TWI389935B - Composition for forming sublayer anti-reflective coating containing polyamic acid - Google Patents
Composition for forming sublayer anti-reflective coating containing polyamic acid Download PDFInfo
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- TWI389935B TWI389935B TW94129891A TW94129891A TWI389935B TW I389935 B TWI389935 B TW I389935B TW 94129891 A TW94129891 A TW 94129891A TW 94129891 A TW94129891 A TW 94129891A TW I389935 B TWI389935 B TW I389935B
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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
- G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
Description
本發明係關於製造半導體裝置之平版印刷過程中所使用之形成下層防反射膜之組成物、及使用此形成下層防反射膜組成物之光阻圖案的形成方法。特別，係關於使用i射線(波長365nm)或g射線(波長432nm)之平版印刷過程中所使用之形成下層防反射膜之組成物。更詳言之，係關於用以形成可經光阻用之鹼性顯像液所顯像之下層防反射膜的形成下層防反射膜之組成物，及使用此形成下層防反射膜組成物之令光阻與下層防反射膜同時顯像之光阻圖案的形成方法。The present invention relates to a composition for forming a lower anti-reflection film used in a lithographic process for fabricating a semiconductor device, and a method for forming a photoresist pattern using the composition for forming a lower anti-reflection film. In particular, it relates to a composition for forming a lower anti-reflection film used in a lithographic process using i-rays (wavelength 365 nm) or g-rays (wavelength 432 nm). More specifically, the composition for forming a lower anti-reflection film for forming an anti-reflection film under the image for forming an alkali-developable photosensitive liquid for photoresist, and the composition for forming the lower anti-reflection film using the same A method of forming a photoresist pattern that simultaneously develops a photoresist and a lower anti-reflection film.
於半導體裝置之製造中，以使用光阻的平版印刷進行微細加工。微細加工為於矽晶圓等之半導體基板上形成光阻薄膜，並於其上透過描繪裝置圖案的光罩圖案照射紫外線等之活性光線，顯像，並以所得之光阻圖案作為保護膜將基板予以蝕刻處理，於基板表面，形成對應前述圖案之微細凹凸的加工法。但是，經由光微影術步驟中曝光所使用之光由基板反射之駐波的影響，利基板段差之亂反射影響而產生令光阻圖案的尺寸精細度降低的問題。於是，檢討解決此間題，於光阻與基板之間設置下層防反射膜(Bottom Anti－Refective Coating,BARC)的方法。In the manufacture of a semiconductor device, microfabrication is performed by lithography using photoresist. Microfabrication is to form a photoresist film on a semiconductor substrate such as a germanium wafer, and irradiate active light rays such as ultraviolet rays through the mask pattern of the drawing device pattern thereon, and develop the image, and use the obtained photoresist pattern as a protective film. The substrate is etched to form a processing method corresponding to the fine unevenness of the pattern on the surface of the substrate. However, the effect of the standing wave reflected by the substrate by the light used for the exposure in the photolithography step is affected by the disordered reflection of the substrate step, which causes a problem that the dimensional fineness of the photoresist pattern is lowered. Therefore, a method of providing a Bottom Anti-Refective Coating (BARC) between the photoresist and the substrate is reviewed and solved.
此等下層防反射膜為了防止與其上所塗佈之光阻的層間混合(intermixing)，乃多使用熱交聯性組成物形成。其結果，防反射膜變成不溶於光阻用之鹼性顯像液，於半導體基板加工前必須以乾式蝕刻進行下層防反射膜的除去(例如，參照專利文獻1)。These lower anti-reflection films are formed by using a thermally crosslinkable composition in order to prevent intermixing of the photoresist applied thereto. As a result, the antireflection film becomes an alkaline developing solution which is insoluble in the photoresist, and the lower antireflection film must be removed by dry etching before the semiconductor substrate is processed (for example, see Patent Document 1).
但是，以乾式蝕刻除去下層防反射膜同時亦令光阻被蝕刻除去。因此，產生難以確保基板加工所必要之光阻膜厚的問題。於提高解像性為目的，使用薄膜之光阻的情形中，成為特別重大的問題。However, the removal of the underlying antireflection film by dry etching also causes the photoresist to be removed by etching. Therefore, there arises a problem that it is difficult to ensure the thickness of the photoresist film necessary for the substrate processing. In the case of using a photoresist of a film for the purpose of improving the resolution, it is a particularly important problem.
製造半導體裝置中的離子植入步驟為以光阻圖案作為模板並且對半導體基板導入雜質的步驟，為了迴避對基板表面造成損傷，乃於光阻之圖案形成時並未進行乾式蝕刻步驟。因此，於離子植入步驟用之光阻圖案的形成中，並無法將必須以乾式蝕刻除去的防反射膜使用於光阻的下層。目前於離子植入步驟中使用作為模板的光阻圖案其線寬為寬，少受到來自基板之曝光光反射之駐波影響、和基板段差之曝光光亂反射之影響，故在使用加入染料之光阻和光阻上層使用防反射膜下可解決反射所造成的問題。但是，隨著近年圖案尺寸的微細化，開始令離子植入步驟所用的光阻亦必須為微細圖案，且變成於光阻下層必須使用防反射膜。The ion implantation step in manufacturing the semiconductor device is a step of using a photoresist pattern as a template and introducing impurities into the semiconductor substrate, and in order to avoid damage to the surface of the substrate, the dry etching step is not performed at the time of pattern formation of the photoresist. Therefore, in the formation of the photoresist pattern for the ion implantation step, the antireflection film which must be removed by dry etching cannot be used for the lower layer of the photoresist. At present, the photoresist pattern used as a template in the ion implantation step has a wide line width, is less affected by the standing wave reflected from the exposure light of the substrate, and is affected by the reflection of the exposure light of the substrate, so that the dye is added. The upper layer of photoresist and photoresist is used under the anti-reflection film to solve the problem caused by reflection. However, with the miniaturization of the pattern size in recent years, the photoresist used in the ion implantation step must also be a fine pattern, and it is necessary to use an anti-reflection film in the lower layer of the photoresist.
由於此類情事，期望開發出溶解於光阻顯像所使用之鹼性顯像液，且可與光阻同時顯像除去的下層防反射膜。然而，直到目前，雖然已檢討可與光阻同時顯像除去的下層防反射膜(例如，參照專利文獻2、專利文獻3、專利文獻4、專利文獻5、專利文獻6)，但於微細加工的適用性、和所形成之圖案形狀等方面，仍未充分。Due to such circumstances, it is desired to develop an underlying antireflection film which is dissolved in an alkaline developing solution used for photoresist development and which can be simultaneously removed by photo-resistance. However, the lower-layer anti-reflection film which can be simultaneously removed by photo-resistance has been reviewed (for example, refer to Patent Document 2, Patent Document 3, Patent Document 4, Patent Document 5, and Patent Document 6), but in microfabrication. The applicability, and the shape of the pattern formed are still insufficient.
[專利文獻1]美國專利第第6156479號說明書[專利文獻2]專利第2686898號公報[專利文獻3]特開平9－78031號公報[專利文獻4]特開平11－72925號公報[專利文獻5]國際公開第03/057678號小冊[專利文獻6]國際公開第03/058345號小冊[Patent Document 1] US Pat. No. 6,156,479 [Patent Document 2] Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. ] International Publication No. 03/057678 booklet [Patent Document 6] International Publication No. 03/058345
本發明為鑑於上述情事，以提供可溶於光阻顯像所使用之鹼性顯像液的下層防反射膜、及用以形成此下層防反射膜的組成物為其目的。The present invention has been made in view of the above circumstances to provide a lower antireflection film which is soluble in an alkaline developing solution used for photoresist development, and a composition for forming the lower antireflection film.
即，本發明之目的為在於提供製造半導體裝置所使用的形成下層防反射膜之組成物。提供不會引起與上層塗佈、形成之光阻的層間混合，且溶解於鹼性顯像液，可與光阻同時顯像除去的下層防反射膜、及用以形成該下層防反射膜之形成下層防反射膜之組成物。That is, an object of the present invention is to provide a composition for forming a lower anti-reflection film used in the manufacture of a semiconductor device. Providing an underlying antireflection film which does not cause interlayer mixing with the upper layer coating and the formed photoresist, and which is dissolved in the alkaline developing solution, can be simultaneously removed by photo-resistance, and is used to form the lower anti-reflection film. A composition of the lower anti-reflection film is formed.
又，本發明為以提供對於i射線(波長365nm)顯示優良之吸收，且可溶於鹼性顯像液之下層防反射膜為其目的。Further, the present invention has an object of providing an antireflection film which exhibits excellent absorption for i-rays (wavelength 365 nm) and is soluble in an alkaline developing solution.
又，本發明之目的為在於提供使用該形成下層防反射膜之組成物並且使用於製造半導體裝置之光阻圖案的形成方法。Further, an object of the present invention is to provide a method of forming a photoresist pattern using the composition for forming an underlying antireflection film and used for fabricating a semiconductor device.
本發明第一觀點為於經由鹼性顯像液與光阻共同顯像形成下層防反射膜用之形成下層防反射膜之組成物中，含有具式(1)及式(2)：
第二觀點為於第一觀點記載的形成下層防反射膜組成物，該聚醯胺酸為由(a)四羧酸二酐化合物、(b)具有至少一個羧基之二胺化合物、及(c)二胺化合物所製造之聚醯胺酸。The second aspect is the formation of a lower anti-reflection film composition according to the first aspect, wherein the polyamic acid is a (a) tetracarboxylic dianhydride compound, (b) a diamine compound having at least one carboxyl group, and (c) a polylysine produced by a diamine compound.
第三觀點為於第二觀點記載的形成下層防反射膜組成物，該(a)四羧酸二酐化合物為具有至少一個苯環構造的四羧酸二酐化合物。The third aspect is the formation of the lower anti-reflection film composition described in the second aspect, wherein the (a) tetracarboxylic dianhydride compound is a tetracarboxylic dianhydride compound having at least one benzene ring structure.
第四觀點為於第二觀點記載的形成下層防反射膜組成物，該(b)具有至少一個羧基之二胺化合物為具有至少一個苯環構造的二胺化合物。The fourth aspect is the formation of the lower anti-reflection film composition described in the second aspect, wherein the (b) diamine compound having at least one carboxyl group is a diamine compound having at least one benzene ring structure.
第五觀點為於第二觀點記載的形成下層防反射膜組成物，該(c)二胺化合物為具有二個苯環構造的二胺化合物。The fifth aspect is the formation of the lower anti-reflection film composition described in the second aspect, wherein the (c) diamine compound is a diamine compound having two benzene ring structures.
第六觀點為於第一觀點記載的形成下層防反射膜組成物，該具有至少二個環氧基之化合物為具有三至五個環氧基之化合物。The sixth aspect is the formation of the lower anti-reflection film composition described in the first aspect, wherein the compound having at least two epoxy groups is a compound having three to five epoxy groups.
第七觀點為於第一觀點記載的形成下層防反射膜組成物，該吸光性化合物為由2－(4－二乙胺基－2－羥基苯甲醯)苯甲酸、2－(4－二丁胺基－2－羥苯甲醯)苯甲酸、2，2'，4，4'－四羥基二苯酮、2，3，3'，4，4'，5'－六羥基二苯酮、地衣酸、苯基螢光酮、玫紅酸、1，8，9－三羥基蒽、2－(4－羥苯基偶氮基)苯甲酸、甲基紅、4，4'－二胺基二苯酮、5，5'－亞甲基雙(2－羥基－4－甲氧基二苯酮)、3，4－二胺基二苯酮、姜黃素、及α－氰基－4－羥基肉桂酸所組成群中選出之化合物。The seventh aspect is the formation of a lower anti-reflection film composition described in the first aspect, wherein the light-absorbing compound is 2-(4-diethylamino-2-hydroxybenzhydrazide)benzoic acid, 2-(4-di) Butylamino-2-hydroxybenzhydrazide)benzoic acid, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,3',4,4',5'-hexahydroxybenzophenone , lichens acid, phenyl fluorescein, rosmarinic acid, 1,8,9-trihydroxyindole, 2-(4-hydroxyphenylazo)benzoic acid, methyl red, 4,4'-diamine Dibenzophenone, 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone), 3,4-diaminobenzophenone, curcumin, and α-cyano-4 a compound selected from the group consisting of hydroxycinnamic acid.
第八觀點為於第一觀點記載的形成下層防反射膜組成物，再含有萘羧酸化合物。The eighth aspect is the formation of the lower anti-reflection film composition described in the first aspect, and further contains a naphthalene carboxylic acid compound.
第九觀點為於第一觀點記載的形成下層防反射膜組成物，再含有萘醌二疊氮基磺酸化合物。The ninth point is that the lower anti-reflection film composition is formed as described in the first aspect, and further contains a naphthoquinonediazidesulfonic acid compound.
第十觀點為製造半導體裝置所用之光阻圖案的形成方法，其包含將第一觀點至第九觀點中任一項記載的形成下層防反射膜組成物於半導體基板上塗佈煅燒形成下層防反射膜之步驟，於該下層防反射膜上形成光阻層之步驟，令該下層防反射膜與該光阻層所覆蓋之半導體基板曝光之步驟，曝光後以鹼性顯像液予以顯像之步驟。A tenth aspect is a method for forming a photoresist pattern for use in a semiconductor device, comprising: forming a lower anti-reflection film composition according to any one of the first aspect to the ninth aspect, and coating the semiconductor substrate to form an underlying anti-reflection a step of forming a photoresist layer on the lower anti-reflection film, exposing the lower anti-reflection film and the semiconductor substrate covered by the photoresist layer, and exposing the image to an alkaline developing solution after exposure step.
第十一觀點為於第十觀點之光阻圖案的形成方法，該曝光為以365nm或432nm波長之光進行。The eleventh aspect is a method of forming a photoresist pattern according to the tenth aspect, wherein the exposure is performed at a wavelength of 365 nm or 432 nm.
經由使用本發明之形成下層防反射膜組成物，則不會引起與光阻的居間混合，且可形成溶解於光阻顯像所使用之鹼性顯像液，並且可與光阻同時顯像除去的下層防反射膜。By using the formation of the lower anti-reflection film composition of the present invention, it does not cause intervening mixing with the photoresist, and can form an alkaline developing solution dissolved in the photoresist display, and can be simultaneously imaged with the photoresist. The lower anti-reflection film is removed.
經由使用本發明之形成下層防反射膜組成物，則可形成對於i射線(波長365nm)顯示優良吸收的下層防反射膜。By forming the lower anti-reflection film composition of the present invention, a lower anti-reflection film exhibiting excellent absorption for i-rays (wavelength 365 nm) can be formed.
由本發明之形成下層防反射膜組成物所形成的下層防反射膜因可不進行乾式蝕刻而除去，故可使用於包含離子植入步驟等之以乾式蝕刻損害基板表面之敏感步驟之半導體裝置的製造過程。Since the lower anti-reflection film formed of the lower anti-reflection film composition of the present invention can be removed without dry etching, it is possible to manufacture a semiconductor device for a sensitive step including dry etching to damage the surface of the substrate by an ion implantation step or the like. process.
又，使用本發明之形成下層防反射膜組成物以形成下層防反射膜之情況，經由改變形成防反射膜時之煅燒條件，則可改變下層防反射膜對於光阻顯像所使用之鹼性顯像液的溶解速度。Further, in the case where the lower anti-reflection film composition of the present invention is formed to form the lower anti-reflection film, the alkalinity of the lower anti-reflection film for photo-resistance can be changed by changing the calcination conditions at the time of forming the anti-reflection film. The dissolution rate of the imaging solution.
本發明之形成下層防反射膜組成物為包含具有式(1)及式(2)所示構造之聚醯胺酸，具有至少二個環氧基之化合物，對於波長365nm之光的莫耳吸光係數為5000~100000(l/mol．cm)的吸光性化合物、及溶劑。此外，本發明之形成下層防反射膜組成物可包含萘醌二疊氮基磺酸化合物等之感光性化合物、萘羧酸化合物等之芳香族羧酸化合物、及界面活性劑等。The underlying antireflection film composition of the present invention is a polyglycine having a structure represented by the formulas (1) and (2), a compound having at least two epoxy groups, and moor light absorption for light having a wavelength of 365 nm. A light absorbing compound having a coefficient of from 5,000 to 100,000 (l/mol.cm) and a solvent. Further, the underlying antireflection film composition of the present invention may contain a photosensitive compound such as a naphthoquinonediazidesulfonic acid compound, an aromatic carboxylic acid compound such as a naphthalenecarboxylic acid compound, or a surfactant.
本發明之形成下層防反射膜組成物中之固形成分的比例只要可令各成分均勻溶解則無特別限定，例如為0.5~50質量%、或1~30質量、或5~25質量%、或10~20質量%。此處所謂固形成分為由形成下層防反射膜組成物之全成分中除去溶劑成分者。The ratio of the solid content in the formation of the lower anti-reflection film of the present invention is not particularly limited as long as the components are uniformly dissolved, and is, for example, 0.5 to 50% by mass, or 1 to 30% by mass, or 5 to 25% by mass, or 10~20% by mass. Here, the solid formation is classified into the removal of a solvent component from the entire composition of the composition for forming the lower antireflection film.
具體說明本發明之形成下層防反射膜組成物。The formation of the underlying antireflection film composition of the present invention will be specifically described.
本發明之形成下層防反射膜組成物為包含具有式(1)所示構造和式(2)所示構造的聚醯胺酸。The underlying antireflection film composition of the present invention is a polylysine comprising a structure represented by the formula (1) and a structure represented by the formula (2).
式(1)中A1 為表示四價有機基，B1 為表示三價有機基。A1 可列舉例如式(3)~(10)(式中X為表示碳數1~5個之烷基、氯原子、溴原子、氟原子、碳數1~5個之烷氧基、羥基、羧基、苯氧基、三氟甲基或硝基、m1 為表示0、1或2之數)。In the formula (1), A 1 represents a tetravalent organic group, and B 1 represents a trivalent organic group. Examples of A 1 include the formulae (3) to (10) (wherein X is an alkyl group having 1 to 5 carbon atoms, a chlorine atom, a bromine atom, a fluorine atom, an alkoxy group having 1 to 5 carbon atoms, or a hydroxyl group; , carboxy, phenoxy, trifluoromethyl or nitro, m 1 is a number representing 0, 1 or 2.
碳數1~5個之烷基為甲基、乙基、異丙基、環戊基及正戊基等。碳數1~5個之烷氧基為甲氧基、乙氧基、異丙氧基、環戊氧基及正戊氧基等。The alkyl group having 1 to 5 carbon atoms is a methyl group, an ethyl group, an isopropyl group, a cyclopentyl group, an n-pentyl group or the like. The alkoxy group having 1 to 5 carbon atoms is a methoxy group, an ethoxy group, an isopropoxy group, a cyclopentyloxy group, a n-pentyloxy group or the like.
B1 可列舉例如式(11)~(18)(式中Y為表示碳數1~5個之烷基、氯原子、溴原子、氟原子、碳數1~5個之烷氧基、羥基、羧基、苯氧基、三氟甲基或硝基、m2 為表示0、1或2之數)。Examples of B 1 include the formulae (11) to (18) (wherein Y represents an alkyl group having 1 to 5 carbon atoms, a chlorine atom, a bromine atom, a fluorine atom, an alkoxy group having 1 to 5 carbon atoms, and a hydroxyl group; , carboxy, phenoxy, trifluoromethyl or nitro, m 2 is a number representing 0, 1 or 2.
於式(2)中A2 為表示四價有機基、B2 為表示二價有機基。A2 可列舉例如式(3)~(10)。In the formula (2), A 2 represents a tetravalent organic group, and B 2 represents a divalent organic group. A 2 can be exemplified by the formulas (3) to (10), for example.
B2 可列舉例如式(19)~(27)(式中Z為表示碳數1~5個之烷基、氯原子、溴原子、氟原子、碳數1~5個之烷氧基、羥基、羧基、苯氧基、三氟甲基或硝基、m3 為表示0、1或2之數)。B 2 is, for example, the formula (19) to (27) (wherein Z is an alkyl group having 1 to 5 carbon atoms, a chlorine atom, a bromine atom, a fluorine atom, an alkoxy group having 1 to 5 carbon atoms, or a hydroxyl group; , carboxy, phenoxy, trifluoromethyl or nitro, m 3 is a number representing 0, 1 or 2.).
本發明所用之聚醯胺酸的重量平均分子量以換算為聚苯乙烯例如為1000~100000、或2000~50000、或3000~30000、或5000~10000。聚醯胺酸之重量平均分子量小於前述值之情形中，所形成之下層防反射膜對於光阻所使用之溶劑的溶解度變高，其結果，引起與光阻的層間混合之情況。聚醯胺酸之重量平均分子量大於前述值之情形中，所形成之下層防反射膜對於光阻顯像中所使用之鹼性顯像液的溶解性不夠充分，於顯像後有時發生殘渣。The weight average molecular weight of the polylysine used in the present invention is, for example, from 1,000 to 100,000, or from 2,000 to 50,000, or from 3,000 to 30,000, or from 5,000 to 10,000 in terms of polystyrene. In the case where the weight average molecular weight of the polyamic acid is less than the above value, the solubility of the underlying antireflection film formed for the solvent used for the photoresist becomes high, and as a result, the interlayer of the photoresist is mixed. In the case where the weight average molecular weight of the polylysine is larger than the above value, the solubility of the underlying antireflection film formed for the alkaline developing solution used in the photoresist development is insufficient, and the residue sometimes occurs after the development. .
取得本發明之形成下層防反射膜組成物所含之聚醯胺酸的方法並無特別限定，可依已知之方法進行製造。例如，令二胺化合物、與四羧酸或其衍生物之四羧酸二酐化合物和二羧酸二鹵化物等，經由反應、聚合則可製造聚醯胺酸。又，經由使用雙甲矽烷基化二胺化合物與四羧酸二酐化合物的聚合合成聚醯胺酸甲矽烷酯後，以酸分解甲矽烷酯部分則可製造聚醯胺酸。The method for obtaining the polylysine contained in the composition for forming the underlying antireflection film of the present invention is not particularly limited, and it can be produced by a known method. For example, a polyamine acid can be produced by reacting or polymerizing a diamine compound, a tetracarboxylic dianhydride compound of a tetracarboxylic acid or a derivative thereof, and a dicarboxylic acid dihalide. Further, by synthesizing the polymethyl decyl methacrylate by polymerization using a bis-methylated diamine compound and a tetracarboxylic dianhydride compound, the polydecyl acid can be produced by decomposing the methacrylate moiety with an acid.
本發明之形成下層防反射膜組成物所含有的聚醯胺酸可由(a)四羧酸二酐化合物、(b)具有至少一個羧基之二胺化合物、及(c)二胺化合物則可製造。The polyphthalic acid contained in the composition for forming the lower antireflection film of the present invention can be produced by (a) a tetracarboxylic dianhydride compound, (b) a diamine compound having at least one carboxyl group, and (c) a diamine compound. .
本發明所用之聚醯胺酸製造中所使用的(a)四羧酸二酐化合物並無特別限定。(a)四羧酸二酐化合物可使用一種，又，可同時使用二種以上。The (a) tetracarboxylic dianhydride compound used in the production of the polyamic acid used in the present invention is not particularly limited. (a) The tetracarboxylic dianhydride compound may be used alone or in combination of two or more.
可使用具有至少一個苯環構造，例如一至四個苯環構造造的四羧酸二酐化合物。A tetracarboxylic dianhydride compound having at least one benzene ring structure, for example, one to four benzene ring structures can be used.
具體例可列舉均苯四甲酸二酐、3，3'，4，4'－聯苯四羧酸二酐、3，3'，4，4'二苯酮四羧酸二酐、3，3'，4，4'－聯苯醚四羧酸二酐、4，4'－(六氟異亞丙基)二苯甲酸二酐及3，3'，4，4'－聯苯碸四羧酸二酐等之芳香族四羧酸二酐、1，2，3，4－環丁烷四羧酸二酐、1，2－二甲基－1，2，3，4－環丁烷四羧酸二酐、1，2，3，4－四甲基－1，2，3，4－環丁烷四羧酸二酐、1，2，3，4－環戊烷四羧酸二酐、1，2，3，4－環己烷四羧酸二酐、及3，4－二羧基－1，2，3，4－四氫－1－萘琥珀酸二酐等之脂環式四羧酸二酐、1，2，3，4－丁烷四羧酸二酐等之脂脂族四羧酸二酐。Specific examples thereof include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4' benzophenonetetracarboxylic dianhydride, and 3,3. ',4,4'-diphenyl ether tetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene)dibenzoic acid dianhydride and 3,3',4,4'-biphenylfluorene tetracarboxylic acid Aromatic tetracarboxylic dianhydride such as acid dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane IV Carboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride , 1,2,3,4-cyclohexanetetracarboxylic dianhydride, and alicyclic four of 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride An aliphatic aliphatic tetracarboxylic dianhydride such as carboxylic acid dianhydride or 1,2,3,4-butane tetracarboxylic dianhydride.
製造本發明所用之聚醯胺酸所使用之(b)具有至少一個羧基之二胺化合物並無特別限定。羧基數例如為一至四個。(b)具有至少一個羧基之二胺化合物可使用一種，又，可同時使用二種以上。The (b) diamine compound having at least one carboxyl group used for producing the polylysine used in the present invention is not particularly limited. The number of carboxyl groups is, for example, one to four. (b) The diamine compound having at least one carboxyl group may be used alone or in combination of two or more.
(b)具有至少一個羧酸之二胺化合物可使用具有至少一個苯環構造，例如一至三個苯環構造之二胺化合物。(b) The diamine compound having at least one carboxylic acid may use a diamine compound having at least one benzene ring structure, for example, one to three benzene ring structures.
具體例可列舉2，4－二胺基苯甲酸、2，5－二胺基苯甲酸、3，5－二胺基苯甲酸、4，6－二胺基－1，3－苯二羧酸、2，5－二胺基－1，4－苯二羧酸、雙(4－胺基－3－羧苯基)醚、雙(4－胺基－3，5－二羧苯基)醚、雙(4－胺基－3－羧苯基)碸、雙(4－胺基－3，5－二羧苯基)碸、4，4'－二胺基－3，3'二羧基聯苯、4，4'－二胺基－3，3'－二羧基－5，5'－二甲基聯苯、4，4'－二胺基－3，3'－二羧基－5，5'－二甲氧基聯苯、1，4－雙(4－胺基－3－羧苯氧基)苯、1，3－雙(4－胺基－3－羧苯氧基)苯、雙[4－(4－胺基－3－羧苯氧基)苯基]碸、雙[4－(4－胺基－3－羧苯氧基)苯基]丙烷、及2，2－雙[4－(4－胺基－3－羧苯氧基)苯基]六氟丙烷等。Specific examples thereof include 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, and 4,6-diamino-1,3-benzenedicarboxylic acid. , 2,5-diamino-1,4-benzenedicarboxylic acid, bis(4-amino-3-carboxyphenyl)ether, bis(4-amino-3,5-dicarboxyphenyl)ether , bis(4-amino-3-carboxyphenyl)anthracene, bis(4-amino-3,5-dicarboxyphenyl)anthracene, 4,4'-diamino-3,3'dicarboxyl linkage Benzene, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5 '-Dimethoxybiphenyl, 1,4-bis(4-amino-3-carboxyphenoxy)benzene, 1,3-bis(4-amino-3-carboxyphenoxy)benzene, double [4-(4-Amino-3-carboxyphenoxy)phenyl]anthracene, bis[4-(4-amino-3-carboxyphenoxy)phenyl]propane, and 2,2-double [ 4-(4-Amino-3-carboxyphenoxy)phenyl]hexafluoropropane or the like.
又，製造本發明所用之聚醯胺酸所使用之(c)二胺化合物並無特別限定。(c)二胺化合物可使用一種，又，可同時使用二種以上。Further, the (c) diamine compound used for producing the polyamic acid used in the present invention is not particularly limited. (c) The diamine compound may be used alone or in combination of two or more.
(c)二胺化合物可使用具有一至三個苯環構造，例如，具有二個苯環構造的二胺化合物。(c) The diamine compound may have a diamine compound having one to three benzene ring structures, for example, having two benzene ring structures.
具體例可列舉2，4－二胺基苯酚、3，5－二胺基苯酚、2，5－二胺基苯酚、4，6－二胺基間苯二酚、2，5－二胺基氫醌、雙(3－胺基－4－羥苯基)醚、雙(4－胺基－3－羥苯基)醚、雙(4－胺基－3，5－二羥苯基)醚、雙(3－胺基－4－羥苯基)甲烷、雙(4－胺基－3－羥苯基)甲烷、雙(4－胺基－3，5－二羥苯基)甲烷、雙(3－胺基－4－羥苯基)碸、雙(4－胺基－3－羥苯基)碸、雙(4－胺基－3，5－二羥苯基)碸、2，2－雙(3－胺基－4－羥苯基)六氟丙烷、2，2－雙(4－胺基－3－羥苯基)六氟丙烷、2，2－雙(4－胺基－3，5－二羥苯基)六氟丙烷、4，4'－二胺基－3，3'－二羥基聯苯、4，4'－二胺基－3，3'－二羥基－5，5'－二甲基聯苯、4，4'－二胺基－3，3'－二羥基－5，5'－二甲氧基聯苯、1，4－雙(3－胺基－4－羥苯氧基)苯、1，3－雙(3－胺基－4－羥苯氧基)苯、1，4－雙(4－胺基－3－羥苯氧基)苯、1，3－雙(4－胺基－3－羥苯氧基)苯、雙[4－(3－胺基－4－羥苯氧基)苯基]碸、雙[4－(3－胺基－4－羥苯氧基)苯基]丙烷、2，2－雙[4－(3－胺基－4－羥苯氧基)苯基]六氟丙烷等之具有酚性羥基的二胺化合物、1，3－二胺基－4－氫硫基苯、1，3－二胺基－5－氫硫基苯、1，4－二胺基－2－氫硫基苯、雙(4－胺基－3－氫硫苯基)醚、及2，2－雙(3－胺基－4－氫硫苯基)六氟丙烷等之具有硫酚基的二胺化合物、1，3－二胺基苯－4－磺酸、1，3－二胺基苯－5－磺酸、1，4－二胺基苯－2－磺酸、雙(4－胺基苯－3－磺酸)醚、4，4'－二胺基聯苯)3，3'－二磺酸、及4，4'－二胺基－3，3'－二甲基聯苯－6，6'－二磺酸等之具有磺酸基的二胺化合物、3，5－二胺基苯甲酸－第三丁酯、3，5－二胺基苯甲酸乙氧甲酯、3，5－二胺基苯甲酸甲酯、3，5－二胺基苯甲酸正丙酯、及3，5－二胺基苯甲酸異丁酯等之含有羧酸酯基的二胺化合物。又，可列舉對－苯二胺、間－苯二胺、4，4'－亞甲基－雙(2，6－乙基苯胺)、4，4'－亞甲基－雙(2－異丙基－6－甲基苯胺)、4，4'－亞甲基－雙(2，6－二異亞丙基)、2，4，6－三甲基－1，3－苯二胺、2，3，5，6－四甲基－1，4－苯二胺、鄰－聯甲苯胺、間－聯甲苯胺、3，3'，5，5'－四甲基聯苯胺、雙[4－(3－胺苯氧基)苯基]碸、2，2－雙[4－(3－胺苯氧基)苯基]丙烷、2，2－雙[4－(3－胺苯氧基)苯基]六氟丙烷、4，4'－二胺基－3，3'－二甲基二環己基甲烷、4，4'－二胺基聯苯醚、3，4－二胺基聯苯醚、4，4'－二胺基聯苯甲烷、2，2－雙(4－苯胺基)六氟丙烷、2，2－雙(3－苯胺基)六氟丙烷、2，2－雙(3－胺基－4－甲苯醯)六氟丙烷、1，4－雙(4－胺苯氧基)苯、1，3－雙(4－胺苯氧基)苯、雙[4－(3－胺苯氧基)苯基)碸、2，2－雙[4－(4－胺苯氧基)苯基]丙烷、及2，2－雙[4－(4－胺苯氧基)苯基]六氟丙烷等之二胺化合物。Specific examples thereof include 2,4-diaminophenol, 3,5-diaminophenol, 2,5-diaminophenol, 4,6-diaminoresorcin, and 2,5-diamine. Hydroquinone, bis(3-amino-4-hydroxyphenyl)ether, bis(4-amino-3-hydroxyphenyl)ether, bis(4-amino-3,5-dihydroxyphenyl)ether , bis(3-amino-4-hydroxyphenyl)methane, bis(4-amino-3-hydroxyphenyl)methane, bis(4-amino-3,5-dihydroxyphenyl)methane, double (3-Amino-4-hydroxyphenyl)indole, bis(4-amino-3-hydroxyphenyl)indole, bis(4-amino-3,5-dihydroxyphenyl)anthracene, 2,2 - bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino- 3,5-Dihydroxyphenyl)hexafluoropropane, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxy-5 , 5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethoxybiphenyl, 1,4-bis(3-amino- 4-hydroxyphenoxy)benzene, 1,3-bis(3-amino-4-hydroxyphenoxy)benzene, 1,4-bis(4-amino-3- Hydroxyphenoxy)benzene, 1,3-bis(4-amino-3-hydroxyphenoxy)benzene, bis[4-(3-amino-4-hydroxyphenoxy)phenyl]anthracene, double [4-(3-Amino-4-hydroxyphenoxy)phenyl]propane, 2,2-bis[4-(3-amino-4-hydroxyphenoxy)phenyl]hexafluoropropane, etc. Diamine compound having phenolic hydroxyl group, 1,3-diamino-4-hydrothiobenzene, 1,3-diamino-5-thiothiobenzene, 1,4-diamino-2-hydrogen a thiophenol group such as thiobenzene, bis(4-amino-3-hydrothiophenyl)ether, and 2,2-bis(3-amino-4-hydrothiophenyl)hexafluoropropane Amine compound, 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-5-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, bis(4-amine Benzo-3-sulfonic acid)ether, 4,4'-diaminobiphenyl) 3,3'-disulfonic acid, and 4,4'-diamino-3,3'-dimethylbiphenyl a diamine compound having a sulfonic acid group such as -6,6'-disulfonic acid, 3,5-diaminobenzoic acid-t-butyl ester, 3,5-diaminobenzoic acid ethoxymethyl ester, 3 , methyl 5-diaminobenzoate, n-propyl 3,5-diaminobenzoate And 3,5-aminobenzoic acid isobutyl-containing carboxylate groups of the diamine compound. Further, examples thereof include p-phenylenediamine, m-phenylenediamine, 4,4'-methylene-bis(2,6-ethylaniline), and 4,4'-methylene-bis(2-iso). Propyl-6-methylaniline), 4,4'-methylene-bis(2,6-diisopropylidene), 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, o-toluidine, m-toluidine, 3,3',5,5'-tetramethylbenzidine, double [ 4-(3-Aminophenoxy)phenyl]anthracene, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminephenoxy) Phenyl]hexafluoropropane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diaminodiphenyl ether, 3,4-diamine Diphenyl ether, 4,4'-diaminobiphenylmethane, 2,2-bis(4-anilino)hexafluoropropane, 2,2-bis(3-anilino)hexafluoropropane, 2,2- Bis(3-Amino-4-toluene)hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, bis[4- (3-Aminophenoxy)phenyl)indole, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and 2,2-bis[4-(4 Amine) phenyl] hexafluoropropane the diamine compound.
於本發明所使用之聚醯胺酸的製造中，所使用之全二胺化合物中所佔之(b)具有至少一個羧基之二胺化合物的比例為例如1~99質量%、或5~80質量%、或10~60質量%、或20~50質量%、或30~40質量%。(b)具有至少一個羧基之二胺化合物的比例更少之情形中，所形成之下層防反射膜對於鹼性顯像液的溶解性不夠充分。In the production of the polylysine used in the present invention, the ratio of (b) the diamine compound having at least one carboxyl group to the total diamine compound used is, for example, 1 to 99% by mass, or 5 to 80. % by mass, or 10 to 60% by mass, or 20 to 50% by mass, or 30 to 40% by mass. (b) In the case where the proportion of the diamine compound having at least one carboxyl group is small, the solubility of the underlying antireflection film formed for the alkaline developing solution is insufficient.
本發明所用之聚醯胺酸為由(a)四羧酸二酐化合物、(b)具有至少二個羧基之二胺化合物、及(c)二胺化合物所製造中，期望所使用之二胺化合物的總莫耳數與四羧酸二酐化合物的總莫耳數之比為0.8~1.2。同一般的縮聚反應，此莫耳比愈接近1則生成之聚醯胺酸的聚合度愈大且分子量愈增加。The polylysine used in the present invention is a diamine which is preferably produced from (a) a tetracarboxylic dianhydride compound, (b) a diamine compound having at least two carboxyl groups, and (c) a diamine compound. The ratio of the total number of moles of the compound to the total number of moles of the tetracarboxylic dianhydride compound is from 0.8 to 1.2. In the same general polycondensation reaction, the closer the molar ratio is to 1, the greater the degree of polymerization of the polylysine formed and the higher the molecular weight.
於聚醯胺酸的製造中，二胺化合物與四羧酸二酐化合物反應之反應溫度可選擇－20℃~150℃、較佳為－5℃~100℃之任意溫度。反應溫度為5℃~40℃、反應時間1~48小時則可取得高分子量的聚醯胺酸。於取得低分子量且保存安定性高之聚醯胺酸上，以40℃~80℃反應1小時以上為更佳。In the production of polylysine, the reaction temperature of the reaction of the diamine compound with the tetracarboxylic dianhydride compound may be any temperature of from -20 ° C to 150 ° C, preferably from -5 ° C to 100 ° C. A high molecular weight polylysine can be obtained at a reaction temperature of 5 ° C to 40 ° C and a reaction time of 1 to 48 hours. It is more preferable to carry out a reaction at 40 ° C to 80 ° C for 1 hour or more on a polylysine having a low molecular weight and high storage stability.
二胺化合物與四羧酸二酐化合物的反應可於溶劑中進行。此時可使用的溶劑可列舉N，N－二甲基甲醯胺、N，N－二甲基乙醯胺、N－甲基吡咯烷酮、N－乙烯基吡咯烷酮、N－甲基己內酯、二甲基亞碸、四甲基脲、吡啶、二甲基碸、間－甲酚、γ－丁內酯、乙酸乙酯、乙酸丁酯、乳酸乙酯、3－甲氧基丙酸甲酯、2－甲氧基丙酸甲酯、3－甲氧基丙酸乙酯、2－甲氧基丙酸乙酯、3－乙氧基丙酸乙酯、2－乙氧基丙酸乙酯、乙二醇二甲醚、二乙二醇二甲醚、二乙二醇二***、二乙二醇甲基***、丙二醇二甲醚、二丙二醇二甲醇、乙二醇單甲醚、乙二醇單***、二乙二醇單甲醚、二乙二醇單***、丙二醇單甲醚、丙二醇單***、二丙二醇單甲醚、二丙二醇單***、丙二醇單甲醚乙酸酯、卡必醇乙酸酯、乙基溶纖劑乙酸酯、環己酮、甲基乙基酮、甲基異丁基酮、及2－庚酮等。其可單獨、或混合使用亦可。更且，亦可將不溶解聚醯胺酸的溶劑，於聚合反應所生成之聚醯胺酸不析出的範圍下，於上述溶劑中混合使用。The reaction of the diamine compound with the tetracarboxylic dianhydride compound can be carried out in a solvent. The solvent which can be used at this time is, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactone, Dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, m-cresol, γ-butyrolactone, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate , methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate , ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethanol, ethylene glycol monomethyl ether, ethylene Alcohol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, carbitol Acetate, ethyl cellosolve acetate, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone. They may be used singly or in combination. Further, a solvent in which polylysine is not dissolved may be used in combination in the above solvent in a range in which polyamic acid produced by the polymerization reaction does not precipitate.
含有如此處理所得之聚醯胺酸的溶液可就其原樣使用於形成下層防反射膜之組成物的調製中。又，將聚醯胺酸投入甲醇、乙醇等等貧溶劑令其沈澱．單離供使用亦可。The solution containing the polylysine thus obtained can be used as it is in the preparation of the composition for forming the underlying antireflection film. 2. In addition, polylysine is added to a poor solvent such as methanol or ethanol to precipitate it. It can also be used separately.
本發明之形成下層防反射膜組成物中所含有的聚醯胺酸，以除去其終端部分，基本上，由式(1)所示構造及式(2)所示構造所成的聚醯胺酸為佳。The polyamic acid contained in the composition for forming a lower anti-reflection film of the present invention is used to remove the terminal portion thereof, and basically, the polyamine produced by the structure represented by the formula (1) and the structure represented by the formula (2) Acid is better.
本發明之形成下層防反射膜組成物中所含有的聚醯胺酸可列舉例如下述之聚醯胺酸(式(29)~(37))(式中P1 、P2 、P3 及P4 為表示聚醯胺酸中的各構造比例，且其和為1)。此處，式(29)~(36)為由一種四羧酸二酐化合物與二種二胺化合物所製造的聚醯胺酸，式(37)為由二種四羧酸二酐化合物與二種二胺化合物所製造的聚醯胺酸。The polylysine which is contained in the composition for forming the lower antireflection film of the present invention may, for example, be a polyglycolic acid (formulas (29) to (37)) (wherein P 1 , P 2 , P 3 and P 4 represents each structural ratio in the poly-proline, and the sum thereof is 1). Here, the formulae (29) to (36) are polyamic acids produced from a tetracarboxylic dianhydride compound and two kinds of diamine compounds, and the formula (37) is composed of two tetracarboxylic dianhydride compounds and two Polylysine produced by a diamine compound.
本發明之形成下層防反射膜組成物為含有具有至少二個環氧基的化合物。此類化合物若為具有環氧基之化合物則無特別限定。可列舉例如三(2，3－環氧丙基)異氰脲酸酯、1，4－丁二醇二縮水甘油醚、1，2－環氧－4－(環氧乙基)環己烷、甘油三縮水甘油醚、二乙二醇二縮水甘油醚、2，6－二縮水甘油苯基縮水甘油醚、1，1，3－[對－(2，3－環氧丙氧基)苯基]丙烷、1，2－環己烷二羧酸二縮水甘油酯、4，4'－亞甲基雙(N，N－二縮水甘油苯胺)、3，4－環氧環己基甲基－3，4－環氧環己烷羧酸酯、三羥甲基乙烷三縮水甘油醚及雙酚A－二縮水甘油醚、及季戊四醇聚縮水甘油醚等。The underlayer antireflection film composition of the present invention contains a compound having at least two epoxy groups. Such a compound is not particularly limited as long as it is a compound having an epoxy group. For example, tris(2,3-epoxypropyl)isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(oxiranyl)cyclohexane , glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidyl phenyl glycidyl ether, 1,1,3-[p-(2,3-epoxypropoxy)benzene Propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl- 3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol A-diglycidyl ether, and pentaerythritol polyglycidyl ether.
又，具有至少二個環氧基之化合物可使用具有環氧基的聚合物。此類聚合物若為具有環氧基之聚合物，則無特別限制可使用。Further, as the compound having at least two epoxy groups, a polymer having an epoxy group can be used. If such a polymer is a polymer having an epoxy group, it can be used without particular limitation.
此類聚合物可經由使用具有環氧基之加成聚合性單體的加成聚合加以製造。又，經由具有羥基之高分子化合物與表氯醇、甲苯磺酸縮水甘油酯等之具有環氧基之化合物的反應則可製造。可列舉例如聚丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯與甲基丙烯酸乙酯之共聚物、及甲基丙烯酸縮水甘油酯與苯乙烯與甲基丙烯酸2－羥乙酯之共聚物等之加成聚合聚合物、和環氧酚醛清漆等之縮聚聚合物。此類聚合物的重量平均分子量例如為500~200000、或1000~100000、或3000~30000。Such a polymer can be produced by addition polymerization using an addition polymerizable monomer having an epoxy group. Further, it can be produced by a reaction of a polymer compound having a hydroxyl group with a compound having an epoxy group such as epichlorohydrin or glycidyl toluenesulfonate. For example, a polyglycidyl polyacrylate, a copolymer of glycidyl methacrylate and ethyl methacrylate, a copolymer of glycidyl methacrylate and a copolymer of styrene and 2-hydroxyethyl methacrylate may be mentioned. A polycondensation polymer of a polymerized polymer, and an epoxy novolac. The weight average molecular weight of such a polymer is, for example, 500 to 200,000, or 1,000 to 100,000, or 3,000 to 30,000.
具有至少二個環氧基之化合物可列舉具有胺基之環氧樹脂YH－434、YH434L(東都化成(股)製)，具有環己烯化氧構造之環氧樹脂Epolid GT－401、同GT－403、同GT－301、同GT－302、Seroxide 2021、Seroxide 3000(Diacel化學(股)製)、雙酚A型環氧樹脂Epicoat 1001、同1002、同1003、同1004、同1007、同1009、同1010、同828(以上，油化Shell Epoxy(股)製)等、雙酚F型環氧樹脂Epicoat 807(油化Shell Epoxy(股)製)等、雙酚酚醛清漆型環氧樹脂Epicoat 152、同154(以上，油化Shell Epoxy(股)製)、EPPN201、同202(以上，日本化藥(股)製)等、甲酚酚醛清漆型環氧樹脂EOCN－102、EOCN－103S、EOCN－104S、EOCN－1020、EOCN－1025、EOCN－1027(以上，日本化藥(股)製)、Epicoat 180S75(油化Shell Epoxy(股)製)等、脂環式環氧樹脂Denacol EX－252(Nagase Chemtex(股)製)、CY175、CY177、CY179(以上，CIBA－GEIGY A－G製)、Araludite CY－182、同CY－192、同CY－184(以上，CIBA－GEIGY A.G製)、Epiclone 200、同400(以上，大日本油墨工業(股)製)、Epicoat 871、同872(以上，油化Shell Epoxy(股)製)、ED－5661、ED－5662(以上，Ceraneeds Coating(股)製)等、脂肪族聚縮水甘油醚Denacoal EX－611、同EX－612、同EX－614、同EX－622、同EX－411、同EX－512、同EX－522、同EX－421、同EX－313、同EX－314、同EX－321(Nagase Chemtex(股)製)等之市售的化合物。Examples of the compound having at least two epoxy groups include an epoxy group YH-434 having an amine group, YH434L (manufactured by Tohto Kasei Co., Ltd.), an epoxy resin Epolid GT-401 having a cyclohexene oxide structure, and the same GT. -403, the same GT-301, the same GT-302, Seroxide 2021, Seroxide 3000 (Diacel Chemical Co., Ltd.), bisphenol A epoxy resin Epicoat 1001, the same 1002, the same 1003, the same 1004, the same 1007, the same 1009, the same as 1010, the same 828 (above, oiled Shell Epoxy (stock)), bisphenol F-type epoxy resin Epicoat 807 (oiled Shell Epoxy (manufactured by the company)), bisphenol novolac type epoxy resin Epicoat 152, 154 (above, oiled Shell Epoxy), EPPN201, 202 (above, Nippon Chemical Co., Ltd.), cresol novolak epoxy resin EOCN-102, EOCN-103S , EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (above, Nippon Kayaku Co., Ltd.), Epicoat 180S75 (oiled Shell Epoxy Co., Ltd.), alicyclic epoxy resin Denacol EX -252 (made by Nagase Chemtex), CY175, CY177, CY179 (above, CIBA-GEIGY A-G), Araludite CY-182, same as CY-192, and CY-184 (above, C IBA-GEIGY AG), Epiclione 200, same 400 (above, Dainippon Ink Industries Co., Ltd.), Epicoat 871, 872 (above, oiled Shell Epoxy), ED-5661, ED-5662 (above, Ceraneeds Coating), aliphatic polyglycidyl ether Denacoal EX-611, same as EX-612, with EX-614, with EX-622, with EX-411, with EX-512, with EX -522, a commercially available compound such as EX-421, EX-313, EX-314, and EX-321 (manufactured by Nagase Chemtex).
具有至少二個環氧基之化合物於使用非聚合物的化合物時，例如，以具有二至十個、或三至五個環氧基之化合物為較佳使用。The compound having at least two epoxy groups is preferably used in the case of using a non-polymer compound, for example, a compound having two to ten or three to five epoxy groups.
上述具有至少二個環氧基之化合物的含量為相對於聚醯胺酸100質量份例如以5~70質量份、或，10~60質量份，較佳為15~45質量份、或20~40質量%。具有至少二個環氧基之化合物的含量小於前述值之情形中，則下層防反射膜的硬化度不足，有時溶解於光阻溶劑，且引起居間混合。具有至少二個環氧基之化合物的含量為大於前述值之情形中，變成無法取得對於光阻顯像所使用之鹼性顯像液之充分的溶解性。The content of the compound having at least two epoxy groups is, for example, 5 to 70 parts by mass, or 10 to 60 parts by mass, preferably 15 to 45 parts by mass, or 20%, per 100 parts by mass of the polyamic acid. 40% by mass. In the case where the content of the compound having at least two epoxy groups is less than the above value, the degree of hardening of the underlying antireflection film is insufficient, and it may be dissolved in the photoresist solvent and cause intervening mixing. In the case where the content of the compound having at least two epoxy groups is larger than the above value, sufficient solubility in the alkaline developing solution used for photoresist development cannot be obtained.
本發明之形成下層防反射膜組成物為包含對於波長365nm光具有大莫耳吸光係數的吸光性化合物。莫耳吸光係數為5000~100000(l/mol．cm)，較佳為10000~80000(l/mol．cm)、或15000~50000(l/mol．cm)。莫耳吸光係數小於5000(l/mol．cm)時，無法取得具有充分衰減係數(k值)的下層防反射膜，且有時無法取得充分的防反射效果。The underlying antireflection film composition of the present invention is a light absorbing compound containing a large molar absorption coefficient for light having a wavelength of 365 nm. The molar absorption coefficient is from 5,000 to 100,000 (l/mol.cm), preferably from 10,000 to 80,000 (l/mol.cm), or from 15,000 to 50,000 (l/mol.cm). When the Mohr absorption coefficient is less than 5,000 (l/mol.cm), a lower antireflection film having a sufficient attenuation coefficient (k value) cannot be obtained, and a sufficient antireflection effect may not be obtained.
對於波長365nm之光具有大莫耳吸光係數的吸光性化合物可列舉例如2－(4－二乙胺基－2－羥苯甲醯)苯甲酸、2－(4－二丁胺基－2－羥苯甲醯)苯甲酸、2，2'，4，4'－四羥基二苯酮、2，3，3'，4，4'，5'－六羥基二苯酮、地衣酸、苯基螢光酮、玫紅酸、1，8，9－三羥基蒽、2－(4－羥苯基偶氮基)苯甲酸、甲基紅、4，4'－二胺基二苯酮、5，5'－亞甲基雙(2－羥基－4－甲氧基二苯酮)、3，4－二胺基二苯酮、姜黃素、及α－氰基－4－羥基肉桂酸等。Examples of the light-absorbing compound having a large molar absorption coefficient for light having a wavelength of 365 nm include, for example, 2-(4-diethylamino-2-hydroxybenzhydrazide)benzoic acid, 2-(4-dibutylamino-2- Benzoic acid, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,3',4,4',5'-hexahydroxybenzophenone, lichenic acid, phenyl Fluorone, rosaceic acid, 1,8,9-trihydroxyindole, 2-(4-hydroxyphenylazo)benzoic acid, methyl red, 4,4'-diaminobenzophenone, 5 5'-methylenebis(2-hydroxy-4-methoxybenzophenone), 3,4-diaminobenzophenone, curcumin, and α-cyano-4-hydroxycinnamic acid.
又，如前述之2－(4－二乙胺基－2－羥苯甲醯)苯甲酸和2，2'，4，4'－四羥基二苯酮般之具有羧基和酚性羥基之吸光性化合物時，此等化合物與具有環氧基之化合物的反應產物，即，經由羧基和酚性羥基之環氧環的開環反應產物，亦可使用作為本發明之形成下層防反射膜組成物中的吸光性化合物。此處，具有環氧基的化合物可列舉例如三(2，3－環氧丙基)異氰脲酸酯、1，4－丁二醇二縮水甘油醚、1，2－環氧－4－(環氧乙基)環己烷、甘油三縮水甘油醚、二乙二醇二縮水甘油醚、2，6－二縮水甘油苯基縮水甘油醚、1，1，3－三(對－(2，3－環氧丙氧基)苯基)丙烷、1，2－環己烷二羧酸二縮水甘油酯、4，4'－亞甲基雙(N，N－二縮水甘油苯胺)、3，4－環氧環己基甲基－3，4－環氧環己烷羧酸酯、三羥甲基乙烷三縮水甘油醚、雙酚－A二縮水甘油醚、及季戊四醇聚縮水甘油醚等之環氧化合物和甲基丙烯酸縮水甘油醚等之含有具有環氧基構造的聚合物。與具有環氧基之化合物的反應產物可列舉例如具有下述式(38)及(39)所示之單位構造的聚合物。Further, as described above, 2-(4-diethylamino-2-hydroxybenzhydrazide)benzoic acid and 2,2',4,4'-tetrahydroxybenzophenone have the absorption of a carboxyl group and a phenolic hydroxyl group. In the case of a compound, the reaction product of these compounds with a compound having an epoxy group, that is, a ring-opening reaction product via an epoxy ring of a carboxyl group and a phenolic hydroxyl group, may also be used as a composition for forming an underlying antireflection film of the present invention. A light absorbing compound in the middle. Here, examples of the compound having an epoxy group include, for example, tris(2,3-epoxypropyl)isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4- (Epoxyethyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidyl phenyl glycidyl ether, 1,1,3-tri(p-(2) , 3-glycidoxy)phenyl)propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3 , 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A diglycidyl ether, pentaerythritol polyglycidyl ether, etc. The epoxy compound, glycidyl methacrylate or the like contains a polymer having an epoxy group structure. The reaction product of the compound having an epoxy group may, for example, be a polymer having a unit structure represented by the following formulas (38) and (39).
吸收性化合物可單獨或組合使用二種以上。吸光性化合物之含量為相對於聚醯胺酸100質量份，例如為1~300質量份、或5~200質量份、或10~100質量份、或20~80質量份、或40~60質量份。吸收性化合物之含量大於前述值之情況，則下層防反射膜對於鹼性顯像液的溶解性低。又，下層防反射膜有時與光阻引起居間混合。The absorbent compounds may be used alone or in combination of two or more. The content of the light absorbing compound is, for example, 1 to 300 parts by mass, or 5 to 200 parts by mass, or 10 to 100 parts by mass, or 20 to 80 parts by mass, or 40 to 60% by mass based on 100 parts by mass of the polyaminic acid. Share. When the content of the absorbent compound is larger than the above value, the solubility of the lower antireflection film for the alkaline developing solution is low. Further, the lower anti-reflection film sometimes causes interstitial mixing with the photoresist.
經由改變吸光性化合物之種類和含量，則可調整下層防反射膜的衰減係數(k值)。By changing the kind and content of the light absorbing compound, the attenuation coefficient (k value) of the lower antireflection film can be adjusted.
本發明之形成下層防反射膜之組成物可經由均勻混合上述各成分而輕易調製，且以溶解於適當溶劑之溶液狀態供使用。此類溶劑可使用例如乙二醇單甲醚、乙二醇單***、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、二乙二醇單甲醚、二乙二醇單***、丙二醇、丙二醇、丙二醇單甲醇、丙二醇單甲醚乙酸酯、丙二醇丙醚乙酸酯、甲苯、二甲苯、甲基乙基酮、環戊酮、環己酮、2－羥基丙酸乙酯、2－羥基－2－甲基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2－羥基－3－甲基丁酸甲酯、3－甲氧基丙酸甲酯、3－甲氧基丙酸乙酯、3－乙氧基丙酸乙酯、3－乙氧基丙酸甲酯、丙酮酸甲酯、丙酮酸乙酯、乙酸乙酯、乙酸丁酯、乳酸乙酯、乳酸丁酯、N，N－二甲基甲醯胺、N，N－二甲基乙醯胺、及N－甲基吡咯烷酮等。此些溶劑可單獨或組合使用二種以上。更且，可混合使用丙二醇單丁醚、丙二醇單丁醚乙酸酯等之高沸點溶劑。The composition for forming the underlying antireflection film of the present invention can be easily prepared by uniformly mixing the above components, and can be used in a solution state dissolved in a suitable solvent. As such a solvent, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol single can be used. Ether, propylene glycol, propylene glycol, propylene glycol monomethanol, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-hydroxypropionic acid Ester, ethyl 2-hydroxy-2-methylpropanoate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, lactate B Ester, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more. Further, a high boiling point solvent such as propylene glycol monobutyl ether or propylene glycol monobutyl ether acetate may be used in combination.
如此所調製之下層防反射膜樹脂組成物溶劑為使用孔徑為0.2μm左右之濾紙等予以過濾後，供使用為佳。如此所調製之下層防反射膜樹脂組成物溶液為於室溫下可長期安定貯藏。The resin composition of the lower antireflection film resin composition thus prepared is preferably filtered using a filter paper having a pore diameter of about 0.2 μm or the like. The thus prepared anti-reflection film resin composition solution can be stably stored for a long period of time at room temperature.
於本發明之形成下層防反射膜組成物中，另外可含有萘醌二疊氮基磺酸環氧化合物等之感光性化合物、萘羧酸化合物等之芳香族羧酸化合物、及界面活性劑等。The lower anti-reflection film composition of the present invention may further contain a photosensitive compound such as a naphthoquinonediazidesulfonic acid epoxy compound, an aromatic carboxylic acid compound such as a naphthalenecarboxylic acid compound, or a surfactant. .
感光性化合物以萘醌二疊氮基磺酸化合物為佳。The photosensitive compound is preferably a naphthoquinonediazidesulfonic acid compound.
使用作為感光性化合物的萘醌二疊氮基磺酸化合物為由1，2－萘醌－2－二疊氮基－5－磺酸及1，2－萘醌－2－二疊氮基－4－磺酸等之磺酸化合物與具有羥基之化合物所得之磺酸酯化合物為佳。又，由1，2－萘醌－2－二疊氮基－5－磺酸及1，2－萘醌－2－二疊氮基－4－磺酸等之磺酸化合物與具有胺基之化合物所得之磺酸醯胺化合物為佳。又，由前述磺酸化合物、與具有羥基及胺基之化合物所得的磺酸酯－醯胺化合物為佳。The naphthoquinonediazidesulfonic acid compound used as the photosensitive compound is 1,2-naphthoquinone-2-diazide-5-sulfonic acid and 1,2-naphthoquinone-2-diazide- A sulfonic acid compound such as 4-sulfonic acid or the like and a sulfonic acid ester compound obtained from a compound having a hydroxyl group are preferred. Further, a sulfonic acid compound such as 1,2-naphthoquinone-2-diazide-5-sulfonic acid and 1,2-naphthoquinone-2-diazide-4-sulfonic acid has an amine group The sulfonate guanamine compound obtained by the compound is preferred. Further, a sulfonic acid ester-guanamine compound obtained from the above sulfonic acid compound and a compound having a hydroxyl group and an amine group is preferred.
前述具有羥基之化合物可列舉例如苯酚、2－甲酚、3－甲酚、4－甲酚、氫醌、間苯二醇、兒荼酚、4，4－異亞丙基二酚、1，1－雙(4－羥苯基)環己烷、4，4'－二羥苯基碸、4，4－六氟異亞丙基二酚、4，4'，4"－三羥基三苯基甲烷、1，1，1－三(4－羥苯基)乙烷、4，4'－[1－[4－[1－(4－羥苯基)－1－甲基乙基]苯基]亞乙基]雙酚、2，4－羥基二苯酮、2，3，4－三羥基二苯酮、2，2'，4，4'－四羥基二苯酮、2，3，4，4'－四羥基二苯酮、2，3，4，2'，4'－五羥基二苯酮、及2，5－雙(2－羥基－5－甲基苄基甲基等之酚化合物、乙醇、2－丙醇、4－丁醇、環己醇、乙二醇、丙二醇、二乙二醇、二丙二醇、2－甲氧基乙醇、2－丁氧基丁醇、2－甲氧基丙醇、2－丁氧基丙醇、乳酸乙酯、及乳酸丁酯等之脂肪族醇化合物。Examples of the compound having a hydroxyl group include phenol, 2-cresol, 3-cresol, 4-cresol, hydroquinone, m-phenylene glycol, catechol, 4,4-isopropylidenediol, and 1, 1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxyphenylhydrazine, 4,4-hexafluoroisopropylidenediol, 4,4',4"-trihydroxytriphenyl Methane, 1,1,1-tris(4-hydroxyphenyl)ethane, 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]benzene Ethylene]bisphenol, 2,4-hydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3, 4,4'-tetrahydroxybenzophenone, 2,3,4,2',4'-pentahydroxybenzophenone, and 2,5-bis(2-hydroxy-5-methylbenzylmethyl, etc. Phenolic compound, ethanol, 2-propanol, 4-butanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxybutanol, 2- An aliphatic alcohol compound such as methoxypropanol, 2-butoxypropanol, ethyl lactate, and butyl lactate.
前述具有胺基之化合物可列舉苯胺、鄰－甲苯胺、間－甲苯胺、對－甲苯胺、4－胺基二苯基甲烷、4－胺基聯苯、鄰－苯二胺、間－苯二胺、對－苯二胺、4，4'－二胺基聯苯甲烷、及4，4'－二胺基聯苯醚等之苯胺化合物、環己胺、正辛胺、及環戊胺等之脂肪族胺化合物。Examples of the compound having an amine group include aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminobiphenyl, o-phenylenediamine, m-benzene. An aniline compound such as diamine, p-phenylenediamine, 4,4'-diaminobiphenylmethane, and 4,4'-diaminodiphenyl ether, cyclohexylamine, n-octylamine, and cyclopentylamine An aliphatic amine compound.
更且，具有羥基及胺基之化合物可列舉例如鄰－胺基苯酚、間－胺基苯酚、對－胺基苯酚、4－胺基間苯二酚、2，3－二胺基苯酚、2，3－二胺基苯酚、4，4'－二胺基－4"－羥基三苯基甲烷、4－胺基－4'，4"－二羥基三苯基甲烷、雙(4－胺基－3－羧基－5－羥苯基)醚。雙(4－胺基－3－羧基－5－羥苯基)甲烷、雙(4－胺基－3－羧基－5－羥苯基)碸、2，2－雙(4－胺基－3－羧基－5－羥苯基)丙烷、及2，2－雙(4－胺基－3－羧基－5－羥苯基)六氟丙烷等之胺基苯酚化合物、2－胺基乙醇、3－胺基丙醇、及4－胺基環己醇等之烷醇胺化合物。Further, examples of the compound having a hydroxyl group and an amine group include o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcin, 2,3-diaminophenol, and 2 , 3-diaminophenol, 4,4'-diamino-4"-hydroxytriphenylmethane, 4-amino-4',4"-dihydroxytriphenylmethane, bis(4-amino group -3-carboxy-5-hydroxyphenyl)ether. Bis(4-amino-3-carboxy-5-hydroxyphenyl)methane, bis(4-amino-3-carboxy-5-hydroxyphenyl)anthracene, 2,2-bis(4-amino-3) -Carboxy-5-hydroxyphenyl)propane, and an aminophenol compound such as 2,2-bis(4-amino-3-carboxy-5-hydroxyphenyl)hexafluoropropane, 2-aminoethanol, 3 An alkanolamine compound such as aminopropanol or 4-aminocyclohexanol.
使用感光性化合物時，其添加量為相對於聚醯胺酸100質量份，例如為1~100質量份、或3~80質量份、或例如5~50質量份、或10~40質量份。感光性化合物為超過100質量份時，下層防反射膜對於鹼性顯像液的溶解性低，又，有時引起下層防反射膜與光阻的居間混合。When the photosensitive compound is used, the amount thereof is, for example, 1 to 100 parts by mass, or 3 to 80 parts by mass, or for example 5 to 50 parts by mass, or 10 to 40 parts by mass, per 100 parts by mass of the polyamic acid. When the photosensitive compound is more than 100 parts by mass, the lower antireflection film has low solubility in an alkaline developing solution, and may cause intervening mixing between the lower antireflection film and the photoresist.
於本發明之形成下層防反射膜組成物中，於調節對於鹼性顯像液之溶解速度的目的下，可添加芳香族羧酸化合物、脂肪族羧酸化合物及具有酚性羥基之化合物等。In the composition for forming the lower antireflection film of the present invention, an aromatic carboxylic acid compound, an aliphatic carboxylic acid compound, a compound having a phenolic hydroxyl group, or the like may be added for the purpose of adjusting the dissolution rate of the alkaline developing solution.
此類化合物可列舉例如三羥苯基乙烷、雙酚－S、雙酚－A、4，4'－異亞丙基－二－鄰－甲酚、5－第三丁基焦棓酚、六氟雙酚－A、3，3，3'，3'－四甲基－1，1'－螺雙茚滿－5，5'，6，6'－呋喃、4，4'－(9－亞芴基)二苯酚、雙酚－AP、雙酚－P、5－α，α－二甲基－4－羥苄基水楊酸、α，α，α－三(4－羥苯基)－1－乙基－4－異丙基、及5，5'－二－第三丁基－2，2'，4，4'－四羥基二苯酮等之酚化合物、均苯四甲酸、3，7－二羥基－2－萘酸、苯二甲酸、偏苯三酸、4－磺基苯二甲酸、苯六羧酸、2，3－萘二羧酸、4－羥基苯二甲酸、3，4－二羥苯二甲酸、4，5－二羥基苯二甲酸、3，3'，4，4'－聯苯四羧酸、3，3'，4，4'－二苯酮四羧酸、3，3'，4，4'－二苯醚四羧酸、3，3'，4，4'－聯苯碸四羧酸、1，2，3，4－環丁烷四羧酸、1，2－二甲基－1，2，3，4－環丁烷四羧酸、1，2，3，4－四甲基－1，2，3，4－環丁烷四羧酸、1，2，3，4－環戊烷四羧酸、1，2，3，4－環己烷四羧酸、3，4－二羧基－1，2，3，4－四氫－1－萘琥珀酸等之羧酸化合物、聚丙烯酸、聚甲基丙烯酸、聚醯胺酸、苯酚酚醛清漆、聚羥基苯乙烯、及萘酚酚醛清漆等之具有羧基或酚性羥基之聚合物化合物。以具有萘環及羧基之萘羧酸化合物為佳。使用此些化合物時，其添加量為相對於聚醯胺酸100質量份，例如為1~100質量份、或3~80質量份、或，例如為5~40質量份、或10~20質量份。Examples of such a compound include trishydroxyphenylethane, bisphenol-S, bisphenol-A, 4,4'-isopropylidene-di-o-cresol, 5-tert-butyl pyrogallol, Hexafluorobisphenol-A, 3,3,3',3'-tetramethyl-1,1'-spirobiindane-5,5',6,6'-furan, 4,4'-(9 -indolyl)diphenol, bisphenol-AP, bisphenol-P, 5-α, α-dimethyl-4-hydroxybenzyl salicylic acid, α,α,α-tris(4-hydroxyphenyl) a phenolic compound such as 1-ethyl-4-isopropyl and 5,5'-di-t-butyl-2,2',4,4'-tetrahydroxybenzophenone, and pyromellitic acid , 3,7-dihydroxy-2-naphthoic acid, phthalic acid, trimellitic acid, 4-sulfophthalic acid, benzene hexacarboxylic acid, 2,3-naphthalene dicarboxylic acid, 4-hydroxy phthalic acid , 3,4-dihydroxyphthalic acid, 4,5-dihydroxyphthalic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 3,3',4,4'-benzophenone Tetracarboxylic acid, 3,3',4,4'-diphenyl ether tetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 1,2,3,4-cyclobutane IV Carboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1, 2,3,4-Tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,3,4-cyclohexane a carboxylic acid compound such as alkanetetracarboxylic acid or 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid, polyacrylic acid, polymethacrylic acid, polyamic acid, phenol novolac A polymer compound having a carboxyl group or a phenolic hydroxyl group such as polyhydroxystyrene or a naphthol novolak. A naphthalene carboxylic acid compound having a naphthalene ring and a carboxyl group is preferred. When these compounds are used, the amount thereof is, for example, 1 to 100 parts by mass, or 3 to 80 parts by mass, or, for example, 5 to 40 parts by mass, or 10 to 20 parts by mass, based on 100 parts by mass of the polyamic acid. Share.
本發明之形成下層防反射膜組成物可含有界面活性劑。界面活性劑可列舉例如聚氧乙烯月桂醚、聚氧乙烯硬脂醚、聚氧乙烯鯨蠟醚、聚氧乙烯油醚等之聚氧乙烯烷醚類、聚氧乙烯辛基苯酚醚、聚氧乙烯壬基苯酚醚等之聚氧乙烯烷基芳基醚類、聚氧乙烯聚氧丙烯分段共聚物類、山梨糖醇酐單月桂酸酯、山梨糖醇酐單棕櫚酸酯、山梨糖醇酐單硬脂酸酯、山梨糖醇酐單油酸酯、山梨糖醇酐三油酸酯、山梨糖醇酐三硬脂酸酯等之山梨糖醇酐脂肪酸酯類、聚氧乙烯山梨糖醇酐單月桂酸酯、聚氧乙烯山梨糖醇酐單棕櫚酸酯、聚氧乙烯山梨糖醇酐單硬脂酸酯、聚氧乙烯山梨糖醇酐三油酸酯、聚氧乙烯山梨糖醇酐三硬脂酸酯等之聚氧乙烯山梨糖醇酐脂肪酸類等之非離子系界面活性劑、Efutop EF 301、EF303、EF352((股)Tochem Products製)、Megafac F171、F173(大日本油墨化學工業(股)製)、Fluroride FC430、FC431(住友3M(股)製)、Asahi Guard AG710、Surfuron S－382、SC101、SC102、SC103、SC104、SC105、SC106(旭硝子(股)製)等之氟系界面活性劑、有機基矽氧烷聚合物KP341(信越化學工業(股)製)等。此些界面活性劑的配合量於本發明之形成下層防反射膜組成物之全成分中，通常為0.2質量%以下，較佳為0.1質量%以下。此些界面活性劑可單獨添加，或添加二種以上之組合亦可。The underlying antireflection film composition of the present invention may contain a surfactant. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and polyoxygen. Polyoxyethylene alkyl aryl ethers such as vinyl nonyl phenol ether, polyoxyethylene polyoxypropylene segmented copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitol Sorbitan fatty acid esters such as anhydride monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitol Anhydride monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan Nonionic surfactant such as polyoxyethylene sorbitan fatty acid such as tristearate, Efutop EF 301, EF303, EF352 (manufactured by Tochem Products), Megafac F171, F173 (Daily Ink Chemistry) Industrial (share) system, Fluroride FC430, FC431 (Sumitomo 3M (share) system), Asahi Guard AG710, S A fluorine-based surfactant such as urfuron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) or an organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The blending amount of the surfactant is usually 0.2% by mass or less, preferably 0.1% by mass or less, based on the total composition of the underlying antireflection film composition of the present invention. These surfactants may be added singly or in combination of two or more.
本發明之形成下層防反射膜組成物為視需要亦可含有其他之液流調整劑、黏著輔助劑等。The composition for forming the lower anti-reflection film of the present invention may contain other liquid flow adjusting agents, adhesion aids, and the like as needed.
以下，說明關於本發明之形成防反射膜組成物的使用。Hereinafter, the use of the antireflection film composition of the present invention will be described.
於半導體基板(例如，矽/二氧化矽覆被基板、矽化氮基板、矽晶圓、玻璃基板、ITO基板等)上，以自旋器、塗覆器等之適當的塗佈方法塗佈本發明之形成下層防反射膜組成物，其後，經由煅燒形成下層防反射膜。煅燒條件為由煅燒溫度80℃~300℃、煅燒時間0.3~60分鐘中適當選擇。較佳為150℃~250℃、0.5~2分鐘。Applying to a semiconductor substrate (for example, a ruthenium/yttrium oxide-coated substrate, a bismuth nitride substrate, a ruthenium wafer, a glass substrate, an ITO substrate, or the like) by a suitable coating method such as a spinner or an applicator In the invention, a lower anti-reflection film composition is formed, and thereafter, a lower anti-reflection film is formed by calcination. The calcination conditions are appropriately selected from the calcination temperature of 80 ° C to 300 ° C and the calcination time of 0.3 to 60 minutes. It is preferably 150 ° C ~ 250 ° C, 0.5 ~ 2 minutes.
所形成之下層防反射膜對於光阻顯像所使用之鹼性顯像液的溶解速度為每秒鐘0.1nm~50nm、較佳為每秒鐘0.2nm~40nm、更佳為0.3~20nm、溶解速度為較小之情形中，除去下層防反射膜所必須的時間變長，造成生產性降低。溶解速度為較大之情形中，光阻未曝光部下層的下層防反射膜亦溶解，其結果，有時無法形成光阻圖型。The dissolution rate of the underlying antireflection film formed for the alkaline developing solution used for photoresist development is 0.1 nm to 50 nm per second, preferably 0.2 nm to 40 nm per second, more preferably 0.3 to 20 nm per second. In the case where the dissolution rate is small, the time required to remove the lower anti-reflection film becomes long, resulting in a decrease in productivity. When the dissolution rate is large, the lower anti-reflection film of the lower layer of the photoresist unexposed portion is also dissolved, and as a result, the photoresist pattern may not be formed.
由本發明之形成下層防反射膜組成物所形成的下層防反射膜為經由改變形成時的煅燒條件，則可控制下層防反射膜對於鹼性顯像液的溶解速度。一定的般燒時間，於煅燒溫度愈高，則可形成對於鹼性顯像液之溶解速度愈小的下層防反射膜。The lower anti-reflection film formed by forming the lower anti-reflection film composition of the present invention can control the dissolution rate of the lower anti-reflection film for the alkaline developing solution by changing the firing conditions at the time of formation. A certain general burning time, the higher the calcination temperature, the lower the anti-reflection film which has a lower dissolution rate for the alkaline developing solution.
其次於下層防反射膜上，形成光阻層。光阻層的形成可根據一般方法，即，將光阻溶液於下層防反射膜上塗佈及煅燒則可進行。Next, a photoresist layer is formed on the lower anti-reflection film. The formation of the photoresist layer can be carried out according to a general method, that is, coating and calcining the photoresist solution on the underlying antireflection film.
於本發明之下層防反射膜上塗佈，形成的光阻，若為對於曝光所使用之光感光則無特別限定，可使用負型及正型光阻的任一種。有由酚醛清漆樹脂與1，2－萘醌二疊氮基磺酸所構成的正型光阻，具有經由酸分解令鹼溶解速度上升之基的黏合劑與光產酸劑所構成的增強化學性型光阻，經由酸分解令光阻的鹼溶解速度上升之低分子化合物與鹼可溶性黏合劑與光產酸劑所構成的增強化學性型光阻，具有經由酸分解令鹼溶解速度上升之基的黏合劑與經由酸分解令光阻的鹼溶解速度上升之低分子化合物與光產酸劑所構成的增強化學性型光阻等。可列舉例如住友化學工業(股)製商品名PFi－58、PFi－88、東京應化工業(股)製商品名iP5200、iP5700、TDMR－AR80、及SHIPLEY公司製商品名S－1808等。The photoresist formed by coating on the underlying antireflection film of the present invention is not particularly limited as long as it is photosensitive for exposure, and any of a negative type and a positive type resist can be used. There is a positive photoresist composed of a novolac resin and 1,2-naphthoquinonediazidesulfonic acid, and an enhanced chemical composed of a binder and a photoacid generator having a base for increasing the alkali dissolution rate by acid decomposition. Sexual photoresist, a chemically resistant photoresist composed of a low molecular compound which accelerates the alkali dissolution rate of the photoresist by acid decomposition, an alkali-soluble binder and a photoacid generator, and has an alkali dissolution rate by acid decomposition. The base-based binder is a chemically-resistant photoresist composed of a low-molecular compound and a photoacid generator in which the alkali dissolution rate of the photoresist is increased by acid decomposition. For example, the product names PFi-58 and PFi-88 manufactured by Sumitomo Chemical Co., Ltd., the trade name iP5200, iP5700, TDMR-AR80 manufactured by Tokyo Chemical Industry Co., Ltd., and the trade name S-1808 manufactured by SHIPLEY Co., Ltd., and the like can be cited.
其次，透過指定的光罩進行曝光。曝光可使用i射線(波長365nm)及g射線(波長432nm)等。曝光後，視需要亦可進行曝光後加熱(PEB：Post Exposure Bake)。Second, exposure is performed through a designated mask. For the exposure, i-ray (wavelength 365 nm), g-ray (wavelength 432 nm), or the like can be used. After the exposure, post-exposure heating (PEB: Post Exposure Bake) may be performed as needed.
其次，以鹼性顯像液進行顯像。藉此，例如使用正型光阻的情況，經曝光部分的光阻及其下層部分之下層防反射膜可經由顯像而被除去。Next, imaging was performed with an alkaline developing solution. Thereby, for example, in the case of using a positive type resist, the photoresist of the exposed portion and the underlying anti-reflection film of the lower portion thereof can be removed by development.
光阻顯像所使用的鹼性顯像液其例可列舉氫化鉀、氫氧化鈉等之鹼金屬氫氧化物的水溶液、氫化四甲銨、氫氧化四乙銨、膽鹼等之氫氧化四級銨的水溶液、及乙醇胺、丙胺、乙二胺等之胺水溶液等之鹼性水溶液。更且，於此些顯像液中亦可加入界面活性劑等。顯像條件為由溫度5℃~50℃、時間10~300秒中適當選擇。Examples of the alkaline developing solution used for the resistive development include an aqueous solution of an alkali metal hydroxide such as potassium hydride or sodium hydroxide, and an aluminum hydroxide such as tetramethylammonium hydrogenhydride, tetraethylammonium hydroxide or choline. An aqueous solution of ammonium chloride and an aqueous alkaline solution such as an aqueous amine solution such as ethanolamine, propylamine or ethylenediamine. Further, a surfactant or the like may be added to these developing solutions. The development conditions are appropriately selected from a temperature of 5 ° C to 50 ° C and a time of 10 to 300 seconds.
由本發明之形成下層防反射膜組成物所形成的下層防反射膜可使用常用作為鹼性顯像液之2.38質量%的氫氧化四甲銨水溶液於室溫下輕易地進行顯像。The lower anti-reflection film formed of the composition for forming the lower anti-reflection film of the present invention can be easily developed at room temperature using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide which is usually used as an alkaline developing solution.
本發明之下層防反射膜可使用作為防止半導體基板與光阻相互作用之層、具有防止光阻所用之材料或對光阻曝光時所生成之物質對於基板不良作用之機能之層、具有防止加熱煅燒時由基板生成之物質對於上層光阻擴散之機能之層、及、減少半導體基板介電體層所造成之光阻層之效果的阻擋層。The underlying anti-reflection film of the present invention can be used as a layer which prevents the semiconductor substrate from interacting with the photoresist, has a function of preventing the photoresist from being used, or a substance which is formed when the photoresist is exposed to the substrate, and has a function of preventing the heating. A layer formed by the substrate during calcination as a barrier layer for the function of the upper photoresist diffusion and a barrier layer for reducing the effect of the photoresist layer caused by the semiconductor substrate dielectric layer.
以下，根據實施例進一步具體說明本發明，但本發明並不被其所限定。Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.
令4，4'－(六氟異亞丙基)雙苯二甲酸二酐17.8克、3，5－二胺基苯甲酸3.12克、雙(4－胺苯基)碸4.92克於丙二醇單甲醇145.6克中，以80℃反應20小時，則取得含聚醯胺酸的溶液[A]。所得之聚醯胺酸為具有式(40)及式(41)所示之構造。Let 4,4'-(hexafluoroisopropylidene)bisphthalic dianhydride 17.8 g, 3,5-diaminobenzoic acid 3.12 g, bis(4-aminophenyl)phosphonium 4.92 g in propylene glycol monomethanol In 145.6 g, the reaction was carried out at 80 ° C for 20 hours to obtain a solution containing poly-proline (A). The obtained polyaminic acid has a structure represented by the formula (40) and the formula (41).
吸光性化合物的莫耳吸光係數為根據下列方法測定。The molar absorption coefficient of the light absorbing compound was measured according to the following method.
將吸光性化合物使用N，N－二甲基甲醯胺作成4×10－ 6 (g/ml)之溶液。此溶液使用島津製作所製、UV測定裝置UV2550測定吸光度。以[莫耳吸光係數]＝[吸光度]/[溶液之重量濃度/吸光性化合物之分子量]算出莫耳吸光係數。The light absorbing compound was made into a solution of 4 × 10 - 6 (g/ml) using N,N-dimethylformamide. The solution was measured for absorbance using a UV measuring device UV2550 manufactured by Shimadzu Corporation. The molar absorption coefficient was calculated by [mole absorption coefficient] = [absorbance] / [weight concentration of the solution / molecular weight of the light absorbing compound].
2－(4－二乙胺基－2－羥苯甲醯)苯甲酸之莫耳吸光係數為20563(l/mol．cm)、α－氰基－4－羥基肉桂酸之莫耳吸光係數為19827(l/mol．cm)。The molar absorption coefficient of 2-(4-diethylamino-2-hydroxybenzhydrazide) benzoic acid is 20563 (l/mol.cm), and the molar absorption coefficient of α-cyano-4-hydroxycinnamic acid is 19827 (l/mol.cm).
於前述溶液[A]14.0克中添加2－[4－二乙胺基－2－羥苯甲醯)苯甲酸1.04、α－氰基－4－羥基肉桂酸0.35克、4，4'－亞甲基雙(N，N－二縮水甘油苯胺)2.77克、3，7－二羥基萘酸0.16克、丙二醇單甲醚37.7克、及丙二醇單甲醚乙酸酯51.6克並於室溫攪拌30分鐘，調製形成下層防反射膜組成物之溶液[1]。To the above solution [A] 14.0 g was added 2-[4-diethylamino-2-hydroxybenzhydrazide)benzoic acid 1.04, α-cyano-4-hydroxycinnamic acid 0.35 g, 4,4'-Asia 2.77 g of methyl bis(N,N-diglycidylaniline), 0.16 g of 3,7-dihydroxynaphthalic acid, 37.7 g of propylene glycol monomethyl ether, and 51.6 g of propylene glycol monomethyl ether acetate and stirred at room temperature 30 In minutes, a solution [1] of the composition of the lower antireflection film is prepared.
將前述溶液[1]於矽晶圓上使用自旋器塗佈後，於熱板上，以170℃，煅燒60秒鐘形成膜厚70nm的下層防反射膜。所得之下層防反射膜為於乳酸乙酯及丙二醇單甲醚乙酸酯中不溶。此下層防反射膜以橢圓計測定結果，於波長365nm下之折射率(n值)為1.74、衰減係數(k值)為0.22。The solution [1] was coated on a tantalum wafer using a spinner, and then fired at 170 ° C for 60 seconds on a hot plate to form a lower antireflection film having a thickness of 70 nm. The resulting underlying antireflection film was insoluble in ethyl lactate and propylene glycol monomethyl ether acetate. The lower anti-reflection film was measured by an ellipsometer, and had a refractive index (n value) of 1.74 at a wavelength of 365 nm and an attenuation coefficient (k value) of 0.22.
又，令煅燒溫度為175℃同樣形成下層防反射膜。其後，確認此下層防反射膜為於乳酸乙酯及丙二醇單甲醚乙酸酯中不溶。Further, the lower anti-reflection film was formed in the same manner at a calcination temperature of 175 °C. Thereafter, it was confirmed that the lower anti-reflection film was insoluble in ethyl lactate and propylene glycol monomethyl ether acetate.
其次，使用光阻顯像分析儀(Rithotech Japan(股)製測定下層防反射膜對於光阻顯像中所使用之鹼性顯像液(東京應化工業(股)製、商品名NMD－3)的溶解速度。以煅燒溫度170℃、煅燒時間60秒所形成之下層防反射膜的溶解速度為每秒4.1nm。又，以煅燒溫度175℃、煅燒時間60秒所形成之下層防反射膜的溶解速度為每秒3.3nm。Next, a photo-sensitive image analyzer (Rithotech Japan Co., Ltd.) was used to measure the underlying antireflection film for alkaline development liquid used in photoresist development (manufactured by Tokyo Ohka Kogyo Co., Ltd., trade name NMD-3). The dissolution rate of the lower anti-reflection film formed at a calcination temperature of 170 ° C and a calcination time of 60 seconds is 4.1 nm per second. Further, the lower anti-reflection film is formed at a calcination temperature of 175 ° C and a calcination time of 60 seconds. The dissolution rate is 3.3 nm per second.
將前述溶液[1]於矽晶圓上使用自旋器塗佈後，於熱板上，以175℃、煅燒60秒鐘形成膜厚70nm的下層防反射膜。於所得之下層防反射膜上形成之i射線用正型光阻膜。其次，透過設定形成600nm之線/空間圖案的光罩，以i射線(波長365nm)曝光。其次，以110℃曝光90秒鐘後進行加熱後，使用2.38%氫氧化四甲銨水溶液(東京應化工業(股)製、商品名NMD－3)作為鹼性顯像液進行60秒鐘槳葉顯像。光阻與下層防反射膜均為曝光部溶解。於600nm之線/空間亦未察見下層防反射膜的殘膜。The solution [1] was applied onto a tantalum wafer using a spinner, and then a lower layer antireflection film having a thickness of 70 nm was formed on a hot plate at 175 ° C for 60 seconds. A positive-type resist film for i-rays formed on the lower anti-reflection film obtained. Next, the mask was formed by i-ray (wavelength 365 nm) by setting a mask which forms a line/space pattern of 600 nm. Next, after heating at 110 ° C for 90 seconds and heating, a 2.38% aqueous solution of tetramethylammonium hydroxide (manufactured by Tokyo Ohka Kogyo Co., Ltd., trade name NMD-3) was used as an alkaline developing solution for 60 seconds. Leaf image. Both the photoresist and the lower anti-reflection film are dissolved in the exposed portion. The residual film of the lower anti-reflection film was not observed in the line/space of 600 nm.
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