-reflective coating comprising: dissolving a compound of the formula 1 of the polymer according to claim 1 of the patent application and a compound of the formula 2 in an organic solvent to obtain a solution; The solution is obtained as a mash; the filtrate is coated on a lower layer of the substrate to deposit a coating on the lower layer; and the coating is hard baked. The preparation method of the anti-reflective coating layer according to claim 19, wherein self-contained ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, cyclohexanone The organic solvent is selected from the group consisting of propylene glycol methyl ether acetate. 2 1 The method for preparing an anti-reflective coating according to claim 19, wherein the organic solvent is used in an amount of from 200 to 50,000 wt% depending on the total weight of the anti-reflective coating used. . 5142-4459-PF2.ptc No. 1295295 No. 90127504 VI. Patent Application Range 2 2 · For example, the scope of the application of the patent scope is 1 g, where the hard-baked step is at 10 (). A semiconductor device prepared from, for example, an anti-reflective coating composition. A semiconductor device prepared from, for example, an anti-reflective coating composition. 25. A semiconductor device made of, for example, an anti-reflective coating composition. A semiconductor device is made of, for example, an anti-reflective coating composition.涂层28. A semiconductor 妒侑 fabricated by a coating composition. Anti-reflective coating composition; 'by * 29. - a semiconductor package. The anti-reflective coating composition 6 was prepared as described in item 18 of the patent application. The preparation of the anti-reflective coating is up to a temperature range of 300 ° C. The patent application scope of claim 1 is the patent application range. 5 of the above-mentioned patent application scope of claim 17 5142-4459-PF2.ptc Page 23 1295295 Representation VI. Scope of Application 22 · The method of claim 19, wherein the hard roasting step is in the i line. 23. A semiconductor device prepared from an anti-reflective coating composition. 24. A semiconductor device comprising: an anti-reflective coating composition. Material 26•-A kind of anti-m material of semiconductor d' 27·--------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- The reflective coating, the address compound 'from the anti-reflective coating combination of the semiconductor type 从 从 从 从 从 ' ' ' ' ' ' ' ' ' 。 。 。 。 。 。 。 。 。 。 00 00 00 00 00 00 00 00 00 00 00 00 00 00 The temperature range is as described in item 12 of the patent application scope as described in item 13 of the patent application scope) as described in item 14 of the patent application scope) as described in item 15 of the patent application scope > If the scope of Article 16 is as described in Article 17 of the scope of application, the scope of the patent application is the 18th item. 5142-4459-PF2.ptc Page 23