TW202229476A - 光可固化組成物 - Google Patents
光可固化組成物 Download PDFInfo
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- TW202229476A TW202229476A TW110141366A TW110141366A TW202229476A TW 202229476 A TW202229476 A TW 202229476A TW 110141366 A TW110141366 A TW 110141366A TW 110141366 A TW110141366 A TW 110141366A TW 202229476 A TW202229476 A TW 202229476A
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- 239000000203 mixture Substances 0.000 title claims abstract description 88
- 239000000178 monomer Substances 0.000 claims abstract description 74
- 239000000463 material Substances 0.000 claims abstract description 49
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 238000006467 substitution reaction Methods 0.000 claims abstract description 10
- 238000011282 treatment Methods 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 61
- 238000000034 method Methods 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 26
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 abstract 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 52
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- SOEDHYUFNWMILE-UHFFFAOYSA-N naphthalen-1-yl prop-2-enoate Chemical compound C1=CC=C2C(OC(=O)C=C)=CC=CC2=C1 SOEDHYUFNWMILE-UHFFFAOYSA-N 0.000 description 5
- BXSPZNVFEYWSLZ-UHFFFAOYSA-N (3-phenoxyphenyl)methyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 BXSPZNVFEYWSLZ-UHFFFAOYSA-N 0.000 description 4
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- 230000003044 adaptive effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 235000010292 orthophenyl phenol Nutrition 0.000 description 2
- 239000004306 orthophenyl phenol Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- AZVUVXPHGDLPCW-UHFFFAOYSA-N 1-adamantyl 2-methylprop-2-enoate 3-(1-adamantyl)-2-methylprop-2-enoic acid Chemical compound C12(CC3CC(CC(C1)C3)C2)C=C(C(=O)O)C.C(C(=C)C)(=O)OC23CC1CC(CC(C2)C1)C3 AZVUVXPHGDLPCW-UHFFFAOYSA-N 0.000 description 1
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
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- B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
- B05D3/065—After-treatment
- B05D3/067—Curing or cross-linking the coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- C08F2/00—Processes of polymerisation
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- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
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- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
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Abstract
光可固化組成物可包含可聚合材料及光引發劑,其中,可聚合材料可包含10-40 wt%之式(1)之單官能單體,其中R1為H或C
1-C
6烷基,以及R2及R3為C
1-C
10烷基或烷基-芳基中之一或多個取代,以及R4、R5為H或C
1-C
10烷基,
Description
本揭露係關於光可固化組成物,特別是關於適於形成在後續烘烤處理期間具有低收縮率之光固化層的用於噴墨適應性平坦化(inkjet adaptive planarization)之光可固化組成物。
噴墨適應性平坦化(Inkjet Adaptive Planarization)(IAP)為藉由將光可固化組成物之液滴噴射於基板之表面上、以及使平坦覆板(flat superstrate)與所加之液體直接接觸以形成平坦液體層而使基板(例如,含有電路之晶圓)的表面平坦化(planarize)之方法。平坦液體層(flat liquid layer)通常於UV光曝露下固化,以及移除覆板之後獲得平坦聚合表面(planar polymeric surface),其可接受後續處理步驟,例如烘烤(baking)、蝕刻(etching)、及/或其他沉積步驟。
所形成之光固化層的後續烘烤經常在高於其玻璃轉移溫度(glass transition temperature)之溫度進行。烘烤通常導致形成聚合層(polymeric layer)之更緻密堆疊(denser packing),其造成不想要的層收縮(shrinking)以及會進一步挑戰平坦化效率。通常,烘烤期間之熱收縮大於光可固化組成物之光固化期間的收縮。
需要能獲致在後續處理期間具有低收縮率(shrinkage)之平坦光固化層的經改良IAP材料。
於一實施態樣中,光可固化組成物可包含光引發劑(photoinitiator)及可聚合材料(polymerizable material),其中,可聚合材料可包含具有式(1)之結構的單官能丙烯酸酯單體(mono-functional acrylate monomer),其中R1為H或C
1-C
6烷基,以及R2及R3為C
1-C
10烷基或烷基-芳基中之一或多個取代,以及R4、R5為H或C
1-C
10烷基,
;
式(1)之丙烯酸酯單體的量,以可聚合材料之總重為基準計,可為至少10 wt%且不大於30 wt%;而光可固化組成物之光固化層(photo-cured layer)的碳含量(carbon content)可為至少74%。
於一態樣中,可聚合材料可進一步包含至少一種多官能丙烯酸酯單體(multi-functional acrylate monomer)。於一具體態樣中,至少一種多官能丙烯酸酯單體可包含雙官能丙烯酸酯單體(bi-functional acrylate monomer)、三官能丙烯酸酯單體(tri-functional acrylate monomer)、四官能丙烯酸酯單體(tetra-functional acrylate monomer)、或其任何組合。於某一具體態樣中,至少一種多官能丙烯酸酯單體可包含雙酚A二甲基丙烯酸酯(bisphenol A dimethacrylate)(BPADMA)。
於光可固化組成物之另某一態樣中,以可聚合材料之總重為基準計,多官能丙烯酸酯單體之量可為至少10 wt%且不大於30 wt%。
於一態樣中,以可聚合材料之總重為基準計,式(2)之單官能丙烯酸酯單體的量可不大於25 wt%。
於另一態樣中,以可聚合材料之總重為基準計,式(2)之單官能丙烯酸酯單體的量可不大於15 wt%。
於另一實施態樣中,光可固化組成物係可使得組成物之光固化層具有不大於7.5 %之熱收縮率(thermal shrinkage),熱收縮率為接受250℃、2分鐘之烘烤處理(baking treatment)之前及之後的光固化層之厚度的差。
於另一態樣中,光可固化組成物之黏度(viscosity)可不大於15 mPa·s。
於又另一態樣中,光可固化組成物係可使得組成物之光固化層具有不大於2.9之Ohnishi數(Ohnishi number)。
於一實施態樣中,積層物(laminate)可包含基板及在該基板上之光固化層,其中,光固化層係由上述光可固化組成物(photocurable composition)形成。
於積層物之一態樣中,光固化層可具有不大於7 %之熱收縮率,熱收縮率為接受250℃、2分鐘之烘烤處理之前及之後的光固化層之厚度的差。
於積層物之另一態樣中,光固化層可具有不大於2.9之Ohnishi數。
於另一實施態樣中,於基板上形成光固化層之方法可包含:於基板上施加光可固化組成物之層,其中,光可固化組成物可包含光引發劑及可聚合材料。可聚合材料可包含10 wt%至30 wt%之具有式(1)之結構的單官能丙烯酸酯單體,其中R1為H或C
1-C
6烷基;R2及R3為C
1-C
10烷基或烷基-芳基中之一或多個取代;以及R4、R5為H或C
1-C
10烷基,
;
使光可固化組成物與覆板(superstrate)接觸;以光照射光可固化組成物以形成光固化層;以及從光固化層移除該覆板。
於方法之一態樣中,光固化層可具有不大於7.5 %之熱收縮率,熱收縮率為接受250℃、2分鐘之烘烤處理之前及之後的光固化層之厚度的差。
於方法之另一態樣中,光可固化組成物之黏度可不大於15 mPa·s。
於方法之某一態樣中,光可固化組成物可進一步包含以可聚合組成物之總重為基準計為10 wt%至30 wt%之量的雙酚A二甲基丙烯酸酯(BPADMA)。
提供以下說明以助理解本文所揭露之教示,以及將著重於該等教示之具體實施及實施態樣。此著重係供協助描述該等教示且不應闡釋為對於該等教示之範圍或應用性的限制。
除非另外界定,否則本文所使用之所有技術及科學術語具有如同本發明所屬領域中具有通常知識者一般暸解之意義。材料、方法及實例僅為舉例說明,且不希望其具有限制性。本文未描述之處,關於具體材料及處理動作的許多細節為慣用的,且可見於教科書及壓印(imprint)和微影(lithography)領域內之其他來源。
如本文所使用之術語「包含(comprises/ comprising)」、「包括(includes/including)」、「具有(has/having)」或其任何其他變化係意欲涵蓋非排他性包括(non-exclusive inclusion)。例如,包含所列特徵之程序、方法、物件、或設備不一定僅限於該等特徵,而是可包含未明確列出或為此程序、方法、物件或設備所固有的其他特徵。
如本文所使用,除非另有相反的明確陳述,否則「或」係指包括性之或(inclusive-or)而非排他性之或(exclusive-or)。例如,下列任一者係符合條件A或B (condition A or B):是(true)(或存在(present))A而不是(false)(或不存在)B,不是(或不存在)A而是(或存在)B,以及,是(或存在)A及B二者。
此外,使用「一(a/an)」描述本文所述之元件及組件。此僅係方便行事,且供發明範圍之一般概念(general sense)。該說明應理解為包含一者或至少一者,以及除非明顯為相反意思,否則單數(singular)亦包含複數(plural)。
本揭露內容係關於包含光引發劑及可聚合材料之光可固化組成物(photocurable composition),其中,可聚合材料可包含具有式(1)之結構的單官能丙烯酸酯單體,其中R1為H或C
1-C
6烷基,以及R2及R3為C
1-C
10烷基或烷基-芳基中之一或多個取代,以及R4、R5為H或C
1-C
10烷基,
。
已意外觀察到式(1)之單體與多官能丙烯酸酯單體之某些組合可獲致於固化之後具有低熱收縮率(thermal shrinkage)之光可固化組成物。於一態樣中,接受於250℃、2分鐘之烘烤處理時,由光可固化組成物所形成之光固化層的熱收縮率可不大於7.5%,諸如不大於7.2%、不大於7.0%、不大於6.8%、不大於6.5%、不大於6.3%、或不大於6.0%。如本文所使用,熱收縮率係計算為烘烤處理之前及之後的光固化層之高度差%。
於一態樣中,可聚合材料之多官能丙烯酸酯單體可為雙官能丙烯酸酯單體、三官能丙烯酸酯單體、四官能丙烯酸酯單體、或其任何組合。多官能丙烯酸酯單體之非限制性實例可為雙酚A二甲基丙烯酸酯(bisphenol A dimethacrylate)、新戊二醇二丙烯酸酯(neopentyl glycol diacrylate)、三羥甲基丙烷三丙烯酸酯(trimethylolpropane triacrylate)、四羥甲基甲烷四丙烯酸酯(tetramethylolmethane tetraacrylate)、或其任何組合。
於一具體態樣中,多官能丙烯酸酯單體可為雙官能丙烯酸酯單體(bi-functional acrylate monomer)。於某一具體態樣中,雙官能丙烯酸酯單體可為雙酚A二甲基丙烯酸酯,其具有式(3)所示之結構:
。
於一態樣中,以可聚合材料之總重為基準計,式(1)之單官能丙烯酸酯單體的量可為至少10 wt% ,諸如至少15 wt%、或至少20 wt%。於另外某一態樣中,以可聚合材料之總重為基準計,式(1)之單體的量可不大於40 wt%、或不大於30 wt%、或不大於25 wt%、或不大於20 wt%、或不大於15 wt%、或不大於12 wt%、或不大於10 wt%。式(1)之單體的量可為在任何上述最小數值及最大數值之間的範圍內之數值。
於另一態樣中,以可聚合材料之總重為基準計,多官能丙烯酸酯單體之量可為至少10 wt%、或至少15 wt%、或至少20 wt%、或至少25 wt%。於另一態樣中,以可聚合材料之總重為基準計,多官能丙烯酸酯單體之量 可不大於50 wt%,諸如不大於40 wt%、不大於30 wt%、不大於25 wt%、或不大於20 wt%。多官能丙烯酸酯單體之量可為在上述任何最小數值及最大數值內之數值,諸如10 wt%至50 wt%、15 wt%至40 wt%、或10 wt%至30 wt%。
於又另一態樣中,式(1)之單官能單體對多官能丙烯酸酯單體之重量%比率可為1:5至5:1,諸如1:3至3:1、或1:1至3:1。
對於選擇單體而言重要的是於固化之前維持可聚合組成物的低黏度之態樣。於一實施態樣中,可固化組成物之黏度可不大於30 mPa·s,諸如不大於25 mPa·s、不大於20 mPa·s、不大於15 mPa·s、或不大於10 mPa·s。於其他某些實施態樣中,黏度可為至少3 mPa·s,諸如至少5 mPa·s、或至少8 mPa·s。於一特佳態樣中,光可固化組成物可具有不大於15 mPa·s之黏度。如本文所使用,所有黏度值係關於在23℃之溫度、以布氏法(Brookfield method)使用布氏黏度計(Brookfield Viscometer)所測量的黏度。
光可固化組成物中之可聚合材料的量以光可固化組成物之總重為基準計可為至少75 wt%,諸如至少80 wt%、至少85 wt%、至少90 wt%、或至少95 wt%。於另一態樣中,以光可固化組成物之總重為基準計,可聚合材料之量可不大於99 wt%,諸如不大於98 wt%、或不大於97 wt%、或不大於95 wt%。可聚合材料的量可為介於上述任何最小值及最大值之間的值。於一具體態樣中,可聚合材料之量可為至少85 wt%且不大於98 wt%。
於另一實施態樣中,除了式(1)之單官能丙烯酸酯單體及至少一種多官能丙烯酸酯單體以外,光可固化組成物之可聚合材料可包含某量之可聚合單體、寡聚物(oligomer)、或聚合物。此等可聚合化合物之非限制性實例可為例如丙烯酸苄酯(benzyl acrylate)、丙烯酸1-萘酯(1-naphthyl acrylate)、二乙烯苯(divinylbenzene)、順丁烯二醯亞胺單體(maleimide monomer)、乙烯基醚(vinylether)、或苯乙烯衍生物(styrene derivative)。
於一態樣中,除了式(1)之單官能丙烯酸酯單體及多官能丙烯酸酯單體以外,可聚合材料可包含至少一種其他的單官能丙烯酸酯單體,諸如至少二或三種另外的單官能丙烯酸酯單體。於一具體態樣中,以可聚合材料之總重為基準計,至少一種另外的單官能丙烯酸酯單體之量可為至少30 wt%、或至少40 wt%、或至少50 wt%、或至少60 wt%。於某一具體態樣中,可聚合材料可包含至少40 wt%之量的丙烯酸苄酯作為另外的單官能丙烯酸酯單體。
於另一態樣中,本揭露內容之可固化組成物可不含溶劑。
為了若曝露於光時引發組成物之光固化,光可固化組成物中可包含一或多種光引發劑。
某一態樣中,固化亦可藉由結合光及熱固化進行。
光可固化組成物可進一步包含一或多種隨意的(optional)添加劑。隨意的添加劑之非限制性實例可為安定劑、分散劑、溶劑、界面活性劑、抑制劑或其任何組合。
於一實施態樣中,光可固化組成物可施加至基板以形成光固化層(photo-cured layer)。如本文所使用,基板及在基板上之光固化層的組合係稱為積層物(laminate)。
可聚合材料之單體的組合可導致光固化層中之高碳含量。於一實施態樣中,光固化層之碳含量(carbon content)可為至少70%,諸如至少72%、至少73%、至少74%、至少75%、至少76%、或至少77%。於一具體態樣中,碳含量可為至少74%。
於另一態樣中,積層物之光固化層可具有不大於2.9、或不大於2.8、或不大於2.7、或不大於2.6之Ohnishi數(Ohnishi number)。於另一態樣中,Ohnishi數可為至少1.8,諸如至少1.9、至少2.0、至少2.1、至少2.2、或至少2.3。
於一具體實施態樣中,光固化層可具有至少74%之碳含量及不大於2.9之Ohnishi數。
本揭露內容進一步關於形成光固化層之方法。該方法可包含於基板上施加上述光可固化組成物之層,使該光可固化組成物與模板(template)或覆板(superstrate)接觸;以光照射光可固化組成物以形成光固化層(photo-cured layer);以及從光固化層移除模板或覆板。
基板及固化的層(solidified layer)可接受另外的處理,例如蝕刻程序,以將對應於固化的層及/或在固化的層下方之圖案化層之一或二者中的圖案(pattern)之影像(image)轉移至基板。基板可進一步接受用於裝置(物件)製造之已知步驟及程序,包括例如,固化、氧化、層形成、沉積、摻雜(doping)、平坦化(planarization)、蝕刻(etching)、可成形材料去除(formable material removal)、切割(dicing)、接合(bonding)、及封裝(packaging)等。
光固化層可進一步用作半導體裝置(諸如LSI、系統LSI、DRAM、SDRAM、RDRAM、或D-RDRAM)之層間絕緣膜(interlayer insulating film)、或作為半導體製程中所使用之抗蝕膜(resist film)。
如進一步於實例中所示,意外發現光可固化組成物中包含式(1)之單官能丙烯酸酯單體的可聚合單體及至少一種包含多官能丙烯酸酯單體的第二單體之某些組合可具有尤其適於IAP處理之性質。本揭露內容之光可固化組成物可具有低於15 mPa·s之所欲低黏度,以及可形成若曝露於高溫烘烤處理時具低熱收縮率之光固化層。
實施例
下列非限制性實例說明如本文所述之概念。
實施例
1
光可固化IAP組成物之製備。
五種光可固化組成物(樣本S1至S5)之各樣本係藉由組合單官能丙烯酸酯單體3-苯氧基苄基丙烯酸酯(3-phenoxybenzyl acrylate)(POBA)與雙官能丙烯酸酯單體雙酚A二甲基丙烯酸酯 (BPADMA)、以及選自丙烯酸苄酯(benzylacrylate)(BA)、丙烯酸酯1-萘酯(1-naphthylacrylate)(1-NA)、及鄰苯基酚EO丙烯酸酯(ortho-phenylphenol EO acrylate)(得自Miwon Specialty Chemical Co.,Ltd之Miramer M1142)之兩種另外的單體而製備。各組成物之可聚合材料的確切組合及單體量彙總於下表1。
此外,兩種比較光可固化組成物係藉由組合雙官能BPADMA與BA及1-NA (比較組成物C1),以及藉由組合BPADMA與BA、1-NA及1-金剛烷基甲基丙烯酸酯(1-adamantyl methacrylate)(1-AMA) (比較組成物C2)而製備。1-AMA之結構顯示於式(4)。
。
比較組成物C1及C2之可聚合材料亦彙總於表1。所有光可固化組成物均進一步包含1-5 wt%之量的光引發劑Irgacure 819以及0.1%-3% wt%之間的量之界面活性劑C10GM2070。
光固化層係由表1所彙總之光可固化組成物製備,係藉由在玻璃基板上施加約300微米厚度之光可固化組成物的液態膜、以及使該液態膜接受4 mW/cm
2之UV光強度達600秒(對應於固化能劑量(curing energy dosage)為2.4 J/cm
2)。於光固化之後,所有光固化層均為固態。
測量熱收縮率
為了評估熱收縮率(thermal shrinkage),於光固化之後將光固化層置於溫度為250℃之熱板(hotplate)上達兩分鐘,其於此處亦稱為烘烤(baking)。所有烘烤處理均於空氣下進行。熱收縮率係藉由使用橢圓偏光計(ellipsometer)測量於烘烤處理之前及之後的受測層之厚度變化、以及根據式:St = (T
u- T
b) / T
u(其中,T
u為在烘烤之前的未烘烤階段中的該層之厚度,T
b為烘烤之後的該層之厚度)計算熱收縮率(St)而獲得。
表2彙總所有樣本之熱收縮率測試結果。表2進一步包含層之所計算的碳含量的重量%以及Ohnishi數。可看出樣本S1至S5的熱收縮率低於比較樣本C1及C2約1至3%。
樣本之黏度係於23℃使用布氏黏度計LVDV-II + Pro於200 rpm (心軸尺寸(spindle size)#18)測量。為進行黏度測試,將約6-7 mL之樣本液體添加至樣本室(sample chamber)至足以覆蓋心軸頭(spindle head)。對於全部黏度測試,進行至少三次測量且計算平均值。
Ohnishi數(Ohnishi number)(ON)已知為經驗參數(empirical parameter)且計算為聚合物重複單元中之原子總數(N
t)除以單元中的碳原子數(Nc)與氧原子數(N
O)之間的差之比率,ON = N
t/ (N
C- N
O)。為計算Ohnishi數,假設固化材料包含100 wt%之藉由加成聚合(addition polymerization)所形成的聚合單體單元(polymerized monomer unit)(於聚合期間無原子損失)。
本文所闡述之實施態樣的詳細說明及例舉說明係欲提供對各種實施態樣之結構的大體理解。詳細說明及例舉說明並非意欲作為使用本文所述之結構或方法的設備及系統之全部元件及特徵的窮盡(exhaustive)且全面(comprehensive)的描述。亦可於單一實施態樣中組合提供個別實施態樣,反之,為求簡潔,於單一實施態樣之內容中所述的各種特徵亦可單獨提供或以任何子組合提供。此外,提及以範圍表示之值係包括在該範圍內之每一值。僅於閱讀本說明書之後,熟習本領域之人士可容易暸解許多其他實施態樣。可使用其他實施態樣及衍生自本揭露內容,以在不偏離本揭露內容之範圍的情況下進行結構替代(structural substitution)、邏輯替代(logical substitution)、或其他改變。因此,本揭露內容應視為例示性(illustrative)而非限制性(restrictive)。
Claims (20)
- 如請求項1之光可固化組成物,其中,該可聚合材料進一步包含至少一種多官能丙烯酸酯單體。
- 如請求項2之光可固化組成物,其中,該至少一種多官能丙烯酸酯單體包含雙官能丙烯酸酯單體、三官能丙烯酸酯單體、四官能丙烯酸酯單體、或其任何組合。
- 如請求項3之光可固化組成物,其中,該至少一種多官能丙烯酸酯單體包含雙酚A二甲基丙烯酸酯(bisphenol A dimethacrylate)(BPADMA)。
- 如請求項3之光可固化組成物,其中,該多官能丙烯酸酯單體之量,以該可聚合材料之總重為基準計,為至少10 wt%且不大於40 wt%。
- 如請求項6之光可固化組成物,其中,該單官能丙烯酸酯單體之量,以該可聚合材料之總重為基準計,為不大於25 wt%。
- 如請求項6之光可固化組成物,其中,該單官能丙烯酸酯單體之量,以該可聚合材料之總重為基準計,為不大於15 wt%。
- 如請求項1之光可固化組成物,其中,該可聚合材料進一步包含至少一種與式1之該單官能丙烯酸酯單體不同的單官能丙烯酸酯單體。
- 如請求項1之光可固化組成物,其中,該光可固化組成物係使得該組成物之光固化層具有不大於7.5 %之熱收縮率(thermal shrinkage),熱收縮率為接受250℃、2分鐘之烘烤處理之前及之後的該光固化層之厚度的差。
- 如請求項1之光可固化組成物,其中,該光可固化組成物之黏度不大於15 mPa·s。
- 如請求項1之光可固化組成物,其中,該光可固化組成物係使得該組成物之光固化層具有不大於2.9之Ohnishi數。
- 一種積層物(laminate),其包含基板及在該基板上之光固化層,其中,該光固化層係由請求項1之光可固化組成物形成。
- 如請求項13之積層物,其中,該光固化層具有不大於7.5 %之熱收縮率,熱收縮率為接受250℃、2分鐘之烘烤處理之前及之後的該光固化層之厚度的差。
- 如請求項13之積層物,其中,該光固化層具有不大於2.9之Ohnishi數。
- 如請求項16之方法,其中,該光固化層具有不大於7.5 %之熱收縮率,熱收縮率為接受250℃、2分鐘之烘烤處理之前及之後的該光固化層之厚度的差。
- 如請求項16之方法,其中,該光可固化組成物之黏度不大於15 mPa·s。
- 如請求項16之方法,其中,該光可固化組成物進一步包含以該可聚合組成物之總重為基準計為10 wt%至30 wt%之量的雙酚A二甲基丙烯酸酯(BPADMA)。
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AU4574701A (en) | 2000-03-15 | 2001-09-24 | Dentsply Int Inc | Reducing polymerization stress by controlled segmental curing |
US6709271B2 (en) | 2001-11-20 | 2004-03-23 | Bisco, Inc. | Low shrinkage dental composite |
DE102005021332B4 (de) | 2005-05-04 | 2008-02-28 | Heraeus Kulzer Gmbh | Kompositmaterialien mit geringer Schrumpfkraft |
JP2010186979A (ja) * | 2008-12-03 | 2010-08-26 | Fujifilm Corp | インプリント用硬化性組成物、パターン形成方法およびパターン |
US8999221B2 (en) * | 2008-12-03 | 2015-04-07 | Fujifilm Corporation | Curable composition for imprints, patterning method and pattern |
JP5968933B2 (ja) | 2008-12-03 | 2016-08-10 | 富士フイルム株式会社 | インプリント用硬化性組成物、パターン形成方法およびパターン |
KR101374368B1 (ko) * | 2010-12-31 | 2014-03-17 | 제일모직주식회사 | 광경화형 수지 조성물 및 이를 이용한 광학필름 제조 방법 |
JP5806501B2 (ja) | 2011-05-10 | 2015-11-10 | キヤノン株式会社 | インプリント装置、及び、物品の製造方法 |
JP6231904B2 (ja) * | 2013-02-25 | 2017-11-15 | 大阪ガスケミカル株式会社 | 硬化性組成物およびその硬化物 |
JP6361664B2 (ja) * | 2013-11-28 | 2018-07-25 | Jnc株式会社 | 光硬化性インクジェットインク |
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JP2018039988A (ja) * | 2016-08-23 | 2018-03-15 | 三洋化成工業株式会社 | 光硬化性組成物 |
EP3778681A4 (en) * | 2018-03-28 | 2022-01-05 | Kuraray Noritake Dental Inc. | COMPOSITION OF LIGHT-CURING RESIN |
TWI704193B (zh) * | 2019-01-15 | 2020-09-11 | 新應材股份有限公司 | 感光性樹脂組成物、光學膜及其製造方法 |
US20200339828A1 (en) * | 2019-04-26 | 2020-10-29 | Canon Kabushiki Kaisha | Photocurable composition |
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KR20230113378A (ko) | 2023-07-28 |
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CN116583406A (zh) | 2023-08-11 |
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