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    • 1. 发明授权
    • Composition for anti-reflective coating or radiation absorbing coating and compounds used in the composition
    • 用于组合物中的抗反射涂层或辐射吸收涂层和化合物的组合物
    • US06803168B1
    • 2004-10-12
    • US09237125
    • 1999-01-26
    • Munirathna PadmanabanWen-Bing KangHatsuyuki TanakaKen KimuraGeorg Pawlowski
    • Munirathna PadmanabanWen-Bing KangHatsuyuki TanakaKen KimuraGeorg Pawlowski
    • G03F7004
    • G03F7/091C08F220/34C08G18/2825C08G18/2865C08G18/728C08G18/8116C09D4/00C09D5/32G03F7/0045
    • A composition for an anti-reflective coating or a radiation absorbing coating which can form an anti-reflective coating or a radiation absorbing coating having high absorption to exposed radiation in the range of 100 to 450 nm, no diffusion of photo-generated acid to anti-reflective coating and so on, no intermixing of resist and anti-reflective coating layer, good shelf-life stability, and good step coverage and novel compounds and polymers being preferably used in the composition are disclosed. The composition contains an acrylic or methacrylic compound or polymer with an isocyanate or thioisocyanate group bonded through an alkylene group to a side chain thereof or with an amino or hydroxyl group-containing organic chromophore which absorbs radiation in the range of 100 to 450 nm wavelength and is bonded, for example, through an alkylene group to the isocyanate or thioisocyanate group. Resist patters with high resolution are formed on a substrate. A composition for an anti-reflective coating or a radiation absorbing coating are applied on the substrate and baked to form an anti-reflective coating or a radiation absorbing coating layer. Then, a chemically amplified resist is coated thereon and after patternwize exposure, developed. During baking of the anti-reflective coating or radiation absorbing coating, hardening or curing of the coating takes place by the presence of the isocyanate or thioisocyanate group. On the other hand, the exposed radiation having wavelength in the range of 100 to 450 nm is absorbed by organic chromophore.
    • 用于抗反射涂层或辐射吸收涂层的组合物,其可以形成对100至450nm范围内的暴露辐射具有高吸收的抗反射涂层或辐射吸收涂层,而不会将光产生的酸扩散到抗 反射涂层等,公开了抗蚀剂和抗反射涂层的互相混合,良好的保质期稳定性和良好的阶梯覆盖率,并且组合物中优选使用的新型化合物和聚合物。 该组合物含有丙烯酸或甲基丙烯酸类化合物或具有通过亚烷基键合到其侧链上的异氰酸酯或硫代异氰酸酯基团或与吸收在波长为100至450nm范围内的辐射的含氨基或羟基的有机发色团的聚合物,以及 例如通过亚烷基键合到异氰酸酯或硫代异氰酸酯基团。 在基板上形成具有高分辨率的抗蚀剂图案。 将用于抗反射涂层或辐射吸收涂层的组合物施加在基材上并烘烤以形成抗反射涂层或辐射吸收涂层。 然后,将化学放大抗蚀剂涂覆在其上,并经过图案化曝光后显影。 在防反射涂层或辐射吸收涂层的烘烤期间,涂层的硬化或固化通过异氰酸酯或硫代异氰酸酯基团的存在进行。 另一方面,波长在100〜450nm的曝光的辐射被有机发色团吸收。
    • 2. 发明授权
    • Radiation absorbing polymer, composition for radiation absorbing coating, radiation absorbing coating and application thereof as anti-reflective coating
    • 辐射吸收聚合物,用于辐射吸收涂层的组合物,辐射吸收涂层及其作为抗反射涂层的应用
    • US06737492B2
    • 2004-05-18
    • US10229219
    • 2002-08-27
    • Wen-Bing KangMunirathna PadmanabanHatsuyuki TanakaKen KimuraTakanori KudoGeorg Pawlowski
    • Wen-Bing KangMunirathna PadmanabanHatsuyuki TanakaKen KimuraTakanori KudoGeorg Pawlowski
    • C08F11636
    • C09D4/00C08F246/00G03F7/091C08F220/26C08F220/58C08F212/00
    • A radiation absorbing polymer having chemically bonded thereto a radiation absorbing dye, which has high absorption at a predetermined wavelength radiation, which shows good adhesion to a substrate and good thin film-forming, which has no dependence upon resists, which is soluble in a solvent for photoresists but becomes insoluble after being baked; a composition for radiation absorbing coating containing this polymer, and a radiation absorbing coating such as an anti-reflective coating formed from this composition are disclosed. The radiation absorbing polymer comprises a copolymer containing at least both a recurring unit composed of a monomer containing a keto group and a divalent group (preferably a methylene group) in its side chain and a recurring unit composed of a monomer containing an organic chromophore bonded directly or through a linkage group to the main chain. This radiation absorbing polymer is dissolved in a solvent such as alcohol, aromatic hydrocarbon, ketone, ester, etc., and the resulting solution is applied to a wafer and baked to form a radiation absorbing coating such as an anti-reflective coating. On this coating is coated, for example, a chemically amplified resist. This coated substrate is then exposed to deep UV rays and is developed to form a fine resist pattern excluding the influence of standing wave.
    • 一种辐射吸收聚合物,其化学键合有辐射吸收染料,该辐射吸收染料在预定波长辐射下具有高吸收性,其对基底具有良好的粘附性,并且与溶于溶剂的抗蚀剂无关的良好的薄膜形成 用于光致抗蚀剂,但在烘烤后变得不溶; 公开了含有这种聚合物的辐射吸收涂层用组合物和由该组合物形成的抗反射涂层等吸收辐射涂层。 辐射吸收聚合物包括共聚物,其至少包含由侧链中含有酮基和二价基团(优选亚甲基)的单体构成的重复单元,以及由含有直接键合的有机发色团的单体构成的重复单元 或通过连接组到主链。 将这种辐射吸收聚合物溶于醇,芳族烃,酮,酯等溶剂中,将所得溶液施加到晶片上并烘烤以形成抗辐射涂层等吸收辐射的涂层。 在该涂层上涂覆例如化学放大抗蚀剂。 然后将该涂覆的基材暴露于深紫外线,并显影以形成除了驻波的影响之外的精细抗蚀剂图案。
    • 3. 发明授权
    • Radiation absorbing polymer, composition for radiation absorbing coating, radiation absorbing coating and application thereof as anti-reflective coating
    • 辐射吸收聚合物,用于辐射吸收涂层的组合物,辐射吸收涂层及其作为抗反射涂层的应用
    • US06468718B1
    • 2002-10-22
    • US09244358
    • 1999-02-04
    • Wen-Bing KangMunirathna PadmanabanHatsuyuki TanakaKen KimuraTakanori KudoGeorg Pawlowski
    • Wen-Bing KangMunirathna PadmanabanHatsuyuki TanakaKen KimuraTakanori KudoGeorg Pawlowski
    • G03C173
    • C09D4/00C08F246/00G03F7/091C08F220/26C08F220/58C08F212/00
    • A radiation absorbing polymer having chemically bonded thereto a radiation absorbing dye, which has high absorption at a predetermined wavelength radiation, which shows good adhesion to a substrate and good thin film-forming, which has no dependence upon resists, which is soluble in a solvent for photoresists but becomes insoluble after being baked; a composition for radiation absorbing coating containing this polymer, and a radiation absorbing coating such as an anti-reflective coating formed from this composition are disclosed. The radiation absorbing polymer comprises a copolymer containing at least both a recurring unit composed of a monomer containing a keto group and a divalent group (preferably a methylene group) in its side chain and a recurring unit composed of a monomer containing an organic chromophore bonded directly or through a linkage group to the main chain. This radiation absorbing polymer is dissolved in a solvent such as alcohol, aromatic hydrocarbon, ketone, ester, etc., and the resulting solution is applied to a wafer and baked to form a radiation absorbing coating such as an anti-reflective coating. On this coating is coated, for example, a chemically amplified resist. This coated substrate is then exposed to deep UV rays and is developed to form a fine resist pattern excluding the influence of standing wave.
    • 一种辐射吸收聚合物,其化学键合有辐射吸收染料,该辐射吸收染料在预定波长辐射下具有高吸收性,其对基底具有良好的粘附性,并且与溶于溶剂的抗蚀剂无关的良好的薄膜形成 用于光致抗蚀剂,但在烘烤后变得不溶; 公开了含有这种聚合物的辐射吸收涂层用组合物和由该组合物形成的抗反射涂层等吸收辐射涂层。 辐射吸收聚合物包括共聚物,其至少包含由侧链中含有酮基和二价基团(优选亚甲基)的单体构成的重复单元,以及由含有直接键合的有机发色团的单体构成的重复单元 或通过连接组到主链。 将这种辐射吸收聚合物溶于醇,芳族烃,酮,酯等溶剂中,将所得溶液施加到晶片上并烘烤以形成抗辐射涂层等吸收辐射的涂层。 在该涂层上涂覆例如化学放大抗蚀剂。 然后将该涂覆的基材暴露于深紫外线,并显影以形成除了驻波的影响之外的精细抗蚀剂图案。
    • 4. 发明授权
    • Antireflection or light-absorbing coating composition and polymer therefor
    • 防反射或光吸收涂料组合物及其聚合物
    • US06329117B1
    • 2001-12-11
    • US09319129
    • 1999-08-09
    • Munirathna PadmanabanWen-Bing KangGeorg PawlowskiKen KimuraHatsuyuki Tanaka
    • Munirathna PadmanabanWen-Bing KangGeorg PawlowskiKen KimuraHatsuyuki Tanaka
    • G03C173
    • G03F7/091Y10S430/106Y10S430/107Y10S430/108Y10S430/111
    • A composition for an anti-reflective coating or a light absorbing coating, which shows good light absorption for lights of 100-450 nm in wavelength, suffers neither footing nor intermixing, and has excellent storage stability and step coverage, and novel copolymers to be used therein. The novel polymers comprise acrylic or methacrylic copolymers or terpolymers, at least having both recurring units (1) wherein an amino group- or hydroxyl-group containing organic chromophore capable of absorbing lights of 100 to 450 nm in wavelength is chemically bound to the carbonyl group bound to a carbon atom in the main chain, directly or through —R1NHCXY— (wherein R1 represents an alkylene group, X represents O or S, Y represents O or NR6, R6 represents H, a substituted or non-substituted, straight chain or cyclic alkyl group or a phenylene group) and for example recurring units (2) wherein a double bond-or epoxy group-containing alkyl group is chemically bound to the carboxyl or oxygen group bound to a carbon atom in the main chain. The composition containing the copolymer is coated on a wafer to form a bottom anti-reflective coating and, after coating thereon a photoresist, deep UV exposure and development are conducted to form a resist image with high resolution.
    • 用于抗反射涂层或光吸收涂层的组合物对于波长为100-450nm的光显示出良好的光吸收,既不起脚也不混合,并且具有优异的储存稳定性和阶梯覆盖率,以及要使用的新型共聚物 其中。 该新型聚合物包含至少具有两个重复单元(1)的丙烯酸或甲基丙烯酸共聚物或三元共聚物,其中能够吸收波长为100至450nm的光的含氨基或羟基的有机发色团与羰基化学键合 直接或通过-R1NHCXY-(其中R1表示亚烷基,X表示O或S,Y表示O或NR6,R6表示H,取代或未取代的直链或未取代的直链或 环状烷基或亚苯基),例如其中双键或含环氧基的烷基与与主链中的碳原子结合的羧基或氧基化学键合的重复单元(2)。 将包含共聚物的组合物涂覆在晶片上以形成底部抗反射涂层,并且在其上涂覆光致抗蚀剂之后,进行深紫外线曝光和显影以形成具有高分辨率的抗蚀剂图像。
    • 7. 发明授权
    • Positive-working radiation-sensitive mixture
    • 正面工作的辐射敏感混合物
    • US5843319A
    • 1998-12-01
    • US902072
    • 1997-07-29
    • Klaus Juergen PrzybillaTakanori KudoSeiya MasudaYoshiaki KinoshitaNatsumi SuehiroMunirathna PadmanabanHiroshi OkazakiHajime EndoRalph DammelGeorg Pawlowski
    • Klaus Juergen PrzybillaTakanori KudoSeiya MasudaYoshiaki KinoshitaNatsumi SuehiroMunirathna PadmanabanHiroshi OkazakiHajime EndoRalph DammelGeorg Pawlowski
    • G03F7/004G03F7/039B01D15/00B01J39/00C02F1/42
    • G03F7/0045G03F7/039
    • A process for producing a solution of a basic or non-basic sulfonium compound (A) of formulae II-V: ##STR1## wherein R.sup.5, R.sup.6 and R.sup.7 each independently represent a C.sub.1 -C.sub.18 alkyl, aryl or heteroaryl group or an aryl group mono-, di- or tri-substituted with an alkyl, an alkylaryl, an aryl, a halogen, an alkoxy, a phenoxy, a thiophenol, a phenylsulfonyl or a phenylsulphenyl; Y represents (CH.sub.2).sub.n (wherein n is 0 or 1), O or S; R.sup.8 and R.sup.9 represent a C.sub.1 -C.sub.4 alkyl, alkoxy or a halogen; R.sup.10 and R.sup.11 represent a C.sub.1 -C.sub.4 alkyl, alkoxy or a halogen; n is 5 or 6; and X.sub.2.sup.- represents a basic anion having a pK.sub.B value of -3 to +5; comprising the steps of: (a) dissolving a sulfonium salt (B) in a metal-ion free polar or non-polar solvent to form a solution, said sulfonium salt (B) being selected from said formulae II-V, wherein R.sup.5 to R.sup.11, Y and n of said sulfonium salt (B) have the sane meaning as above and X.sub.2.sup.- represents a non-nucleophilic anion; (b) contacting said solution for a sufficient amount of time with a basic ion-exchange resin having a quaternary ammonium group to replace the anion of (B) with a hydroxide ion and to form a sulfonium hydroxide solution; (c) separating said sulfonium hydroxide solution from the resin; and optionally (d) adding an active hydrogen containing compound or its base-labile precursor to said sulfonium hydroxide solution to yield a solution of the sulfonium compound (A) wherein X.sub.2.sup.- represents a basic anion other than a hydroxy ion.
    • 制备式II-V的碱性或非碱性锍化合物(A)的溶液的方法:[SR5R6R7] + X2-Ⅱ其中R5,R6和R7各自独立地 独立地表示C1-C18烷基,芳基或杂芳基或被烷基,烷基芳基,芳基,卤素,烷氧基,苯氧基,苯硫酚,苯基磺酰基或苯基磺酰基单 - ,二 - 或三 - 取代的芳基 苯基磺酰基; Y表示(CH 2)n(其中n为0或1),O或S; R8和R9代表C1-C4烷基,烷氧基或卤素; R10和R11表示C1-C4烷基,烷氧基或卤素; n为5或6; X2-表示pKB值为-3〜+5的碱性阴离子; 包括以下步骤:(a)将锍盐(B)溶解在无金属离子的极性或非极性溶剂中以形成溶液,所述锍盐(B)选自所述式II-V,其中R5至 所述锍盐(B)的R 11,Y和n具有如上所述的正义,X2-表示非亲核阴离子; (b)用具有季铵基团的碱性离子交换树脂将所述溶液接触足够的时间以用氢氧根离子代替(B)的阴离子并形成氢氧化锍溶液; (c)从树脂中分离出氢氧化锍溶液; 和任选地(d)在所述氢氧化锍溶液中加入含活性氢的化合物或其碱不稳定的前体,得到其中X2代表羟基离子以外的碱性阴离子的锍化合物(A)的溶液。
    • 8. 发明授权
    • Radiation sensitive composition
    • 辐射敏感组合物
    • US5738972A
    • 1998-04-14
    • US864375
    • 1997-05-28
    • Munirathna PadmanabanNatsumi SuehiroYoshiaki KinoshitaSatoru FunatoSeiya MasudaHiroshi OkazakiGeorg Pawlowski
    • Munirathna PadmanabanNatsumi SuehiroYoshiaki KinoshitaSatoru FunatoSeiya MasudaHiroshi OkazakiGeorg Pawlowski
    • G03F7/00G03F7/004G03F7/033G03F7/039G03F7/085H01L21/027G03F7/38
    • G03F7/0045Y10S430/106
    • A chemically amplified resist material comprising: a) a homopolymer or a copolymer of hydroxystyrene or hydroxystyrene partly protected by a group sensitive to an acid such as a tetrahydropyranyl or t-butoxycarbonyl group, b) a dissolution inhibitor such as poly(N,O-acetal) or phenol or bisphenol protected by a group cleavable with an acid, c) a photosensitive compound capable of generating an acid upon exposure, d) a base capable of degrading upon radiation to regulate the line width in a period between the exposure step and the processing steps after exposure, e) a low-molecular weight phenolic or polyphenolic compound having a structure represented by the following general formula or a mixture of the phenolic or polyphenolic compounds: ##STR1## where n is an integer of 1 to 5, m is an integer of 0 to 4, n+m.ltoreq.5, and p is an integer of 1 to 10, each R is a C.sub.1 -C.sub.12 alkyl group or an unsubstituted or substituted cycloalkyl group or a C.sub.1 -C.sub.5 hydroxyalkyl group, provided that hydrogen atoms may be substituted with a halogen atom and, when m is not less than 2, each R may be the same or different; A represents a hydrocarbon atomic grouping, having a valence of p, including an unsubstituted or substituted C.sub.1 -C.sub.100 alicyclic, chain aliphatic, or aromatic hydrocarbon or a combination thereof with the carbon atoms being optionally substituted with an oxygen atom, provided that when p is 1, A may represent a hydrogen atom and, when p is 2, A may represent --S--, --SO--, --SO.sub.2 --, --O--, --CO--, or a direct bond, and f) a solvent for dissolving the components a) to e).
    • 一种化学放大抗蚀剂材料,包括:a)部分由对酸如四氢吡喃基或叔丁氧基羰基敏感的基团部分保护的羟基苯乙烯或羟基苯乙烯的均聚物或共聚物,b)溶解抑制剂如聚(N, 乙缩醛)或苯酚或双酚被被一个酸可裂解的基团保护,c)一种能够在暴露时产生酸的感光性化合物,d)能够在辐射下降解以在曝光步骤和 曝光后的处理步骤,e)具有由以下通式表示的结构的低分子量酚或多酚化合物或酚类或多酚化合物的混合物:n为0〜4的整数,n + m = 5 ,p为1〜10的整数,R为C1-C12烷基或未取代或取代的环烷基或C1-C5羟烷基,条件是氢原子可被卤素原子取代, en不小于2,每个R可以相同或不同; A表示具有p价的烃原子团,包括未取代或取代的C1-C100脂环族,链脂族或芳族烃或其任选被氧原子取代的碳原子的组合,条件是当p为 1中,A可以表示氢原子,当p为2时,A可以表示-S-,-SO-,-SO2-,-O-,-CO-或直接键,f)溶解溶剂 组件a)至e)。