TWI697738B - Composition for hard mask - Google Patents
Composition for hard mask Download PDFInfo
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- TWI697738B TWI697738B TW106112551A TW106112551A TWI697738B TW I697738 B TWI697738 B TW I697738B TW 106112551 A TW106112551 A TW 106112551A TW 106112551 A TW106112551 A TW 106112551A TW I697738 B TWI697738 B TW I697738B
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- BIJNHUAPTJVVNQ-UHFFFAOYSA-N Oc1ccc(cc2)c3c1ccc1cccc2c31 Chemical compound Oc1ccc(cc2)c3c1ccc1cccc2c31 BIJNHUAPTJVVNQ-UHFFFAOYSA-N 0.000 description 2
- FXLOVSHXALFLKQ-UHFFFAOYSA-N Cc1ccc(C=O)cc1 Chemical compound Cc1ccc(C=O)cc1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
Abstract
Description
本發明關於一種硬遮罩用組成物。 The present invention relates to a composition for hard masks.
微電子學產業和顯微結構物(例如，微機械、磁電阻(magnetoresist)頭等)等產業領域中，持續要求減小結構形狀的大小。再者，微電子學產業中，存在如下要求：減小微電子設備的大小，對指定的晶片大小提供更多的迴路。 In the industry of microelectronics and microstructures (for example, micromachines, magnetoresist, etc.), there is a continuous demand for reducing the size of the structure shape. Furthermore, in the microelectronics industry, there are requirements as follows: reduce the size of microelectronic equipment and provide more circuits for the specified chip size.
為了減小形狀大小，有效的光刻技術是必須的。 In order to reduce the shape size, effective photolithography is necessary.
典型的光刻步驟，首先，在下層材料上塗佈抗蝕劑後，進行放射線曝光，形成抗蝕劑層。接著，將抗蝕劑層用顯影液進行顯影而形成經圖案化的抗蝕劑層，對存在於圖案化的抗蝕劑層的開口部內的物質進行蝕刻，將圖案轉印至下層材料。轉印結束後，伴隨使感光性抗蝕劑以圖案方式暴露，形成圖案化的抗蝕劑層之過程。接著，藉由使經暴露的抗蝕劑層與任意物質(典型為水性鹼性顯影液)接觸，從而進行顯影。接著，藉由對存在於圖案化的抗蝕劑層的開口部內的物質進行蝕刻，使圖案轉印至下層 材料。轉印結束後，去除殘留的抗蝕劑層。 In a typical photolithography step, first, after coating a resist on the underlying material, radiation exposure is performed to form a resist layer. Next, the resist layer is developed with a developer to form a patterned resist layer, and the substance present in the opening of the patterned resist layer is etched to transfer the pattern to the underlying material. After the transfer, the photosensitive resist is exposed in a pattern to form a patterned resist layer. Next, development is performed by contacting the exposed resist layer with any substance (typically an aqueous alkaline developer). Then, by etching the substance present in the opening of the patterned resist layer, the pattern is transferred to the lower layer material. After the transfer, the remaining resist layer is removed.
為了使抗蝕劑層與下層材料之間的反射性最小化，前述光刻步驟的大部分步驟中使用抗反射塗層(anti-refractive coating；ARC)來增加解析度。惟，在將圖案化後之抗反射塗層進行蝕刻的步驟中，抗蝕劑層也被大量消耗，有在後續蝕刻步驟中必須追加圖案化之情形。 In order to minimize the reflectivity between the resist layer and the underlying material, anti-refractive coating (ARC) is used in most of the aforementioned photolithography steps to increase the resolution. However, in the step of etching the patterned anti-reflective coating, the resist layer is also consumed in a large amount, and there are cases in which patterning must be added in the subsequent etching step.
換言之，在一部分光刻圖像化步驟的情況，所使用的抗蝕劑有對於蝕刻階段不具有充分的耐受性足以使預定的圖案有效地轉印至下層材料的程度的之情形。因此，對於需要將抗蝕劑物質極薄地使用的超薄膜抗蝕劑層的情況，在欲蝕刻處理的基板為較厚的情況、要求蝕刻深度為較深的情況、或者在預定的下層材料中必須使用特定蝕刻劑(etchant)的情況等中，使用了抗蝕劑下層膜。 In other words, in the case of a part of the photolithography imaging step, the resist used may not have sufficient resistance to the etching step to the extent that the predetermined pattern can be effectively transferred to the underlying material. Therefore, in the case of an ultra-thin resist layer in which the resist material needs to be used extremely thinly, when the substrate to be etched is thick, when the etching depth is required to be deep, or in a predetermined underlying material In cases where a specific etching agent (etchant) must be used, etc., a resist underlayer film is used.
抗蝕劑下層膜，係在抗蝕劑層與可從圖案化的抗蝕劑藉由轉印而圖案化的下層材料之間發揮中間層的作用。該抗蝕劑下層膜必須耐受從圖案化的抗蝕劑層接受圖案、使圖案轉印至下層材料時所需的蝕刻步驟。 The resist underlayer film functions as an intermediate layer between the resist layer and the underlying material that can be patterned from the patterned resist by transfer. The resist underlayer film must withstand the etching steps required to receive the pattern from the patterned resist layer and transfer the pattern to the underlying material.
為了形成此下層膜，嘗試了許多材料，但仍然持續要求經改善的下層膜組成物。 In order to form this underlayer film, many materials have been tried, but an improved underlayer film composition continues to be demanded.
以往，用於形成下層膜的材料，由於難以塗佈於基板，因此利用例如化學或物理蒸鍍、特殊溶劑或高溫燒成，惟存在有該等方法為高價的問題。由此，近年來，進行著無需實施高溫燒成之可利用旋轉塗佈方法來塗佈的下層膜組成物的研究。 In the past, the material used to form the underlayer film was difficult to be applied to the substrate. Therefore, for example, chemical or physical vapor deposition, special solvents, or high-temperature firing were used, but there was a problem that these methods were expensive. Therefore, in recent years, research has been conducted on an underlayer film composition that can be applied by a spin coating method without high-temperature firing.
再者，進行著關於下述下層膜組合物的研究：將形成於上部的抗蝕劑層作為遮罩而可進行容易且選擇性地蝕刻，同時，特別是在下層為金屬層的情況下，對於將下層膜作為遮罩並且將下層進行圖案化所需的蝕刻步驟具有耐受性之下層膜組合物。 In addition, studies are being conducted on the composition of the lower layer film that can be easily and selectively etched by using the resist layer formed on the upper layer as a mask. At the same time, especially when the lower layer is a metal layer, The underlayer film composition is resistant to the etching step required to use the underlayer film as a mask and pattern the underlayer.
韓國公開專利第2010-0082844號揭示關於抗蝕劑下層膜形成組成物的技術。 Korean Patent Publication No. 2010-0082844 discloses a technology related to a resist underlayer film forming composition.
韓國專利公開第2010-0082844號 Korean Patent Publication No. 2010-0082844
本發明的目的在於，提供一種能夠形成耐熱性及平坦性優異的抗蝕劑下層膜(硬遮罩)的硬遮罩用組成物。 The object of the present invention is to provide a hard mask composition capable of forming a resist underlayer film (hard mask) excellent in heat resistance and flatness.
1.一種硬遮罩用組成物，其包含具有下述化學式1所表示的重複單元的共聚物和溶劑，
(式中，Ar為碳數6至35的芳烴三基(Arenetriyl)，R為氫原子、碳數1至6的烷基或碳數6至18的芳基，前述 V為乙烯基、乙炔基、或者經乙烯基或乙炔基取代的苯基，前述X為氫原子、碳數1至6的烷基、碳數6至18的芳基、或碳數4至16的雜芳基，前述Ar、R、V和X各自獨立為可經碳數1至6的烷基、羥基、甲氧基或苯基進一步取代者，n為1至190的整數)。 (In the formula, Ar is an Arenetriyl group having 6 to 35 carbons, R is a hydrogen atom, an alkyl group having 1 to 6 carbons or an aryl group having 6 to 18 carbons, the aforementioned V is a vinyl group, an ethynyl group, or a phenyl group substituted with a vinyl group or an ethynyl group, and the aforementioned X is a hydrogen atom, an alkyl group having 1 to 6 carbons, an aryl group having 6 to 18 carbons, or a carbon number of 4 to 16 In the heteroaryl group, the aforementioned Ar, R, V, and X are each independently one that may be further substituted with an alkyl group, a hydroxyl group, a methoxy group or a phenyl group having 1 to 6 carbon atoms, and n is an integer from 1 to 190).
2.如1所述的硬遮罩用組成物，前述化學式1中，前述Ar為選自由下述化學式1-1至下述化學式1-5所表示者所成群組中的至少一種，
3.如1所述的硬遮罩用組成物，前述化學式1中，前述X為選自由氫原子、下述化學式2-1和下述化學式2-2所表示者所成群組中的至少一種，
4.如1所述的硬遮罩用組成物，前述具有化學式1所表示的重複單元的共聚物，係在由碳數6至35的芳基化合物與下述化學式p-1所表示的化合物的縮合反應製造的預聚物中添加下述化學式p-2所表示的化合物而製造的化合物，
(式中，前述X為氫原子、碳數1至6的烷基、碳數6 至18的芳基或碳數4至16的雜芳基，R為氫原子、碳數1至6的烷基或碳數6至18的芳基，前述V為乙烯基、乙炔基、或者經乙烯基或乙炔基取代的苯基，Z為-OH或-OR1，R1為碳數1至6的烷基，前述芳基化合物、R、V和X各自獨立為可經碳數1至6的烷基、羥基、甲氧基或苯基進一步取代者)。 (In the formula, the aforementioned X is a hydrogen atom, an alkyl group having 1 to 6 carbons, an aryl group having 6 to 18 carbons, or a heteroaryl group having 4 to 16 carbons, and R is a hydrogen atom, an alkyl group having 1 to 6 carbons Group or an aryl group having 6 to 18 carbons, the aforementioned V is a vinyl group, an ethynyl group, or a phenyl group substituted with a vinyl group or an ethynyl group, Z is -OH or -OR 1 , and R 1 is a carbon number of 1 to 6 The alkyl group, the aforementioned aryl compound, R, V, and X are each independently one that may be further substituted with an alkyl group having 1 to 6 carbons, a hydroxyl group, a methoxy group, or a phenyl group).
5.如1所述的硬遮罩用組成物，前述化學式1所表示的重複單元，在前述共聚物中含有5至50莫耳%。 5. The composition for a hard mask according to 1, wherein the repeating unit represented by the aforementioned chemical formula 1 contains 5 to 50 mol% in the aforementioned copolymer.
6.如1所述的硬遮罩用組成物，相對於組成物的總重量，含有前述具有化學式1所表示的重複單元的共聚物5至15重量%，含有前述溶劑85至95重量%。 6. The composition for a hard mask according to 1 contains 5 to 15% by weight of the copolymer having the repeating unit represented by Chemical Formula 1 and 85 to 95% by weight of the solvent, relative to the total weight of the composition.
7.如1所述的硬遮罩用組成物，進一步包含交聯劑和催化劑中的至少一種。 7. The composition for a hard mask according to 1, further comprising at least one of a crosslinking agent and a catalyst.
本發明的硬遮罩用組成物能夠形成耐熱性及平坦性優異的硬遮罩(抗蝕劑下層膜)。 The hard mask composition of the present invention can form a hard mask (resist underlayer film) excellent in heat resistance and flatness.
本發明的硬遮罩用組成物中所包含的共聚物係容易製造。 The copolymer system contained in the composition for hard masks of this invention is easy to manufacture.
本發明的一實施方式係關於一種硬遮罩用組成物，其包含具有化學式1所表示的重複單元的共聚物 和溶劑，藉此能夠形成耐熱性及平坦性優異的抗蝕劑下層膜(硬遮罩)。 One embodiment of the present invention relates to a composition for a hard mask, which comprises a copolymer having a repeating unit represented by Chemical Formula 1. With a solvent, it is possible to form a resist underlayer film (hard mask) excellent in heat resistance and flatness.
以下，說明本發明的具體實施形態。惟，該具體實施形態僅為例示，本發明並不限於此。 Hereinafter, specific embodiments of the present invention will be described. However, this specific embodiment is only an example, and the present invention is not limited to this.
本發明中，化學式所表示的化合物或樹脂存在異構物的情況下，相關化學式所表示的化合物或樹脂是指其異構物也包括在內的代表化學式。 In the present invention, when the compound or resin represented by the chemical formula has isomers, the compound or resin represented by the related chemical formula refers to a representative chemical formula including its isomers.
<硬遮罩用組成物> <Composition for Hard Mask>
本發明的硬遮罩用組成物包含具有化學式1所表示的重複單元的共聚物(A)和溶劑(B)。 The composition for a hard mask of the present invention contains a copolymer (A) having a repeating unit represented by Chemical Formula 1 and a solvent (B).
具含化學式1所表示的重複單元的共聚物(A)
(式中，Ar為碳數6至35的芳烴三基(Arenetriyl)，R為氫原子、碳數1至6的烷基或碳數6至18的芳基，前述V為乙烯基、乙炔基、或者經乙烯基或乙炔基取代的苯基，前述X為氫原子、碳數1至6的烷基、碳數6至18的芳基或碳數4至16的雜芳基，前述Ar、R、V或X各自獨立為可經碳數1至6的烷 基、羥基、甲氧基或苯基進一步取代者，n為1至190的整數)。 (In the formula, Ar is an arenetriyl group with 6 to 35 carbons, R is a hydrogen atom, an alkyl group with 1 to 6 carbons or an aryl group with 6 to 18 carbons, and the aforementioned V is a vinyl group or an ethynyl group. , Or a phenyl group substituted with a vinyl group or an ethynyl group, the foregoing X is a hydrogen atom, an alkyl group having 1 to 6 carbons, an aryl group having 6 to 18 carbons or a heteroaryl group having 4 to 16 carbons, the foregoing Ar, R, V or X are each independently an alkane having 1 to 6 carbon atoms Group, hydroxy group, methoxy group or phenyl group is further substituted, n is an integer from 1 to 190).
本說明書中，雜芳基包含一個以上非碳原子即雜原子者，具體而言，前述雜原子可為選自由O、N、Se和S等所成群組中的至少一種原子。 In the present specification, the heteroaryl group includes one or more non-carbon atoms, that is, heteroatoms. Specifically, the aforementioned heteroatoms may be at least one atom selected from the group consisting of O, N, Se, and S.
本發明包含具有前述化學式1所表示的重複單元的共聚物(A)，藉此能夠使本發明的硬遮罩用組成物所形成的硬遮罩表現出優異的耐熱性及平坦性。 The present invention includes the copolymer (A) having the repeating unit represented by the aforementioned chemical formula 1, whereby the hard mask formed from the composition for hard mask of the present invention can exhibit excellent heat resistance and flatness.
由此觀點而言，本發明的一實施形態的化學式1中之前述Ar，較佳可為選自由下述化學式1-1至下述化學式1-5所表示者所成群組中的至少一種。 From this point of view, the aforementioned Ar in the chemical formula 1 of one embodiment of the present invention may preferably be at least one selected from the group consisting of the following chemical formula 1-1 to the following chemical formula 1-5 .
再者，從使所形成的硬遮罩表現出優異的耐熱性及平坦性之觀點而言，本發明的一實施形態的化學式1中之前述X較佳可為選自由氫原子、下述化學式2-1和下述化學式2-2所表示者所成群組中的至少一種。 Furthermore, from the viewpoint of making the formed hard mask exhibit excellent heat resistance and flatness, the aforementioned X in the chemical formula 1 of one embodiment of the present invention may preferably be selected from a hydrogen atom and the following chemical formula At least one of the group represented by 2-1 and the following chemical formula 2-2.
本發明的一實施形態的前述具有化學式1所表示的重複單元的共聚物(A)，係可藉由在由碳數6至35的芳基化合物與下述化學式p-1所表示的化合物的縮合反應製造的預聚物中，添加下述化學式p-2所表示的化合物而製造。 The aforementioned copolymer (A) having the repeating unit represented by Chemical Formula 1 in one embodiment of the present invention can be obtained by combining an aryl compound having 6 to 35 carbon atoms and a compound represented by the following Chemical Formula p-1 The prepolymer produced by the condensation reaction is produced by adding a compound represented by the following chemical formula p-2.
(式中，前述X為氫原子、碳數1至6的烷基、碳數6至18的芳基或碳數4至16的雜芳基，R為氫原子、碳數1至6的烷基或碳數6至18的芳基，前述V為乙烯基、乙炔基、或者經乙烯基或乙炔基取代的苯基，Z為-OH或-OR1，R1為碳數1至6的烷基，前述芳基化合物、R、V和X各自獨立為可經碳數1至6的烷基、羥基、甲氧基或苯基進一步取代者)。 (In the formula, the aforementioned X is a hydrogen atom, an alkyl group having 1 to 6 carbons, an aryl group having 6 to 18 carbons, or a heteroaryl group having 4 to 16 carbons, and R is a hydrogen atom, an alkyl group having 1 to 6 carbons Group or an aryl group having 6 to 18 carbons, the aforementioned V is a vinyl group, an ethynyl group, or a phenyl group substituted with a vinyl group or an ethynyl group, Z is -OH or -OR 1 , and R 1 is a carbon number of 1 to 6 The alkyl group, the aforementioned aryl compound, R, V, and X are each independently one that may be further substituted with an alkyl group having 1 to 6 carbons, a hydroxyl group, a methoxy group, or a phenyl group).
在藉由前述方法來製造本發明的一實施形態的共聚物(A)時，由於能夠以相同條件進行兩種反應(預聚物的製造反應及化學式p-2的添加反應)，因而能夠容易地製造，並能夠減少製造成本。 When the copolymer (A) of one embodiment of the present invention is produced by the aforementioned method, two kinds of reactions (prepolymer production reaction and chemical formula p-2 addition reaction) can be carried out under the same conditions. It can be manufactured at a high level and can reduce manufacturing costs.
再者，在將碳數6至35的芳基化合物、前述化學式p-1所表示的化合物和前述化學式p-2所表示的化合物一次性投入時，由於共聚反應容易終止，因而有難以形成本實施例的共聚物(A)之情形。 Furthermore, when the aryl compound having 6 to 35 carbon atoms, the compound represented by the aforementioned chemical formula p-1, and the compound represented by the aforementioned chemical formula p-2 are put in at once, the copolymerization reaction is likely to be terminated, which makes it difficult to form a cost In the case of the copolymer (A) of the example.
另一方面，在碳數6至35的芳基化合物被 可有效提供電子的官能基進一步取代時，共聚物(A)的製造會變得容易，例如，作為電子供給體，較佳為可被羥基或甲氧基進一步取代，更佳為可被羥基進一步取代。 On the other hand, aryl compounds with carbon numbers 6 to 35 are When the functional group that can effectively donate electrons is further substituted, the production of the copolymer (A) becomes easier. For example, as an electron donor, it is preferably further substituted by a hydroxyl group or a methoxy group, and more preferably can be further substituted by a hydroxyl group. replace.
本發明的一實施形態的前述碳數6至35的芳基化合物，例如可為下述化學式ar-1至化學式ar-5中的任一個所表示的化合物，
本發明的一實施形態的前述化學式p-1所表示的化合物，例如可以為下述化學式p-1-1至化學式p-1-3中的任一個所表示的化合物， 化學式p-1-1 HCHO The compound represented by the aforementioned chemical formula p-1 in one embodiment of the present invention may be, for example, a compound represented by any one of the following chemical formula p-1-1 to chemical formula p-1-3, Chemical formula p-1-1 HCHO
本發明的一實施形態的前述化學式p-2所表示的化合物，例如可為下述化學式p-2-1至化學式p-2-4中的任一個。 The compound represented by the aforementioned chemical formula p-2 in an embodiment of the present invention may be any of the following chemical formula p-2-1 to chemical formula p-2-4, for example.
本發明的一實施形態的化學式1所表示的重複單元，係在共聚物(A)中可含有5至50莫耳%。若滿足前述範圍時，所形成的硬遮罩可顯示優異的耐熱性及平坦性。 The repeating unit represented by the chemical formula 1 in one embodiment of the present invention may contain 5 to 50 mol% in the copolymer (A). If the aforementioned range is satisfied, the formed hard mask can exhibit excellent heat resistance and flatness.
本發明的一實施形態的具有化學式1所表示的重複單元的共聚物(A)，可具有根據前述n值的重量平均分子量。可舉具體例，例如，共聚物(A)的重量平均分子量可為1000至10000，較佳可為2000至10000。 The copolymer (A) having the repeating unit represented by Chemical Formula 1 according to one embodiment of the present invention may have a weight average molecular weight based on the aforementioned n value. Specific examples can be given. For example, the weight average molecular weight of the copolymer (A) may be 1,000 to 10,000, preferably 2,000 to 10,000.
具有化學式1所表示的重複單元的共聚物(A)的多分散指數(PDI，Polydispersity index)[重量平均均分子量(Mw)/數量平均分子量(Mn)]，較佳為1.3至6.0，更佳為1.5至4.0。 Polydispersity index (PDI, Polydispersity index) [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the copolymer (A) having the repeating unit represented by chemical formula 1, preferably 1.3 to 6.0, more preferably From 1.5 to 4.0.
若前述多分散指數[重量平均分子量(Mw)/數量平均分子量(Mn)]為前述範圍內時，由於由具有前述化學式1所表示的重複單元的共聚物(A)所致之效果會變得更加優異，因而較佳。 If the aforementioned polydispersity index [weight average molecular weight (Mw)/number average molecular weight (Mn)] is within the aforementioned range, the effect due to the copolymer (A) having the repeating unit represented by the aforementioned chemical formula 1 becomes More excellent, therefore better.
本發明的一實施形態的具有化學式1所表示的重複單元的共聚物(A)的含量，只要是能夠達成本發明目的者就沒有特別限制，例如，相對於組成物的總重量，可為5至15重量%。滿足前述範圍時，能夠有效地表現出前述本發明的效果。若相對於組成物的總重量，具有化學 式1所表示的重複單元的共聚物(A)的含量未達5重量%時，則難以獲得具有目的塗佈厚度之塗佈層，若超過15重量%時，則液相的塗佈均勻性有降低之情形。 The content of the copolymer (A) having the repeating unit represented by Chemical Formula 1 in one embodiment of the present invention is not particularly limited as long as it can achieve the purpose of the invention. For example, it may be 5 relative to the total weight of the composition. To 15% by weight. When the aforementioned range is satisfied, the aforementioned effects of the present invention can be effectively exhibited. If relative to the total weight of the composition, it has a chemical When the content of the copolymer (A) of the repeating unit represented by Formula 1 is less than 5% by weight, it is difficult to obtain a coating layer with the desired coating thickness, and when it exceeds 15% by weight, the coating uniformity of the liquid phase There is a decrease.
溶劑(B) Solvent (B)
本發明的一實施形態的溶劑只要是對於前述具有化學式1所表示的重複單元的共聚物(A)具有充分溶解性的有機溶劑就沒有特別限制，可列舉例如，丙二醇單甲基醚乙酸酯(propylene glycol monomethyl ether acetate；PGMEA)、丙二醇單甲基醚(propylene glycol monomethyl ether；PGME)、環己酮、乳酸乙酯、γ-丁內酯(γ-butyrolactone；GBL)、乙醯丙酮(acetyl acetone)等，較佳可為丙二醇單甲基醚乙酸酯(propylene glycol monomethyl ether acetate；PGMEA)。 The solvent of one embodiment of the present invention is not particularly limited as long as it is an organic solvent that has sufficient solubility for the copolymer (A) having the repeating unit represented by Chemical Formula 1, and for example, propylene glycol monomethyl ether acetate (propylene glycol monomethyl ether acetate; PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, ethyl lactate, γ-butyrolactone (GBL), acetyl acetone acetone), etc., preferably propylene glycol monomethyl ether acetate (PGMEA).
本發明一實施形態的溶劑(B)的含量只要能夠達成本發明的目的就沒有特別限制，可包含本發明的組成物中除去包含化學式1所表示的重複單元的共聚物(A)的反應成分以及其他添加劑以外的殘餘量。例如，在組成物中僅使用化學式1的化合物的情況，相對於組成物的總重量，溶劑可為85至95重量%。當滿足前述範圍時，可有效地表現前述本發明的效果。 The content of the solvent (B) in one embodiment of the present invention is not particularly limited as long as it can achieve the purpose of the present invention. The composition of the present invention may contain the reaction component of the copolymer (A) containing the repeating unit represented by Chemical Formula 1 And the residual amount other than other additives. For example, in the case where only the compound of Chemical Formula 1 is used in the composition, the solvent may be 85 to 95% by weight relative to the total weight of the composition. When the aforementioned range is satisfied, the aforementioned effects of the present invention can be effectively expressed.
交聯劑及催化劑 Crosslinking agent and catalyst
再者，根據需要，本發明的一實施形態的硬遮罩用組成物可進一步包含交聯劑和催化劑中的至少一種。 Furthermore, if necessary, the composition for a hard mask of one embodiment of the present invention may further contain at least one of a crosslinking agent and a catalyst.
前述交聯劑，係可在利用所產生的酸進行催化劑作用的反應中，藉由加熱使聚合物的重複單元進行交聯者，只要是能夠以利用所產生的酸而催化劑作用化的方式而與共聚物(A)的羥基反應的交聯劑就沒有特別限定。作為如此之交聯劑，可使用選自由三聚氰胺、胺基樹脂、羥乙醯基化合物和雙環氧基化合物所成群組中的任一種。 The aforementioned crosslinking agent is one that can crosslink the repeating unit of the polymer by heating in a reaction that uses the generated acid to perform the catalytic action, as long as it can be used in a manner that the generated acid can act as a catalyst. The crosslinking agent that reacts with the hydroxyl group of the copolymer (A) is not particularly limited. As such a crosslinking agent, any one selected from the group consisting of melamine, amine-based resins, glycolyl compounds, and biepoxy compounds can be used.
藉由進一步包含前述交聯劑，可更強化硬遮罩用組成物的硬化特性。 By further including the aforementioned crosslinking agent, the hardening properties of the hard mask composition can be further enhanced.
作為前述交聯劑的具體例，可列舉經醚化的胺基樹脂，例如甲基化或丁基化的三聚氰胺(具體而言，N-甲氧基甲基-三聚氰胺或N-丁氧基甲基-三聚氰胺)、以及甲基化或丁基化的尿素(urea)樹脂(作為具體例，Cymel U-65樹脂或UFR 80樹脂)；下述化學式L-1所表示的羥乙醯基衍生物(作為具體例，Powderlink 1174)；化學式L-2所表示的雙(羥基甲基)-對甲酚化合物等。此外，下述化學式L-3所表示的雙環氧系化合物和下述化學式L-4所表示的三聚氰胺系化合物亦可用作交聯劑。 As a specific example of the aforementioned crosslinking agent, etherified amine-based resins such as methylated or butylated melamine (specifically, N-methoxymethyl-melamine or N-butoxymethyl -Melamine), and methylated or butylated urea (urea) resin (as specific examples, Cymel U-65 resin or UFR 80 resin); the hydroxyacetin derivative represented by the following chemical formula L-1 (As a specific example, Powderlink 1174); bis(hydroxymethyl)-p-cresol compound represented by chemical formula L-2, etc. In addition, the diepoxy compound represented by the following chemical formula L-3 and the melamine compound represented by the following chemical formula L-4 can also be used as a crosslinking agent.
作為前述催化劑，可使用酸催化劑或鹼性催化劑。 As the aforementioned catalyst, an acid catalyst or a basic catalyst can be used.
前述酸催化劑可以使用熱活化的酸催化劑。作為酸催化劑的例子，可使用如對甲苯磺酸單水合物(p-toluene sulfonic acid monohydrate)之有機酸，再者，可舉出具有保存穩定性的TAG(thermal acid generator，熱產酸劑)系化合物。熱產酸劑是成為在熱處理時釋放酸的產酸劑化合物，例如可以使用對甲苯磺酸吡啶鎓鹽(pyridinium p-toluene sulfonate)、2,4,4,6-四溴環己二烯酮、苯偶姻甲苯磺酸酯、2-硝基苄基甲苯磺酸酯、有機磺酸的烷基酯等。 The aforementioned acid catalyst may be a thermally activated acid catalyst. As an example of the acid catalyst, organic acids such as p-toluene sulfonic acid monohydrate can be used, and further, TAG (thermal acid generator) with storage stability can be mentioned. Department of compounds. Thermal acid generators are compounds that release acid during heat treatment. For example, pyridinium p-toluene sulfonate, 2,4,4,6-tetrabromocyclohexadienone can be used. , Benzoin tosylate, 2-nitrobenzyl tosylate, alkyl esters of organic sulfonic acid, etc.
作為前述鹼性催化劑，可使用選自NH4OH或NR4OH(R為烷基)所表示的氫氧化銨中的任一種。 As the aforementioned basic catalyst, any one selected from ammonium hydroxide represented by NH 4 OH or NR 4 OH (R is an alkyl group) can be used.
再者，在抗蝕劑技術領域中公知的其他感光性催化劑，只要其與抗反射組成物的其他成分具有相容性就可使用。 Furthermore, other photosensitive catalysts known in the field of resist technology can be used as long as they are compatible with other components of the anti-reflection composition.
在包含前述交聯劑的情況，相對於前述共聚物(A)100重量份，交聯劑的含量可為0.001重量份至50重量份，較佳可為0.1重量份至20重量份，更佳可為1重量份至20重量份。又，在包含前述催化劑的情況，相對於前述共聚物(A)100重量份，催化劑的含量可為0.001重量份至50重量份，較佳可為0.1重量份至20重量份，更佳可為1重量份至20重量份。 In the case where the aforementioned crosslinking agent is included, relative to 100 parts by weight of the aforementioned copolymer (A), the content of the crosslinking agent may be 0.001 to 50 parts by weight, preferably 0.1 to 20 parts by weight, more preferably It can be 1 part by weight to 20 parts by weight. In addition, when the aforementioned catalyst is included, relative to 100 parts by weight of the aforementioned copolymer (A), the content of the catalyst may be 0.001 parts by weight to 50 parts by weight, preferably 0.1 parts by weight to 20 parts by weight, and more preferably 1 part by weight to 20 parts by weight.
前述交聯劑的含量為前述範圍時，能夠使所形成的下層膜的光學特性不產生變化，並且得到適當的交聯特性。 When the content of the aforementioned crosslinking agent is in the aforementioned range, it is possible to obtain appropriate crosslinking characteristics without changing the optical characteristics of the underlayer film formed.
再者，前述催化劑含量為前述範圍時，能夠得到適當的交聯特性，並且能夠適當地維持對保存穩定性造成影響的酸度。 In addition, when the content of the catalyst is in the above range, appropriate crosslinking characteristics can be obtained, and acidity that affects storage stability can be appropriately maintained.
添加劑 additive
根據需要，本發明的硬遮罩用組成物可進一步包含界面活性劑等添加劑。作為前述界面活性劑，可以使用烷基苯磺酸鹽、烷基吡啶鎓鹽、聚乙二醇類、四級銨鹽等，但並不限於此。此時，相對於前述共聚物(A)100重量份，界面活性劑的含量可為1重量份至30重量份。前述表面活性劑的含量為前述範圍時，能夠使所形成的下層膜的光學特 性不產生變化，並且得到適當的交聯特性。 If necessary, the composition for a hard mask of the present invention may further contain additives such as a surfactant. As the aforementioned surfactant, alkylbenzene sulfonate, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt, etc. can be used, but it is not limited thereto. At this time, relative to 100 parts by weight of the aforementioned copolymer (A), the content of the surfactant may be 1 part by weight to 30 parts by weight. When the content of the aforementioned surfactant is in the aforementioned range, the optical characteristics of the formed underlayer film can be improved There is no change in performance and proper crosslinking properties are obtained.
以下，為了幫助理解本發明，提供較佳的實施例，但該等實施例只是例示本發明，並非限制隨附的申請專利範圍者。在本發明的範疇和技術思想範圍內可對實施例進行各種變更和修改，這對於本領域技術人員來說是顯而易見的，該等變形和修改當然也屬於隨附的申請專利範圍。 Hereinafter, in order to help understand the present invention, preferred embodiments are provided, but these embodiments are only examples of the present invention and do not limit the scope of the accompanying patent applications. Various changes and modifications can be made to the embodiments within the scope of the present invention and the scope of technical ideas, which is obvious to those skilled in the art. Of course, such changes and modifications also belong to the scope of the attached patent application.
實施例及比較例 Examples and comparative examples
調製下述表1和表2中記載的組成和含量(重量%)的硬遮罩用組成物。 The composition for hard masks of the composition and content (weight%) described in the following Table 1 and Table 2 were prepared.
A-1：在以
A-2：在以
A-3：在以
A-4：在以
A-5：在以
A-6：在以
A-7：在以
A-8：在以
A’-1：以
A’-2：以
A’-3：以
A’-4：在以
B-1：丙二醇單甲基醚乙酸酯(propylene glycol monomethyl ether acetate；PGMEA) B-1: propylene glycol monomethyl ether acetate (PGMEA)
C-1：N-甲氧基甲基-三聚氰胺樹脂 C-1: N-methoxymethyl-melamine resin
D-1：對甲苯磺酸吡啶鎓鹽 D-1: pyridinium p-toluenesulfonate
E-1：三乙二醇 E-1: Triethylene glycol
實驗例 Experimental example
1.耐熱性評估 1. Heat resistance evaluation
將組合物真空乾燥而去除溶劑，取一部分樣品，在氮下，使用熱重分析(thermogravimetric analysis，TGA)，一邊升溫至800℃，一邊測定質量損失率。 The composition was vacuum-dried to remove the solvent, a part of the sample was taken, and the mass loss rate was measured while raising the temperature to 800° C. using thermogravimetric analysis (TGA) under nitrogen.
品質損失率={(初始質量-800℃時的質量)/初始質量}x100% Quality loss rate={(initial quality-quality at 800℃)/initial quality}x100%
<耐熱性之判定> <Judgment of heat resistance>
◎：質量損失率未達10%， ◎: The quality loss rate is less than 10%,
○：質量損失率為10%以上未達15% ○: The quality loss rate is more than 10% and less than 15%
△：質量損失率為15%以上未達25% △: The quality loss rate is over 15% and less than 25%
×：質量損失率為25%以上 ×: The quality loss rate is more than 25%
2.平坦性 2. Flatness
將組成物乾燥後，以厚度成為1μm之方式旋轉塗佈於玻璃基板上，用100℃熱風乾燥機乾燥後，藉由反射模式確認表面的均勻性。 After the composition was dried, it was spin-coated on a glass substrate so that the thickness became 1 μm, and dried with a hot air dryer at 100°C, and then the surface uniformity was confirmed by a reflection mode.
<平坦性之判定> <Determination of Flatness>
○：整面未看到不均勻的反射 ○: No uneven reflection on the entire surface
△：在末端附近以肉眼確認到微細的表面不均勻 △: Fine surface unevenness is visually confirmed near the end
×：整面看到表面不均勻 ×: The surface is not uniform across the entire surface
由表3可確認到，實施例的耐熱性及平坦性 兩者皆優異，惟比較例的耐熱性及平坦性皆不優異。 It can be confirmed from Table 3 that the heat resistance and flatness of the examples Both are excellent, but the heat resistance and flatness of the comparative example are not excellent.
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| KR101572594B1 (en) | 2015-04-01 | 2015-11-27 | 최상준 | A Composition of Anti-Reflective Hardmask |
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2016
- 2016-06-16 KR KR1020160075050A patent/KR102452808B1/en active IP Right Grant
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2017
- 2017-04-14 TW TW106112551A patent/TWI697738B/en active
- 2017-05-18 CN CN201710353841.4A patent/CN107526252B/en active Active
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| TW200801818A (en) * | 2006-03-14 | 2008-01-01 | Jsr Corp | Composition for forming under film and method for forming pattern |
| US20140235059A1 (en) * | 2011-09-29 | 2014-08-21 | Nissan Chemical Industries, Ltd | Diarylamine novolac resin |
| EP2821421A1 (en) * | 2012-02-27 | 2015-01-07 | Mitsubishi Gas Chemical Company, Inc. | Acidified mono alkyl naphthalene formaldehyde resin |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR102452808B1 (en) | 2022-10-07 |
| KR20170141960A (en) | 2017-12-27 |
| CN107526252B (en) | 2022-01-25 |
| TW201809886A (en) | 2018-03-16 |
| CN107526252A (en) | 2017-12-29 |
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