TW567404B - Multilayer elements containing photoresist compositions and their use in microlithography - Google Patents

Abstract

A photoresist element comprising a substrate; an etch resistant layer; and at least one photoresist layer prepared from a photoresist composition comprising a polymer selected from the group consisting of: (a) a fluorine-containing copolymer comprising a repeat unit derived from at least one ethylenically unsaturated compound characterized in that at least one ethylenically unsaturated compound is polycyclic; (b) a branched polymer containing protected acid groups, said polymer comprising one or more branch segment(s) chemically linked along a linear backbone segment; (c) fluoropolymers having at least one fluoroalcohol group having the structure: -C(Rf)(Rf')OH, wherein Rf and Rf' are the same or different fluoroalkyl groups of from 1 to about 10 carbon atoms or taken together are (CF2)n wherein n is 2 to 10; (d) amorphous vinyl homopolymers of perfluoro(2,2-dimethyl-1,3-dioxole) or CX2=CY2 where X=F or CF3 and Y=-H or amorphous vinyl copolymers of perfluoro(2,2-dimethyl-1,3-dioxole) and CX2=CY2; and (e) nitrile/fluoroalcohol-containing polymers prepared from substituted or unsubstituted vinyl ethers; and (B) at least one photoactive component.

Description

567404 A7 ---______ Β7 V. Description of the invention χ-Scope of the invention The hand 1 / U, 畲 41 of the present invention is in photophase, and especially uses photoresist (positive operation and / or production) For imaging in the manufacture of semiconductor components. The present invention 1 has UV transparency (especially at a short wavelength, such as 157 nm) < permanent body composition, which can be used for multilayer components. A background of the invention is the micro-etching method for semiconductor manufacturing, in which the wafer design is patterned on a silicon wafer. At present, the semiconductor industry uses a tool with a wavelength of 248 nm from a W excimer laser to Produce wafers with surface features as small as 180 nm. The next level of technology in this technology is to use 193nm light from ArF lasers, and it is expected that the optical lithography etching will extend to wafers with surface features as low as 100nm. " Although it is generally estimated that some non-optical lithographic etching (X-rays, extreme ultraviolet ... i sub-beams, etc.) will eventually replace the lithographic lithographic engraving, it is expected that this technique will be available in the next ten years. Therefore, the importance of 157 nm lithography d has exploded in recent months, and it is currently regarded as a key bridge to bridge the gap between optical and non-optical etching. The development of the technology using 157nm light from the dagger laser will expand the use of optical lithography etching to at least 70nm nodes. The imaging layer used for lithographic etching is a photoresist, which must be nearly transparent to the wavelength of the light used. The basic requirements for single-layer photoresist include good plasma etching resistance, high Tg, and the traditional aqueous alkali developer.

567404 A7

Compatibility, and imaging with favorable development / dissolution characteristics. Or, etchability can be provided by a photoresist-coated substrate (sometimes called a "hard mask,"). This strategy is used for the opacity of photoresist to prevent it from acting as a thick, single layer When a photoresist is used. A double-layer or multi-layer photoresist suitable for 157 nm imaging is still needed. SUMMARY OF THE INVENTION In a first aspect, the present invention provides a photoresist element comprising: (L) a substrate; (M) ) An anti-surname engraving layer; and (N) at least one photoresist layer, made from a photoresist composition, comprising: (A) at least one polymer selected from the group consisting of: (a) a fluorocopolymer, which Comprising repeating units derived from at least one ethylenic unsaturated compound, characterized in that at least one ethylenic unsaturated compound is polycyclic; (b) a branched polymer containing a protected acid group, the polymer Contains one or more branched segments that are chemically connected along a linear main segment; (c) A fluoropolymer having at least one fluoroalcohol group having the following structure:

-C (Rf) (Rf,) 0H wherein Rf and Rf are the same or different fluoroalkyl groups of 1 to about 10 carbon atoms, or are used together as (CF2) n, where η is 2 to 10; (d ) Perfluoro (2,2-dimethyl-1,3-dioxolane) or amorphous ethylene homopolymer with cx2 = CY2, where X = F or CF3 and Y = -Η, or Amorphous ethenyl copolymer of perfluoro (2,2-dimethyl-1,3-dioxolane) and CX2 = CY2; and _ -6- This paper size applies to China National Standard (CNS) A4 Specification (210X297 mm) 567404 A7 B7 V. Description of the invention (3) (e) Nitrile / fluoroalcohol-containing polymer, made from substituted or unsubstituted vinyl ethers; and (B) at least one kind of light Active ingredient. Typically, this polymer has an absorption coefficient of less than 5.0 microns-1 in the blend 'at a wavelength of 157 nm. In a second aspect, the present invention provides a method for preparing a photoresist image on a substrate, including: (X) exposing the photoresist element in an image copying manner to form an imaged and unimaged area, wherein the photoresist element It includes a substrate, an anti-etching layer, and at least one photoresist layer, and is made from a photoresist composition, comprising: (A) a polymer selected from the above ⑷_ (e) and a mixture thereof; and (B) light Active ingredients; and 00 develops an exposed photoresist layer with imaged and unimaged areas to form a relief image on the substrate. DETAILED DESCRIPTION OF THE INVENTION The photoresistive element includes a carrier, an anti-etching layer and at least one photoresistive layer, wherein the photoresistive layer is made of a photoresist composition and comprises a polymer selected from the group consisting of ⑷ to (e) and a mixture thereof. ; And photoactive ingredients. Substrate The substrate used in the present invention, in terms of description, η ″ horse silicon, lice silicon, lice silicon, or various other materials used in semiconductor manufacturing. Anti-engraving: Anti-etching hard mask. The layer may be selected from a wide variety of known materials. These materials are sometimes referred to-some suitable materials include inorganic materials such as silicon oxide, nitride

567404 V. Description of the invention (4: Lice silicon, etc. These materials can be applied to the substrate by any conventional method. For example, chemical vapor deposition (CVD) can be used to apply an anti-etching layer to a substrate. The photoresist layer contains Polymers and photoactive components. -1 With these polymers, the body can be used in photoresist compositions / for semiconductor lithographic etching. In particular, 'because of the low optical absorption system of less than 193 mm, the present invention = The "principal trait" should be particularly useful at this wavelength. These condensers are not required at a wavelength of about 157 nm but may have an absorption coefficient of less than about 5.0 microns-1, which is typically here The wavelength D is less than about 40 micrometers M, and more typically, at this wavelength is less than about 3.5 micrometers (ΔΙΚ complex: the fluorinated copolymer (a) contains at least one ethylenic unsaturated compound The repeating unit is characterized in that the at least one ethylenic unsaturated compound is polycyclic. The copolymer is selected from the group consisting of: ⑷) fluorinated copolymers, which include at least one ethylenic unsaturated Compound repeating unit 'is characterized by at least _ species Actinic unsaturated compounds are polycyclic, and at least one other ethylenically unsaturated compound contains ^ at least-one fluorine atom 'covalently attached to the ethylenically unsaturated compound; and, (a2) fluorine-containing Copolymer comprising repeating units derived from at least one polycyclic acetamidine unsaturated compound, the compound containing at least one gasogen, a perfluoroalkyl group, and a perfluoro: feoxy group, which are covalently linked To carbon atom -8-This paper size applies to China National Standard (CNS) A4 (210X297 mm) 567404

The completed atom is enclosed in each ethylene-based unsaturated S ′ structure and is separated from the atom of the ethylenically unsaturated compound. Exterminate ^, Yu through at least one covalently linked carbon revealed in (al) to ^. A type of ethylenically unsaturated compounds, can be selected from the package-9-This paper is a national standard (cns) A4 size (2ig x 297 public love)

567404 V. Description of the invention (6 is °, 1 or 2 each, p is an integer of at least 3; a and b are independently 1 to 3, but when the native J Juntian b = 2, & not = 1, or vice versa The same is true; the soil Rs are all the same or different, and each represents a chlorine atom, a quotient atom, and a hydrocarbon group containing 1 to 14 carbon atoms, typically 1 to 10 carbon atoms, as the case may be, at least: 0, N, s, P or substituted by an atom, such as a radical; such as a primary or secondary alkyl carboxylic acid group or a carboxylic acid ester group, R1) is a saturated alkyl group of about 4 to 20 carbon atoms, optionally containing one or The multi-solid-bonded oxygen '纟 condition is that carbon atom to hydrogen atom is 0.58; ^ R 6 to R 21 are each independently a hydrogen atom, a CjC alkyl group, ㈣qC〇2A, = (CH2) qCO2A4CO2A, where qAa12, and a is hydrogen or an acid sulfonyl group, with the proviso that at least one of R18 to r21 is% a. The key feature of the present invention (and the photoresist containing these copolymers) is the polycyclic repeating unit and the same or different fluorine-containing repeating unit, and further, the aromatic copolymer is not contained in the copolymer. A synergistic combination of all repeating units of a group functional group. For the copolymer to be highly resistant to plasma etching (such as reactive ion etching), it is important that polycyclic repeating units are present in the copolymer. Many percent repeat units also tend to provide high glass transition temperatures, which is important for dimensional stability on photoresist films. For the copolymer to be optically transparent, meaning low optical absorption in extreme and extreme UV, the presence of repeating units containing fluorine is important. In order for the polymer to be optically transparent, it is also required that aromatic functional groups are not present in the repeating units of the copolymer. In certain embodiments of the present invention, the fluorocopolymer may include derivative binding

567404 A7 B7

A repeating unit of a polycyclic ethylenically unsaturated compound that has at least one atom or group selected from the group consisting of a fluorine atom, a perfluoroalkyl group, and a perfluoroalkoxy group, covalently attached to A carbon atom contained in a ring structure. Fluorine atom, perfluoroalkyl group, and perfluoroalkoxy group. When such a group is directly connected to the ethylenic unsaturated carbon atom, it tends to inhibit the cyclic ethylenic unsaturated compound from metal-catalyzed addition polymerization. Or the polymerization of metathesis polymerization. Therefore, it is important in this case that the at least one fluorine atom, perfluoro group, and perfluoroalkoxy group are each an ethylenically unsaturated carbon atom of the ethylenic unsaturated compound with at least one covalently Carbon atoms separated by way of connection. Furthermore, having this atom and / or group directly attached to the ring minimizes the presence of unwanted unfluorinated aliphatic carbon atoms. The co-products of the present invention are surprisingly balanced in nature, which is important for imparting the necessary properties of photoresist compositions for semiconductor applications. First, these copolymers have surprisingly low optical absorption in extreme and extreme UV, including 193 nm and 157 nm wavelengths. Making the copolymer with low optical absorption is very important for the deployment of high light speed photoresist. Most of the UV light is absorbed by the photoactive component and will not be lost due to the absorption by the copolymer (the matrix of the photoresist). . Secondly, the photoresist containing the fluorine-containing polymer of the present invention shows an extremely low plasma engraving rate. The properties described below are important in obtaining the precision photoresistance of the directional rod required in the semiconductor. Achieving appropriate values for these properties at the same time is particularly important for imaging at 157 nm. In this case, an ultra-thin photoresist is required to provide high resolution, but these thin photoresists must be highly etch resistant so that the photoresist remains on the imaged substrate and protects the area of the underlying substrate during etching ___ -11- This paper size applies to China National Standard (CNS) A4 (210X297 mm)

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567404 A7 B7 V. Description of the Invention (8) Domain. In a preferred embodiment of the present invention, the photoresist composition comprises a copolymer comprising a comonomer derived from at least one polycyclic comonomer (meaning, a comonomer comprising at least two rings, such as n ) Of the repeating unit. This is important for three main reasons: 1) Polycyclic monomers have a relatively high carbon-to-hydrogen ratio (C: H), which can cause a base material consisting of repeating units of such polycyclic monomers Polymers, generally having good resistance to plasma etching; 2) Polymers having repeating units derived from polycyclic monomers, which are preferably fully saturated during polymerization, and generally have good transparency characteristics; and 3) Polymers made from polycyclic monomers often have relatively high glass transition temperatures to provide improved dimensional stability during processing. The ethylenically unsaturated group may be contained in a polycyclic partial group, such as in n-sulene, or may be pendant to a polycyclic partial group, such as in 1-adamantanecarboxylic acid ethylammonium ester. Contains repeating units derived from polycyclic comonomers, a polymer with a high C: Η ratio and a relatively low Ohnishi value (O.N.), where: ON = N / (Nc -N0) where N is The number of atoms in the polymer repeating unit, Ne is the number of carbon atoms in the polymer repeating unit, and N. Is the number of oxygen atoms in the polymer repeat unit. There is a rule of thumb discovered by Ohnishi et al. (J. Electrochem. Soc ·, Solid-State Sci · Technol ·, 130, 143 (1983)), which states the reactive ion ionization (RIE) rate of polymers It is a linear function of Ohnishi value (ON). Taking the following as an example, poly (n-furene) has a chemical formula of poly (C7Hi 0) and O.N. = 17/7 = 2.42. It is mainly composed of carbon and hydrogen, a polymer with polycyclic partial groups and relatively few oxygen-containing functional groups, and has a relatively low ON. -12- This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm)

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Line 567404 Invention Description (9 and according to Ohnishi's rule of thumb, it has a fairly low (in an approximately linear manner) RIE rate. As is well known to those skilled in the art of polymer polymerization, ethylenically unsaturated compounds are involved in radical polymerization. And obtain a polymer derived from an ethylenically unsaturated compound and repeating an early position. Specifically, an ethylenically unsaturated compound having the following structure undergoing a radical polymerization reaction:

c = c / \ S τ is a polymer with the following repeating units ...

Binding where P, Q, S and T can be independently represented but not limited to H, F, c 丨, Br, alkyl groups containing 1 to 14 carbon atoms, aryl groups containing 6 to 14 carbon atoms, aralkyl groups, Or a cycloalkyl group containing 3 to 14 carbon atoms.

If only one kind of ethylidene-based unsaturated compound is polymerized, the polymer formed is a homopolymer. If two or more different ethylenically unsaturated valences are polymerized, the polymer formed is a copolymer. Some representative examples of ethylenically unsaturated compounds and their corresponding repeating units are shown below: ~ ^

F " F \ / C = C / \

F F -13- 567404 Description of the invention Η \ c = c / Η Η Η Η \ /, Cf 〇

CH,, ch3 > In the next and subsequent paragraphs, the photoresist composition of the present invention is described in terms of its component part β "" "The photoresist of the present invention includes a fluorinated copolymer which includes a derivative derived from at least one = Is a repeating unit of unsaturated compound, characterized in that at least one ethylenic unsaturated compound is polycyclic, and at least one ethylenic unsaturated compound contains at least one fluorogen [covalently connected to ethylenic unsaturated carbon Atoms. Representative ethylenic saturated compounds that are suitable for the fluorinated copolymers of the present invention include, but are not limited to, tetrafluoroacetamidine, chlorotrifluoroacetamidine, difluoropropene, trifluoroethanesox, difluoroethyleneamidine, Fluoroethylene, perfluoro- (2,2-dimethyl-1,3-dioxolene), perfluoro- (2-methylene-4-methyl-fluorene, 3_dioxolane ), CF2 = CF〇 (CF2) tCF = CF2, where ^] or 2, and Rf〇CF = cF2, where & is a saturated fluorocarbon group having 1 to about 1G carbon atoms. The fluorine-containing copolymerization of the present invention ^ Other fluorinated comonomers that may include any integer include, but are not limited to, those listed above. Preferred comonomers are tetrafluoroethylene, trifluorofluoride Hexafluorohexafluoride, trifluoroacetamidine, and Rf0CF = CF2, which are Rf4l to about 10 carbon atoms of saturated fluorocarbon. More preferred comonomers are tetramethylacetonium, chlorotrifluoroethylene, Hexapropene and? Ocfcf2 'saturated perfluoroalkyl with tRf4l to about 10 carbon atoms. The best comonomers are tetrafluoroethylene and chlorotrifluoroethylene. Representative comonomers with the structure Η include but not limited to:

Order

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567404 A7 B7 V. Description of the invention (11)

Representative comonomers with structure I, including but not limited to:

Representative comonomers with structure L, including but not limited to: -15- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 567404 A7

Representative comonomers with structure M, including but not limited to:

All copolymers according to the invention comprising comonomers having the structures K, L and M are characterized by fluorinated olefins and vinyl vinegars of the formula CH2 = CH02CR22, or ethyl acetate of the formula CH2 = CHOCH2R22 or CH2 = CHOR22 Ethers, in which R22 is a hydrocarbon group of about 4 to 20 carbon atoms, where the ratio of c: Η is relatively high, and its ratio is greater than 0.58, because the ratio of South C: Η is equivalent to good plasma resistance (this is related to Copolymers containing fluorinated fluorene and ethylenic esters of the formula CH2 = CH〇2 CR2 3, or vinyl mysteries of the formula CH2 = CHOCH2 R2 3 or CH2 = CHOR2 3, where R23 has C · · The ratio of plutonium is relatively low and less than 0.58. R22 and R23 are selected from the group consisting of alkyl, aryl, aralkyl, and cycloalkyl.) Representative comonomers having structure N, including but not limited to:

Where A = H, (CH3) 3C, (CH3) 3Si. -16- This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) 567404 A7 B7 Description of invention 13 In the above-mentioned preferred embodiment, the unsaturated η having at least one structure HN is used as the second type The listed comonomers are limited to the second comonomer if (and only if) the fluorinated copolymer does not contain other comonomers having a functional group selected from a carboxylic acid and a protective acid group. In this case, the fluorinated copolymer has only two comonomers (the two listed comonomers and no other unlisted comonomers) ^ In this case, there must be sufficient functionality The eight series are selected from carboxylic acids and protective acid groups, and are present in the at least one unsaturated compound (meaning the second listed comonomer), so that the photoresist of the present invention composed of a fluoropolymer can be used in The image is reproduced upon exposure, as explained in more detail below. In these specific examples using a fluorinated copolymer having only two comonomers, the mole percentages of the two comonomers in the copolymer are individually determined for the fluorine-based monomer (the first listed Monomer) and the first comonomer, which can range from 90%, 10% to 10%, 90%. Typically, these two comonomers have a mole percentage, and the individual fluoro-based monomers (the first listed monomer) and the second comonomer range from rhenium, fiber to dish, and rhenium. For some examples, in addition to the two listed comonomers (that is, (1) at least one ethylidene unsaturated compound, containing at least one fluorine atom, is conjugated to the ethylene system Unsaturated carbon atoms; with at least one unsaturated compound 'selected from the group of structures H_N), each of the fluorocopolymers of the present invention may contain an integer of ㈣ and no other co-monomers represented by ^ May include, but are not limited to, propionate, methyl acetic acid, tertiary butyl methacrylate, tertiary butyl methacrylate, tertiary butyl methacrylate, tertiary pentyl methacrylate, acrylic acid Isobutyl ester, isobutyl methylpropionate

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-17 · 567404 A7 B7 V. Description of the invention (14) Ester ethylene, ethyl acetate, decomposition of aconitic acid and acetic alcohol. In a specific embodiment in which the fluorinated copolymer has two listed comonomers and contains three or more comonomers, the second listed comonomer (meaning (ii) at least one unsaturated The compound, selected from the group of structures HN), has a mole percentage ranging from about 20 mole% to about 80 mole%, preferably from about 30 mole% to about 70 mole%, and more preferably about 40 Molar% to about 70 Molar% and most preferably about 50 to about 70 Molar%. The sum of the mole percentages of all other comonomers that make up this copolymer means that the balance adds up to 100% when added to the mole percentage of the second listed comonomer. Except for the second listed total The sum of the mole percentages of all other co-monomers present in the copolymer, other than the monomers, is in the broad range of about 80 mole% to about 20 mole%. The sum of the mole percentages of all other comonomers is preferably in the range of about 70 mole% to about 30 mole%. The sum of the mole percentages of all other comonomers is more preferably about 60 mole% to In the range of about 30 mole%, and more preferably, the sum of the mole percentages of all other comonomers is in the range of about 50 mole% to about 30. mole%. When the compound is a trimer, the appropriate ratio of the fluorine-based monomer (the first listed monomer) to the other comonomers can be summarized, which can range from 5:95 to 95: 5. When this fluorinated copolymer contains other comonomers having an acid group or a fumaric acid functional group in a sufficient amount necessary for developability, the functional group may or may not be present in the second listed co-monomer. One of the monomers is not limited. A specific gas-containing copolymer of the photoresist composition of the present invention includes a repeating unit derived from a white co-monomer having at least one fluorine atom. China National Standard (CNS) A4 specification (210 x 297 mm) 567404 A7 __B7 V. Description of the invention (15) Connected to ethylenic unsaturated carbon atom, the copolymer can be made by free radical polymerization. Polymers can be made by using bulk, solution, suspension, or emulsion polymerization techniques known to those skilled in the art, using free radical initiators such as azo compounds or peroxides. A specific fluorinated copolymer of the photoresist composition of the present invention, which contains only repeating units derived from all cyclic comonomers, and is completely lacking derived from having one or more fluorine atoms and connected to ethylene. The repeating unit of a comonomer of saturated carbon atoms. The copolymer can also be made by free radical polymerization, but in addition, it can be made by other polymerization methods, including vinyl addition polymerization and ring-opening metathesis polymerization (ROMP). . Two polymerization methods described later are known to those skilled in the art. Vinyl addition polymerization using nickel and palladium catalysts is disclosed in the following references: 1) Okoroanyanwu U .; Shimokawa, T .; Byers, JD ϊ Willson, CGJ Mol. Catal. A · Chemical 1998, 133, 93 »2) PCT WO 97/33198 (9/12/97) belongs to BF Goodrich; 3) Reinmuth, A .; Mathew, JP; Melia, J .;

Risse, W. Macromol. Rapid Commun. 1996, 17, 173; and 4) Breimig, S .; Risse, W. Makromol. Chem. 1992, 193, 2915. The ring-opening metathesis polymerization system is disclosed in the references 1) and 2) described above, using ruthenium and iridium catalysts; and 5) Schwab, P .; Grubbs, R. Η .; Ziller, JWJ Am. Chem · Soc. 1996, 118, 100; and 6) J Schwab, P .; France, M.B .;

Ziller, JW; Grubbs, R. H. Angew. Chem. Int. Ed. Engl. 1995, 34, 2039. Some of the fluorine-containing dimers of the photoresist composition of the present invention, wherein the dimers contain fluorine-based monomers (Such as TFE) and cyclic olefins (such as Zhengfang), the display is __ -19- This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm) 567404 A7 B7 V. Description of the invention ( 16) Alternating or approximately alternating dimers, having but not limited to the structure shown below ...

In this case, the present invention includes such alternating or approximately alternating copolymers, but is not limited in any way to only alternating copolymer structures. Such polymerization systems are described in WO 00/17712 published on March 20, 2000. The polymer (b) is a branched polymer containing a protected acid group, the polymer comprising one or more branched segments, which are chemically connected along a linear main segment. This branched polymer can be formed during radical addition polymerization of at least one ethylenically unsaturated macromonomer component and at least one ethylenically unsaturated comonomer. This ethylene-based unsaturated macromolecule has a number average molecular weight (Mn) between hundreds and 40,000, and a linear main chain segment formed by a polymerization reaction, and has a number average molecular weight (Mn) between about 2,000 and about 500,000. between. The weight ratio of the linear main chain segment to the branched chain segment is in a range of about 50/1 to about 1/10, and preferably in a range of about 80/20 to about 60/40. Typically, the macrocomponent has a number average molecular weight (Mn) of 500 to about 40,000, and more typically about 1,000 to about 15,000. Typically, such ethylenically unsaturated macromonomers can have a number average molecular weight (Mft4, which is equivalent to about 2 to about 500 monomer units, used to form macromonomers, and typically between 30 and 200 monomers In a typical embodiment, the branched polymer contains 25% to 100% by weight of a compatibility-promoting group, which means that the presence of these functional groups is to increase the Standards apply to Chinese National Standard (CNS) A4 specifications (210X 297 mm) 567404 A7 B7 V. Description of the invention (17) Compatibility of photoacid generator, preferably about 50% to 100% by weight, and better About 75% to 100% by weight. Suitable compatibilizing groups for ionic photoacid generators include, but are not limited to, non-hydrophilic polar groups and hydrophilic polar groups. Suitable non-hydrophilic polar groups Including but not limited to cyano (-CN) and nitro (-N02). Suitable hydrophilic polar groups include, but are not limited to, protic groups, such as hydroxyl (OH), amine (NH2), ammonium, amidoamine , Hydrazone, urethane, urea or mercapto; or carboxylic acid (C02H), sulfonic acid, sulfinic acid, phosphorus An acid or a salt thereof. The compatibility-promoting group is preferably present in the branched segment. Typically, the protected acid group (described below) is exposed to UV or other actinic radiation and then baked after exposure ( Meaning that after deprotection), carboxylic acid groups will be generated. The branched polymers present in the photosensitive composition of the present invention typically contain between about 3% and about 40% by weight The acid-protecting monomer unit is preferably between about 5% and about 50%, and more preferably between about 5% and about 20%. Branching chains of such preferred branched polymers Segments typically contain between 35% and 100% of the protected acid groups present. Such branched polymers, when completely unprotected (all protected acid groups are converted to free acid groups), It has an acid value between about 20 and about 500, preferably between about 30 and about 330, and more preferably between about 30 and about 130. Similarly, the ethylenically unsaturated macromolecular composition is preferred The system has an acid value between about 20 and about 650, more preferably between about 90 and about ^, and most of the free acid groups are in the branched segments. This aspect of the invention Each of the photosensitive compositions contains a branched polymer, also known as a comb polymer, which contains a protected acid group. This branched polymer has a branched segment, called a polymer arm, and is relatively For Linear Main Chain-21-This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm)

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Line 567404 A7 B7 V. Description of the invention (18) paragraph, has a limited molecular weight and a limited weight ratio. In a preferred embodiment, most of the protected acid groups are present in the branched segments. This composition also contains an ingredient, such as a photoacid generator, which makes the composition reactive to light energy, especially to radiant energy in the ultraviolet region of the electromagnetic spectrum, and most particularly to far or extreme In the ultraviolet region. In a specific embodiment, the branched polymerization system includes one or more branched segments that are chemically connected along a linear main segment, wherein the branched polymers have a number average molecular weight (Mn) of about 500. To 40,000. This branched polymer contains at least 0.5% by weight of branched segments. Branching segments, also known as polymer arms, are typically randomly distributed along a linear main segment. A "polymer arm" or branched segment is a polymer or oligomer of at least two repeating monomer units, which is connected to the linear main segment by a covalent bond. This branched segment or polymer arm can be incorporated into the branched polymer during the addition polymerization process of the macromonomer and the comonomer as a macromolecular component. For the purposes of the present invention, "macro pi is a polymer, copolymer or oligomer having a molecular weight ranging from hundreds to about 40,000, containing terminal ethylenic unsaturated polymerizable groups. This macro is preferably Linear polymers or copolymers terminated with ethylenic groups. Typically, this branched polymer is a copolymer with one or more polymer arms, and preferably at least two polymer arms, and its It is characterized in that it is between about 0.5 and about 80% by weight, preferably about 5 and 50% by weight: the monomer component used in the polymerization method is a giant. Typically, the giant is used in the polymerization method along with the macro The comonomer component in the same also contains a single ethylenic group, which can be copolymerized with an ethylenically unsaturated macrosome. This ethylenic unsaturated macrosome and the branches of the branched polymer formed _-22-_ This paper size applies to China National Standard (CNS) Α4 specification (210 X 297 mm)

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567404 A7 B7 V. Description of the Invention (19) The main chain of the segment and / or branched polymer may have one or more protected acid groups bonded to it. For the purposes of the present invention, 'f protected acid group' means a functional group that, when removed from protection, will obtain a free acid functional group that will strengthen the macrosome and / or the branched form to which it is bound The solubility, swelling or dispersing ability of the polymer in the aqueous environment. Protected acid groups can be incorporated into the ethylenic unsaturated giants and the branched segments and / or branched polymers of the branched polymers formed. In the main chain of the body, either during or after its formation. Although the addition polymerization of the macro and at least one ethylenic unsaturated monomer is preferred, it is preferred for the formation of branched polymers, but All known methods, whether by addition or condensation reactions to prepare branched polymers, can be used in the present invention. Furthermore, utilizing either preformed main chains and branched segments or on-site polymerized segments It can also be used in the present invention. The branched segment connected to the linear main segment can be derived from the ethylenic unsaturated giant, which is made according to the general instructions of US Patent 4,680,352 and US Patent 4,694,054. Giant system Free radical polymerization , Using a cobalt compound as a catalytic chain transfer agent, and especially a cobalt (II) compound. The cobalt (II) compound may be a pentacyanocobalt (II) compound, or a cobalt (II) chelate of the following compounds, Pirimido hydroxyimino compound, dihydroxy imino compound, diazadihydroxy imino dialkyldecadiene, diazadihydroxy imino-dialkyl fluorene--alkane hydrazone, tetra Azotetraalkyl ring: tetradecane tetrafluorene, tetraazatetraalkylcyclododecanetetraene, bis (difluoroboryl) diphenylglyoxal oxime, bis (difluoroboryl) di Methylglyoxal oxime, N, > Γ-bis (salicylidene) ethylenediamine, dialkyldiazepine-dioxodialkyldodecadiene, or dialkyldiazadioxydioxide Alkyl-tridecadiene. Low-molecular-weight methacrylate giant, also pentacyanide _-23-_ This paper size applies to China National Standard (CNS) A4 specification (210X297 mm)

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567404 A7 B7 V. Description of the invention (20) A cobalt (II) -based catalytic chain transfer agent is made, as disclosed in U.S. Patent No. 4,722,984. Illustrative macros that use this approach are methacrylic acid ester polymers with acrylate or other ethylenic monomers, where the polymer or copolymer has a terminal ethylenic group and a hydrophilic functional group. The preferred monomer components for preparing macros include: tertiary butyl methacrylate (tBMA), tertiary butyl acrylate (tBA), methyl methyl propionate (MMA); methyl propyl Ethyl gallate (EMA); Butyl methyl propionate (BMA); 2-ethylhexyl methyl propionate; Methyl acrylate (MA); Ethyl propionate (EA); Butyl acrylate (BA); 2-ethylhexyl propionate; 2-hydroxyethyl methacrylate (HEMA); 2-hydroxyethyl acrylate (HEA); methacrylic acid (MA); propionic acid (AA) ); Esters of acrylic acid and methacrylic acid, in which the ester group contains 1 to 18 carbon atoms; nitriles and amines of malonic acid and methylpropionic acid (such as acrylonitrile); methyl Glycidyl esters of valproic acid and malonic acid; decomposition of aconitic acid (IA) and decomposition of aconitic anhydride (ITA), half-esters, and stilbene imines; maleic acid and maleic anhydride, half-esters, and stigmas Amine; Aminoethyl methacrylate; Tertiary-butylaminoethyl methacrylate; Dimethylaminoethyl methacrylate; Diethylamino 'ethyl methacrylate; Amine amine Ethyl ester; acrylic acid dimethylamino ethyl ester; diethyl acetic acid Ethyl acetate; Acrylamide; N-Third-octylpropanamide; Ethyl methyl ether, phenethyl ethyl (STY); Methyl phenyl ethyl: acetyl (AMS); ethyl ethyl acetate; chloroethyl Woman waiting. Decomposition aconitic anhydride (ITA, 2-methylene succinic anhydride, CAS number = 2170-03-8) is a particularly advantageous comonomer for branched polymers, because it has two active T-energy groups, presenting Anhydride form, which becomes three when ring-opening, and ___ -24- This paper is applicable in g @ 家 standard (CNS) A4 specification (21G X 297 public director) — ------ " ~

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Line 567404 A7 B7 V. Description of the invention (21.) Diacid is obtained. The ethylenic unsaturated group is the first functional group, which provides the ability of this comonomer to be incorporated into the copolymer, such as by free radical polymerization. The anhydride moiety is a second functional group that can react with a variety of other functional groups to obtain a covalently bonded product. An example of a functional group with which an anhydride portion group can react is a hydroxyl group in an alcohol to form an ester chain. When the anhydride portion of ITA reacts with a hydroxyl group, it forms an ester chain, and the free-state carboxylic acid portion group is a third functional group. This carboxylic acid functional group can be used to impart aqueous solution processing properties to the photoresist of the present invention. If a PAG with a radical is used, as shown in some examples, it can be covalently bonded to the PAG (or other optical link) via an ester link (or other covalent link such as amidine, etc.) of this type. Active ingredient) is linked (tethered) to a branched polymer containing ITA comonomer or its analog. This branched polymer can be made by any conventional addition polymerization method. This branched polymer or comb polymer can be prepared from one or more compatible ethylenic unsaturated macromonomer components and one or more compatible conventional ethylenically unsaturated comonomer components. The addition-polymerizable ethylenically unsaturated comonomer components are preferably propionate, methylpropionate, phenethylaceous substance, and mixtures thereof. Appropriate addition-polymerizable ethylenic unsaturated comonomer components, including: tertiary-butyl methacrylate (tBMA), tertiary butyl acrylate (tBA), and methyl methacrylate (MMA) -I ethyl methacrylate (EMA); butyl methacrylate (BMA); 2-ethylhexyl methacrylate; methyl propionate (MA); ethyl acrylate (EA); propionate. Acid Butyl ester (BA); 2-ethylhexyl acrylate; 2-hydroxyethyl methacrylate (HEMA); 2-hydroxyethyl acrylate (HEA); methacrylic acid (MAA); propionic acid (AA) ); Acrylonitrile (AN); Methacrylonitrile-25- This paper size applies to China National Standard (CNS) A4 (210X 297 mm)

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567404 A7 ___B7___ V. Description of the Invention (22) (MAN); Decompose aconitic acid (IA), and decompose aconitic anhydride (ΓΓΑ), half esters and succinimide; maleic acid, and maleic anhydride , Half-esters and ammonium imines; aminoethyl methylpropionate; third-butylaminoethyl methacrylate; dimethylaminoethyl methylpropionate; diethyl methylpropionate Aminoethyl ester; Aminoethyl propionate; Dimethylaminoethyl propionate; Diethylaminoethyl acrylate; Allylamine; N-Third-octylpropenylamine; Ethylfluorenyl Methyl ethers; phenethylhydrazone (S); α-methylphenethylhydrazone; ethylacetoacetate; chloroacetamido and the like. Most of the copolymerizable monomers must be propanoic acid or phenyl ethylenic substances or copolymers of these monomers with acrylates and other ethylenic monomers. Each component of the branched polymer of the present invention may contain a linear main segment and / or a branched segment ' which may contain various functional groups. A "functional group" is considered to be a group capable of being attached to any part of the main segment or branch segment by a direct valence bond or by a linking group. Examples of functional groups that can be carried by the main chain or branched chain are -COOR24; -OR24; _SR24, where R24 can be hydrogen, an alkyl group having i to 12 carbon atoms; 3-12 Carbon alkyl cycloalkyl; aryl, alkaryl or aralkyl having 6 to 14 carbon atoms; heterocyclic group containing 3 to 12 carbon atoms' and additionally containing s, o, N or P atoms Or -〇R27, where R27 may be an alkyl group of 2 carbon atoms, an aryl, alkaryl or aralkyl group having 6 to 14 carbon atoms; -CN; -NR25R26, or 0-c-nr25r26 /, In which R and r6 may be hydrogen's alkynyl group having 1 to 12 carbon atoms; cycloalkyl group having 12 carbon atoms; aryl group, aryl group having 6 to 14 carbon atoms, ----- ---___- 26-This paper is suitable for financial standards (CNS) α4 · (2ι () χ 297 public director) 567404 A7

Aromatic radicals; -CH2〇R28, where R28 — its ·, R is lice, alkane group of 1 to 12 carbon atoms, or ring enthalpy of 3-12 carbon atoms, its butyl group has Aromatic earth ^ square, aralkyl, or R25i ^ R26 ring 4p ^ ^ m ^ 7 to 14 carbon atoms, Han can be formed together with 3 to 12 Tibetan atoms, and contains at least one 『王 乂A heterocyclic ring of S, N, 0 or P; p29 ——O = CR30R31 R, R30 and r3 1 in eight may be hydrogen, an alkyl group of π to π carbon atoms, or an alkyl group of 3 carbon atoms Aryl, alkaryl, square alkyl, or -COOR24 of 6 to 14 carbon atoms, or when used together with r29, r30, and / or r31 'can form a cyclic group, s03h; amine Isocyanate groups; isocyanates or isocyanates that are 'blocked by engineering'; | diarrhea group; ethylene oxide group; aziridine group; quinone group; nitride group; azo group; azide Diazo; ethanoyl ethoxy; -SiRWR33R34, wherein r32, r33 and r34 may be an alkyl group having 3] fluorene atoms, or a cycloalkyl group having 3 to 12 carbon atoms, or -0R35, Where R35 is an alkyl group of M2 carbon atoms, or 3-12 carbon atoms Cycloalkyl; aryl, alkaryl or aralkyl of 6 to 14 carbon atoms; or _〇s〇3R36, ^ 〇〇〇２〇36, -P〇2R36, _PR36R37R38, -〇Ｏ〇〇36, ^ 36 ^ 7 or N + R36R37R38 group (where r36, r37 and r38 can be hydrogen, 1 to 12 carbon atoms, or 3 to 12 carbon atoms, and 6 to 14 carbon atoms, Aryl, alkaryl, or aralkyl; or any of the foregoing salts or sulfonium salts. Preferred functional groups are -COON, -OH, -NH2, amido, vinyl, urethane, and isocyanate , Blocked isocyanate group, or a combination thereof. The functional group can be located at any position on the branched polymer. However, sometimes it is necessary to choose ___- 27- This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm)

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567404 A7 B7 V. Description of the invention (24.) Select comonomers that give overall polymer characteristics to the linear main segment of the branched polymer, and in addition to hydrophilicity, give physical and chemical properties to the branched segments Functional macro, such as solubility, reactivity, etc. In certain preferred embodiments of the present invention, the branched polymer contains a functional group compatible with the photoacid generator, and the functional group is distributed in the branched polymer such that 25 to 100% The functional group is present in the segment of the branched polymer containing most of the protected acid groups. These functional groups are satisfactory because photoacid generators have a greater compatibility with branched polymer segments protected by acid groups, resulting in higher light speeds and possibly higher Resolution, and / or other desirable properties of photoresists, which include branched polymers having such functional groups to promote compatibility. For ionic PAGs, such as triarylsulfonium salts, functional groups that promote compatibility include but are not limited to polar non-hydrophilic groups (such as nitro or cyano) and polar hydrophilic groups (such as hydroxyl, carboxyl ). For non-ionic PAGs, such as the structure III below, the preferred functional group used to impart compatibility is less polar than the polar groups listed above. For the case described below, suitable functional groups include, but are not limited to, groups that impart fairly similar chemical and physical properties to non-ionic PAGs. Taking the following as two specific examples, aromatic and perfluoroalkyl functional groups are effective to promote the compatibility of branched polymers with nonionic PAGs (such as the structure III given below). In some preferred embodiments, the branched polymer is an acrylic / methacrylic / styrenic copolymer, which is at least 60% by weight acrylate and has at least 60% methacrylate repeating units, present in Regardless of the first position or the second position, the first position is one of the key segments (Italy-28- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm)

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567404 V. Description of the invention (25) (Branch segment or linear main segment), the second position is a different segment from the first position, in which at least 60% of the repeating units of acrylate are present in the second Positions. In some embodiments, the branched polymer is a gas-containing graft copolymer, which comprises repeating units derived from at least one ethylenically unsaturated compound, the compound contains at least one fluorogen + and is covalently linked To the ethylenically unsaturated carbon atom. The repeating unit with at least one fluorine atom may be either in the main segment of the linear polymer or in the branched polymer segment; it is preferably in the main segment of the linear polymer. Suitable for the gas-containing graft copolymer of the present invention, the representative ethylenic unsaturated compounds include, but are not limited to, tetrakisene, chlorotrifluoroacetamidine, hexafluoropropylene, trifluoroethylene, difluoroethylene, etc. Acetyl and Taogang 2, in which Rf4l is a saturated fully branched group of about 10 carbon atoms. The fluorinated copolymer of the present invention may contain any other integers, monomers, and monomers. Including but not limited to those listed above. Preferred comonomers: four are ethylammonium, chlorotrifluoroethylene, hexafluoropropene, trifluoroethylene, and tritium, and their = Rf is a saturated perfluoroalkyl group having 1 to about 1G carbon atoms. More preferred comonomers are tetrafluoroethylene, fluorodifluoroethane, hexafluoropropylene, and saturated perfluorofluorenyl groups of 1 to about carbon atoms. Best co-, ethylene and chlorotrifluoroethylene. ^ In some preferred embodiments, the house gas graft copolymer further comprises a repeating unit derived from at least one unsaturated compound, and is selected from the group including the structure shown in the above polymer (a). In a specific embodiment of the present invention, the pag is connected to the fluorine-containing graft copolymer by a covalent bond (that is, retained) to obtain a photoresist. This paper rule Qiancaiguan-29- 567404 A7 B7 Five invention descriptions (26 In some preferred embodiments, the branched polymer is a fluorinated copolymer, which is derived from at least one ethylidene unsaturated compound The repeating unit 'This compound contains a fluoroalcohol functional group and has the following structure:

-C (Rf) (Rf,) OH where Rf and Rf are the same or different fluorocarbon groups of 1 to about 10 carbon atoms, and (CF2) n is used together, where η is 2 to 10. A specific fluorine-containing branched copolymer according to the present invention, which comprises a repeating unit derived from at least one ethylfluorene-based unsaturated compound containing a fluoroalcohol functional group, and the copolymer may have a fluoroalkyl group as The fluoroalcohol functional group is a part. These fluoroalkyl systems are called core and Rf, and they can be partially fluorinated or fully fluorinated (meaning perfluoroalkyl). Broadly speaking, the same or different fluoroalkyl groups of 1 to about 10 carbon atoms are used together or (CF2) n 'where η is 2 to 10 (in this last sentence, the term "used together" is used It means that Rf and Rf are not individual, discontinuous fluorinated alkyl groups, but form a ring structure together, as shown in the following 5-membered ring case:

According to the present invention, Rf and Rf may be partially fluorinated alkyl groups without limitation, but there must be a sufficient degree of fluorination to impart acidity to the hydroxyl group (-0H) of the fluoroalcohol functional group, so that It is essentially removed in the test medium, such as in aqueous sodium hydroxide solution or tetraalkylammonium hydroxide solution. In the preferred case according to the present invention, there is sufficient fluorine substitution in the fluorinated alkyl group of the fluoroalcohol functional group, so that the hydroxyl group has a pKa value as follows: -30- This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 567404 A7 B7 V. Description of the invention (27) 5 < pKa < ll. Rf and Rf are preferably perfluoroalkyl groups having 1 to 5 carbon atoms independently, and Rf and Rf are most preferably trifluorofluorenyl (CF3). Each fluorinated copolymer according to the present invention preferably has an absorption coefficient of less than 4.0 microns'1 at a wavelength of 157 nm, more preferably less than 3.5 microns · 1 at this wavelength, and more preferably at This wavelength is below 3.0 micrometers. The fluorinated polymer, photoresist and method of the present invention containing a fluoroalcohol functional group may have the following structure:

-ZCH2 C (Rf) (Rf,) OH where Rf and Rf are the same or different fluoroalkyl groups of 1 to about 10 carbon atoms, or used together as (CF2) n, where η is 2 to 10; Z series It is selected from the group consisting of oxygen, sulfur, nitrogen, phosphorus, other VA group elements, and other VIA group elements. The terms "other VA group elements" and "other VIA group elements" should be understood to mean that these terms refer here to any other element in one of these groups of the periodic table and are not listed in this group Element (meaning oxygen, sulfur, nitrogen, phosphorus). Oxygen is the preferred Z group. Some illustrative but non-limiting examples of representative comonomers that contain fluoroalcohol functionality and are within the scope of the present invention are set out below:

CH2C (CF3) 2OH ch2och2c (cf3) 2〇h

CH2C (CF3) 2〇H ch2och2c (cf3) 2oh ch2 = ch〇ch2ch2〇ch2c (cf3) 2〇h ch2 = ch〇 (ch2) 4och2c (cf3) 2〇h -31-This paper standard applies Chinese national standard ( CNS) A4 specification (210X 297 mm) 567404 A7 B7 V. Description of the invention (28) As is well known to those skilled in the art of polymer polymerization, ethyl ethene unsaturated compounds undergo free radical polymerization, and they are derived from ethyl ethene Polymers of repeating units of unsaturated compounds. Specifically, the ethyl fluorene unsaturated compound having the following structure: p \ xi c = c S D is as described above with respect to the copolymer (al). · A fluoropolymer having at least one fluoroalcohol group (c), selected from the group consisting of: (cl) a fluoropolymer containing repeating units derived from at least one ethylenic unsaturated compound, the compound containing a fluoro group Alcohol functional group with the following structure:

-C (Rf) (Rf,) OH where & and 1 ^ are as described above; (c2) a fluorinated copolymer comprising repeating units derived from at least one ethylenic unsaturated compound, characterized in that At least one ethylenically unsaturated compound is cyclic or polycyclic, at least one ethylenic unsaturated compound contains at least one fluorine atom, is covalently connected to an ethylenic unsaturated carbon atom, and at least one ethylenic unsaturated compound. The unsaturated compound contains a meryl alcohol functional group and has the following structure:.

-C (Rf) (Rf,) OH wherein Rf and Rf are as described above; (c3)-a fluorocopolymer, comprising: (i) a repeating mono-32 derived from at least one ethylidene unsaturated compound -This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) 567404 A7 B7 5. Description of the invention (29) position, the compound contains at least three fluorine atoms, covalently connected to two vinyl Saturated carbon atom; and (ii) a repeating unit derived from an ethyl acetate unsaturated compound, which contains a fluoroalcohol functional group, and has the following structure:

• C (Rf) (Rf,) OH where Rf ^ Rf are as described above; (c4) an allegorical copolymer comprising repeating units derived from at least one ethylenically unsaturated compound, the compound containing a fluoro alcohol Functional group with the following structure:

_ZCH2C (Rf) (Rf,) OH wherein Rf and Rf are as described above; and Z is an element selected from the VA group and other VIA groups of the periodic table (CAS version). Typically, X is a sulfur, oxygen, nitrogen or phosphorus atom; (c5)-a fluorine-containing polymer, which contains the following structure ...

Each of R40, R41, R42, and R43 is independently a hydrogen atom, a halogen atom, a hydrocarbon group containing 1 to 10 carbon atoms, substituted with at least one 0, S, N, P, or halogen and having 1 to 12 carbon atoms. Hydrocarbon group, such as alkoxy group, carboxylic acid-33- This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) 567404 A7 B7 V. Description of the invention (30) group, polyacid group or those containing the following structure Functional group: -C (Rf) (Rf,) OR44 where Rf and Rf are as described above; R44 is a hydrogen atom, or an acid- or base-unstable protecting group; v is the number of repeating units in the polymer; w Is 0-4; at least one repeating unit has a structure in which at least one of R4 0, R4 1, r4 2 and R43 contains the structure C (Rf) (Rf,) OR44, for example R40, R4l & R42 are hydrogen atoms, and R4 3 is CH2 OCH2 C (CF3) 2 OCH2 C02 C (CH3) 3, where ch2 C02 c (ch3) 3 is an acid or base labile protecting group, or R43 is 0CH2C (CF3) 2OCH2C02CCCH3) 3, where 0CH2C02C (CH3 ) 3 is an acid or base labile protecting group; and (c6) a polymer comprising: (i) a repeating monomer derived from at least one ethylidene unsaturated compound The fluorine-containing alcohol compound functional group having the following structure:

-C (Rf) (Rf.) OH where Rf and Rf. Are as described above; and (ii) a repeating unit derived from at least one ethylenic unsaturated compound having the following structure: (H) (R45) C = C (R46) (CN) wherein R45 is a hydrogen atom or CN; R46 is a (^-(^ alkyl, hydrogen atom, or C02R47 group, where three is < ^-0: 8 alkyl or hydrogen atom. This fluorine polymerization The block or copolymer contains repeating units (discussed below) derived from at least one ethylenically unsaturated compound that contains a fluoroalcohol functional group which may have a fluoroalkyl group as part of the fluoroalcohol group, and Is described in the foregoing about the copolymer (b). Such fluoroalkyl systems are referred to as Rf _ -34- t ^ # ^. (CNS) A4W (21〇X297 ^)

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567404 A7 B7 V. Description of the invention (31) and Rf. As is well known to those skilled in the art of polymerizing St polymers, ethylenically unsaturated compounds undergo radical polymerization to obtain polymers having repeating units derived from ethylenically unsaturated compounds. Specifically, the ethylene-based unsaturated compound having the following structure: P \ 'c = cο / \ is described above with respect to the copolymer (al). Each fluorinated copolymer according to the present invention has an absorption coefficient at a wavelength of 157 nm of less than 4.0 μm · 1, preferably at a wavelength of less than 3.5 μm_1, and more preferably at a wavelength of less than 3.0 μm · 1, and at this wavelength it is more preferably below 2.5 μm4. The fluorinated polymer, photoresist and method of the present invention containing a fluoroalcohol functional group may have the following structure:

-ZCH2C (Rf) (Rf,) OH Where Rf and Rf are as described above; Z is as described above. Some illustrative but non-limiting examples of representative comonomers that contain fluoroalcohol functionality and are within the scope of the present invention are set out below:

--CH2C (CF3) 20H-~ CH2〇CH2C (CF3) 2〇H

CH2C (CF3) 2〇H

ch2och2c (cf3) 2〇h -35- This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 567404 A7 B7 V. Description of the invention (32)

CH2 = CHOCH2CH2OCH2C (CF3) 2OH CH2 = CH0 (CH2) 40CH2C (CF3) 20H

Various bifunctional compounds which can be initially provided with cross-linking and subsequent cleavage (for example when exposed to strong acids) can also be used as comonomers in the copolymers of the present invention. As an illustrative but non-limiting example, the bifunctional comonomer NB-F-OMOMO-F-NB is satisfactory as a comonomer in the copolymers of the present invention. It is similar to a bifunctional co-monomer, and when present in the copolymer component of the photoresist composition of the present invention, a copolymer can be obtained, which is a relatively high molecular weight and a lightly crosslinked material. Photoresist compositions incorporating such copolymers containing bifunctional monomers may have improved imaging and imaging characteristics, since upon exposure (which produces a strong acid photochemically, as explained below), Factors such as the splitting of bifunctional groups, and therefore a significant reduction in molecular weight, can provide greatly improved imaging and imaging characteristics (eg, improved contrast). These fluoroalcohol groups and their specific examples are described in more detail above and in PCT / US00 / 11539, filed on April 28, 2000. At least a portion of the nitrile functional groups present in the nitrile / fluoroalcohol polymer are caused by the incorporation of repeating units derived from at least one ethylenically unsaturated compound, which has at least one nitrile group and has the following structure: (H ) (R48) C = C (R49) (CN) where R48 is a hydrogen atom or a cyano group (CN); R49 is a carbon source ranging from 1 to about 8 carbon atoms __ This paper size applies to China National Standard (CNS) A4 specifications (210X 297 mm) 567404 A7 B7 V. Description of the Invention The alkyl group of (33), C02R50 group, where R50 is an alkyl group, or hydrogen atom, ranging from 1 to about 8 carbon atoms. The ratios of propionitrile, methylpropionitrile, transbutyronitrile (trans-1,2-dicyanoethylene) and cisbutyronitrile (cis-1,2-dicyanoethylene) are good. Acrylonitrile is the best. Nitrile / fluoroalcohol polymers are typically characterized by having repeating units derived from at least one ethylenic unsaturated compound, which contain fluoroalcohol functional groups, which are present in the nitrile / fluoroalcohol polymer, about 10 to about 60 moles. Ear percentages, and repeating units derived from at least one ethylidene-based unsaturated compound, which contain at least one nitrile group present in the polymer, from about 20 to about 80 mole percentages. More typically, a nitrile / fluoroalcohol polymer that achieves a low absorption coefficient value is characterized by having repeating units derived from at least one ethylenically unsaturated compound, which contains a fluoroalcohol functional group, at 45 or less The mole percentage is present in the polymer, and is more typically less than or equal to 30 mole percentage, and has a relatively small amount of repeating units containing nitrile groups, resulting in at least a portion of the polymer's balance. In a specific embodiment, the polymer comprises at least one protected functional group. The functional group of the at least one protected functional group is typically selected from the group consisting of an acidic functional group and a basic functional group. Non-limiting examples of protected functional groups are carboxylic acids and fluoroalcohols. In another embodiment, the nitrile- 1: fluoro alcohol polymer may include an aliphatic polycyclic functional group. In this specific embodiment, the percentage of repeating units of the nitrile / fluoroalcohol polymer containing aliphatic polycyclic functional groups ranges from about 1 to about 70, preferably about 10 to about 55 mole%; and A more typical range is from about 20 to about 45 mole%. -37-

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k This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 567404 A7 B7 V. Description of the invention (34) Except as explicitly stated and referred to herein, this nitrile / fluoroalcohol polymer may contain Other functional groups are subject to the condition that aromatic functional groups are preferably absent from the nitrile / fluoroalcohol polymer. The presence of aromatic functional groups in these polymers has been found to detract from their transparency and cause them to absorb too strongly in the far and extreme UV regions, making them unsuitable for imaging at these wavelengths. In some embodiments, the polymerization system is a branched polymer containing one or more branched segments, which are chemically connected along a linear main segment. This branched polymer can be formed during radical addition polymerization of at least one ethylenically unsaturated macromonomer component and at least one ethylenic unsaturated co-monomer. This branched polymer can be made by any conventional addition polymerization method. This branched polymer or comb-type polymer can be made from one or more compatible ethylenic unsaturated giant components, and one or more compatible conventional ethylene-based unsaturated giant components, and one or more A variety of compatible conventional acetamidine unsaturated monomer components. Typically, the addition-polymerizable ethylenically unsaturated monomer components are acrylonitrile, methacrylonitrile, transbutadionitrile, maleimonitrile, and protected and / or unprotected unsaturated fluorine Alcohols and protected and / or unprotected unsaturated carboxylic acids. The structure and method of making this type of branched polymer is discussed with respect to the polymer type (b) above and as described in WO 00/25178. · — _ Fluoropolymer with at least one fluoroalcohol, which may further include a spacer, selected from the group consisting of ethylene, α-olefins, 1, Γ-disubstituted fluorenes, vinyl alcohols, vinyl ethers, and 1, 3-dienes. Polymer ⑹ includes perfluorinated (2,2-dimethyl-1,3-dioxolene) or CX2 = CY2 -38- This paper size applies to China National Standard (CNS) A4 (210X 297 mm)

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567404 A7 B7 V. Amorphous vinyl homopolymer of invention description (35), where X = F or CF3, and Y = -H, or perfluoro (2,2-dimethyl-1,3-dioxy Wu Yi) and CX2 = CY2 amorphous ethylene-based copolymer, the homopolymer or copolymer contains one or more comonomers CR51R52 = CR53R54, where each R51, R52, R53 is independently selected from Η or F, and wherein R54 is selected from the group consisting of -F, -CF3, -OR55, where R55 is CnF2n + l, where n = 1 to 3, -OH (when R53 = H), and C1 (when R51, R52, and R53) = F). The polymer (d) may further include CH2 = CHCF3 and CF2 = CF2, in a ratio of 1 ·· 2 to 2: 1, CH2 = CHF and CF2 = CFC1, in a ratio of 1 ·· 2 to 2: 1, and CH2 = CHF and CC1H = CF2, in a ratio of 1: 2 to 2: 1: perfluoro (2-methylene acetomethyl-1,3-dioxolane) in any ratio with perfluoro (2,2-dimethyl- 1,3-dioxofluorene), an amorphous ethylene copolymer of perfluoro (2-methylene-4-methyl-1,3-dioxofluorene) and difluoroethylene in any proportion It is an amorphous, homopolymer of perfluoro (2-methylene-4-methyl-1,3-dioxolane). These polymerization systems are made by polymerization methods known in the art about fluoropolymers. All these polymers can be made from monomers, inert fluids (such as CF2 C1CC12 F, CF3 CFHCFHCF2 CF3, or carbon dioxide) and soluble free radical initiators such as HFPO dimer peroxide 1 or Perkadox® 16N, sealed in a cooled autoclave, and then heated in an appropriate manner to initiate polymerization. CF3 CF2 CF2 OCF (CF3) (C = 0) 0d (C = 0) CF (CF3) OCF2 CF2CF3 1 For HFPO dimer peroxides, room temperature (~ 25 ° C) is the appropriate polymerization temperature, For Perkadox®, temperatures of 60 to 90 ° C can be used. Depending on the temperature of the monomer and polymerization reaction, the pressure can be changed from atmospheric pressure to ___- 39-_ This paper size applies to China National Standard (CNS) A4 (210X 297 mm)

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Line 567404 A7 B7 V. Description of the invention (36 ·)

500psi or higher. Then, when the polymer is formed as an insoluble precipitate, it can be separated by filtration, or when it is soluble in the reaction mixture, it can be separated by evaporation or precipitation. In many cases, apparently dried polymers still retain considerable solvents and / or unreacted monomers, and must be further dried in a vacuum oven, preferably under nitrogen flow. Many polymers can also be made by aqueous emulsion polymerization, which is achieved by deionized water, initiators such as ammonium persulfate or Vazo® 56 WSP, monomers, surfactants such as ammonium perfluorooctanoate, or dispersants For example, methyl cellulose is sealed in a cooling autoclave and heated to initiate the polymerization reaction. This polymer can be separated by breaking up any formed emulsion, filtering and drying. In all cases, oxygen should be excluded from the reaction mixture. Chain transfer agents such as chloroform can be added to reduce molecular weight. Order

Nitrile / fluoroalcohol-containing polymers ⑷ made from substituted or unsubstituted acetamyl ethers, comprising: (el) a polymer comprising: (i) derived from at least one ethylenically unsaturated compound Repeating unit, the compound contains an ethyl ether functional group and has the following structure: ch2 = cho-r56 where R5 6 is an alkyl group having 1 to 12 carbon U, an aryl group having 6 to about 20 carbon atoms, Aralkyl or alkaryl, or the group is substituted by S, O, N or P atoms; and (ii) a repeating unit derived from at least one ethylenic unsaturated compound having the structure: -40- present Paper size applies to China National Standard (CNS) A4 (210X297 mm) ^ 0/404

(H) (R5 7) 〇C (R5 8) (CN), in which R is a hydrogen atom or a cyano group; R5 S is a range from 1 to about 8 carbon atoms, and soil C0R2, where R59 is a range An alkyl group from i to about 8 carbon atoms, or a hydrogen atom; and (111) a repeating unit derived from at least one ethylenic unsaturated compound containing an acidic group; and (e2) a polymer comprising (1) A repeating unit derived from at least one ethylenically unsaturated compound, the compound containing a vinyl ether functional group and a fluoroalcohol functional group, and having the following structure:

C (R6 0) (R6 1) = c (R6 2). 〇-DC (Rf) (Rf t) 〇H, middle R, r6 1 and R6 2 are independently hydrogen atoms, ranging from i to about 3 Carbon = carbon atom; D is at least one atom, which is a carbon atom connected to ethynyl functional soil, via an oxygen atom, to a fluoroalcohol functional group; Rf and Rf are as described above; and ⑻ is derived Repeating units from at least one ethylenically unsaturated compound having the following structure: (H) (R5 7) C = C (R5 8) (CN), where R is a hydrogen atom or a cyano group; R5 8 is a range from 丨 to About 8 carbon atoms < alkyl, Co2R59, where R59 is an alkyl 'or hydrogen atom with i ranging from i to about 8 carbon atoms; and (ii) derived from at least one ethyl group containing an acidic group This is a repeating unit of unsaturated compounds. This fluoroalcohol group and specific examples are more detailed for the polymer (c6) above.

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567404 A7 B7 5. Description of the invention (38 ·). Some illustrative but non-limiting examples of vinyl ether monomers that fall into the general structural formula (previously) containing fluoroalcohol functional groups and are within the scope of the present invention are presented below: ch2 = choch2 ch2 OCH2 C (CF3) 2 OH CH2 = CHO (CH2) 4 OCH2 C (CF3) 2 OH nitrile groups and specific examples thereof, and linear and branched polymers made of nitrile and fluoroalcohol groups, and The specific embodiment is also described and referred to the polymer (c6) in more detail. These polymers may be present in an amount of about 10 to about 99.5% by weight, based on the weight of the entire composition (solid). Method for forming a photoresist image The method for preparing a photoresist image on a substrate includes the following sequence: (X) exposing the photoresist element in an image copying manner to form an imaged and unimaged area, wherein the photoresist element Comprising a substrate; an etch-resistant layer; and at least one photoresist layer made from a photoresist composition comprising: (A) a polymer selected from the group consisting of ⑷- (e) above, and mixtures thereof; and ( B) a photoactive component; and (Y) developing an exposed photoresist layer having imaged and unimaged areas to form a relief image on a substrate. The photoresist layer is exposed by image replication. The photoresist layer is formed by applying a photoresist combination j to a substrate with an anti-etching layer and drying to remove the solvent. For example, the etch-resistant layer is applied to a substrate by chemical vapor deposition (CVD). The photoresist layer thus formed is sensitive in the ultraviolet region of the electromagnetic spectrum, and especially for wavelengths of $ 365 nanometers. The image copy exposure of the photoresist composition of the present invention can be applied in many different sizes. _-42-_ This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm).

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567404 A7 B7 5. Description of the invention (39 ·) Achieved at the same UV wavelength, including but not limited to 365 nm, 248 nm, 193 nm, 157 nm and lower wavelengths. Exposure by image reproduction method, which is achieved with UV light of 248 nm, 193 nm, 157 nm, or lower wavelengths, and is better achieved with UV light of 193 nm, 157 nm, or lower wavelengths And the best is achieved with ultraviolet light of 157 nm or lower wavelength. Exposure by image reproduction can be achieved either numerically using a laser or equivalent device, or non-numerically using a photomask. Numerical imaging using lasers is preferred. Suitable laser devices for numerical imaging of the composition of the present invention include, but are not limited to, argon-fluorine lasers using UV output at 193 nm, krypton-fluorine lasers using UV output at 248 nm , And fluorine (F2) laser, use output at 157nm. As discussed earlier, because the use of lower wavelength light for image reproduction exposure is equivalent to a higher resolution (lower resolution), the use of lower wavelengths (such as 193nm or 157nm or lower) is usually Better than using higher wavelengths (eg 248 nm or higher). Development The components in the photoresist composition of the present invention must contain sufficient functionality γ for development after the image is copied and exposed to UV light. This functional group is preferably an acid or a protected acid so that an aqueous developer can use an alkaline developer such as a sodium hydroxide solution, a potassium hydroxide solution, or an ammonium hydroxide solution. β For example, the polymer (c) of the photoresist composite vermiculite of the present invention is typically an acid-containing material, containing at least one fluorine-containing alcohol-containing monomer, and has the following structural unit ... -C (Rf) (Rf, ) Pj where Rf and Rf are the same or different fluoroalkyl groups of 1 to 10 carbon atoms, or are used together as (CF2) n, where n42 to ⑴. Content of acidic fluoroalcohol groups, 567404 A7 B7

It is measured for a specific composition by optimizing the amount required for good development of gas in an aqueous alkaline developer.

-When the water-containing processable photoresist is coated or otherwise applied to the laughing material and exposed to UV light by image reproduction, it may be necessary for the photoresist composition ^ It may be necessary that the adhesive substance should be Contains a sufficient amount of acid groups (such as fluoroalcohol group) and / or protected acid groups, which are at least partially removed from protection during exposure, so that the photoresist (or other photoimageable coating composition) can be used in Processing in water-based diagnostic imaging agents. In the case where the photoresist layer is positively operated, the photoresist layer is removed during the development, and is removed on the part exposed to the UV radiation, and on the unexposed part, during the development, it is not substantially changed. In the imaging direction, the imaging is performed by using an aqueous alkaline liquid, such as tetrahydroxide containing 0.262N, and a full aqueous solution (where the imaging system is under 251, which usually takes less than or equal to 120 seconds). & In the case of a negative-acting photoresist layer, the photoresist layer is removed during the development, on a portion not exposed to UV radiation, but during the development, on the exposed portion, the Substantially unaffected, the imaging system uses either a critical fluid or an organic solvent. f Critical fluids, as used herein, are one or more substances that are heated to a temperature near or below their critical temperature and compressed to a pressure near or above their critical pressure. The critical fluid in the present invention is a material higher than 15 t at least below the critical temperature of the fluid, and a pressure T higher than 5 atmospheres at least below the fluid's boundary pressure. Carbon dioxide can be used as a critical fluid in the present invention. Various organic solvents can also be used as the developer in the present invention.纟 Including but not limited to dentified solvents and non-self-solvent solvents, H is typical, while fluorinated solvents are more typical. -44-

567404 A7 B7 5. Description of the invention (41.) The anti-etching layer can be developed by any known conventional method. For example, the pattern of the photoresist layer can be transferred to the anti-etching layer by etching the exposed area of the anti-etching layer in an anisotropic manner. -45- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

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Claims (1)

567404 Six patent application Fan Yuan The wavelength of rice has an absorption coefficient of less than 5.0 microns -1. 3. For example, the photoresistive element of the first patent range, wherein the polymer has an absorption coefficient of less than 4.0 microns-1 at a wavelength of 157 nm. 4. The photoresist element according to item 1 of the patent application range, wherein the polymer has an absorption coefficient of less than 3.5 microns-1 at a wavelength of 157 nm. 5. The photoresistive element according to item 1 of the scope of the patent application, wherein the polymer (a) is a fluorinated copolymer containing repeating units derived from at least one ethylenically unsaturated compound, which is characterized by at least one ethylenic resin The unsaturated compound is polycyclic, and at least one ethylenically unsaturated compound contains at least one fluorine atom, and is covalently connected to the ethylenically unsaturated carbon atom. 6. The photoresistive element of the scope of application for patent application, wherein the polymer ⑷ is a fluorinated copolymer, which contains a repeating monofluorene derived from at least one polycyclic ethylfluorene unsaturated compound, the compound having at least one The atom or group is selected from the group consisting of a fluorine atom, a perfluoroalkyl group, and a perfluoroalkoxy group, and is characterized in that the at least one atom or group is covalently connected to a carbon atom, and the hindrance system is included in The ring is rich, and it is separated from each unsaturated carbon atom of the B # unsaturated compound by at least one carbon atom connected by formula. /, 彳 only 10,000 7. If the photoresistance element in the scope of application for the patent, the poly-blocked poly-free with protected acid group! The polymer contains mouth branched segments that are chemically connected along a linear main segment. S option 8. If the photoresistive element in item i of the patent application scope includes self-recognized k (C) is a saturated (cl) fluorine-containing polymer 'which contains derived from at least one ethylenic system ----- 47- This paper size applies to China National Standard (CNS) A4 specifications (2i0x297 public love) A repeating unit of a compound containing a fluoroalcohol functional group having the following structure: -C (Rf) (Rf,) 0H, the center of which is the same or different from the fluoroalkyl group of 1 to 10 carbon atoms, or (CF2) n, where η is 2 to 10; (c2) fluorinated copolymer, which contains repeating units derived from at least one ethylenically unsaturated compound, which is characterized by at least one ethylenically unsaturated compound Saturated compounds are cyclic or polycyclic, at least one ethylenic unsaturated compound S has at least one fluorine atom, is covalently connected to an ethylenically unsaturated atom, and at least one ethylenically unsaturated compound contains a fluoro group An alcohol functional group having the following structure: -C (Rf) (Rft) OH where 1 ^ and Rf are the same or different fluoroalkyl groups of 1 to 10 carbon atoms, or used together as (CF2) n, where 11 is 2 to 10; (c3) a fluorinated copolymer comprising: W is a repeating unit derived from at least one ethylidene-based unsaturated compound containing at least three fluorine atoms, covalently connected to two Ethylene-based unsaturated carbon atoms; derived from (11) ethylenically unsaturated The repeating unit of the compound, the compound contains a fluoroalcohol official group, and has the following structure: -C (Rf) (Rfl) OH where Rf and Rf · are the same or different fluoroalkyl groups of 1 to 10 carbon atoms, or together Adopted as (CF2) n, where η is 2 to 10; " (c4) fluorinated copolymer, which contains at least one kind of ethylenic unsaturated 8 8 8 8 A BCD 567404 6. Scope of patent application. And the repeating unit of the compound, the compound contains a fluoroalcohol functional group, and has the following structure: -ZCH2 C (Rf) (Rf,) OH where Rf and Rf · are 1 To 10 carbon atoms of the same or different fluoroalkyl groups, or taken together as (CF2) n, where η is 2 to 10; and Z is an element from Group VA or VIA of the Periodic Table of Elements; (c5) fluorine-containing An aggregate that contains the following structure: Each of R40, R41, R42, and R43 is independently a hydrogen atom, a halogen atom, a hydrocarbon group containing 1 to 10 carbon atoms, a substituted hydrocarbon group, an alkoxy group, a carboxylic acid, a carboxylic acid ester, or a functional group containing the following structure : -C (Rf) (Rf,) OR44 where Rf and Rf are the same or different fluoroalkyl groups of 1 to 10 carbon atoms, or they are used together as (CF2) n, where 11_ is _2 to 10; R44 Is a hydrogen atom, or an acid- or base-unstable protecting group; v is the number of repeating units in the polymer; w is 0-4; at least one repeating unit has a structure, at least one of which is R40, R41, R42, and R43 Contains structure C (Rf) (Rf,) OR44; and (c6) aggregates, which include: -49- This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm) 567404 A8 B8 (1) He Shengzi is a repeating unit of at least one ethylenic unsaturated compound, which contains a fluoroalcohol functional group, and has the following structure ... Rf and Rf in C (Rf) (Rf,) 0H, which is 1 to 10 carbon atoms of the same or different fluoroalkyl groups, or taken together as (α? 2) η, where η is 2 to 10; and 0) derived from at least one ethylenically unsaturated compound having the following structure Repeating unit: (H) (R45) C = C (R46) (CN) where R45 is a hydrogen atom or CN; R46 is a Ci-C8 alkyl group, a hydrogen atom, or co2R47, where r47 is a Ci < v ^ group or A hydrogen atom. 9. The photoresistive element according to item 8 of the claimed β patent range, wherein the polymer (c) further comprises a spacer selected from the group consisting of ethylene, α-olefin, 1, Γ-disubstituted alkane, ethynyl alcohol, Ethyl ethers and difluorenes. 10. The photoresist element according to item i of the patent application scope, wherein the polymer ⑼ further comprises one or more comonomers CR51R52 = CR53R54, wherein each of RS1, R52, and R53 is independently selected from Η or F, and wherein R54 is selected Since · F, _ CF3, -OR5 5 'where R5 5 is cnF2n + 1, where η = 1 to 3, -OH (when R5 3 = Η), and Cl (when R5 1, R5 2 and R5 3 = F). 11. The light of the scope of the patent application: color element, wherein the polymer further includes an amorphous vinyl copolymer, selected from the group consisting of ch2 = chcf3 and CF2 = CF2, with a ratio of 1: 2 to 2: 1 . Example: CH2 = CHF and CF2 = CFC1, in a ratio of 1: 2 to 2: 1; CH2 = CHF and CC1H = CF2, in a ratio of 1: 2 to 2: 1; perfluoro (2-amidino-4- Methyl-1,3-dioxolane) at any ratio and -50- This paper size applies to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) Less, please patent scope Gold fluoride (2,2 -Dimethyldioxolium); perfluoro (2-fluorenylidene_4_methyl_1,3-dioxolidine) with difluoroethylenefluorene at any ratio, which is amorphous; And perfluoro (2-methylene-4-methyl · U_dioxine) homopolymer. 12. The photoresistive element according to item i of the application, wherein the polymer is selected from the group consisting of (el) polymers, which include: ① a repeating unit derived from at least one ethylenically unsaturated compound, and 1¾ the compound contains ethylene Ether. Functional group, and has the following structure: CH2 = CHO-R5 6 where R56 is a substituted or unsubstituted alkyl, aryl, aralkyl, or alkanearyl group, having 1 to 20 carbon atoms; and (ii) Repeating units derived from at least one ethylenically unsaturated compound having the following structure: (H) (R5 7) C = C (R5 8) (CN) where R57 is a hydrogen atom or a cyano group; R58 is a range An alkyl group of from 8 to 8 carbon atoms, a co2: r59 group, wherein R59 is an alkyl group ranging from 1 to 8 carbon atoms, or a hydrogen atom; and (iii) derived from at least one acidic group Repeating units of ethylenically unsaturated compounds: and (e2) a polymer comprising ... (1) repeating units derived from at least one ethylenically unsaturated compound, the compound comprising an ethylenic ether functional group and A fluoroalcohol functional group and has the following structure: -51- Sixth, the scope of patent application C (R6 0) (R6 1) = C (R6 2) -0-DC (Rf) (Rf,) 0H where R0〇, R6 1 and R62 are independently hydrogen atoms, ranging from 1 to 3 slave atoms <alkyl; D is at least one atom, which is connected to the ethyl ether ether energy group, passes the oxygen atom to the carbon atom of the fluoroalcohol functional group; and Rf · contains 1 to 10 Carbon atoms of the same or different fluoroalkyl groups, or taken together as (Cp2) n, where η is an integer ranging from 2 to 10; and (η) is derived from at least one ethylenically unsaturated compound having the following structure Unit: (H) (R5 7) C = C (R5 8) (CN) where R57 is a hydrogen atom or a cyano group; r58 is an alkyl group ranging from one carbon atom, and a C02r59 group, where R59 is a range From an alkyl group of a carbon atom, or a hydrogen atom; and a repeating unit of a compound ... 13. If the photo-resistance-step of the patent application range includes a solvent. The first-blocking composition in K: Please refer to the patent range The photoresistance of item} is related to the photoresistive component in the female dungeon H 1 15 "° to a polymer selected from the group consisting of ⑷ to (e). 15. For example, the photoresistive element in the scope of the patent, including Shi Xi, oxygen cutting and nitrogen cutting, and holding the mixture. * It is selected from the photoresistive element of the 1st patent scope, where the anti-surname engraved layer is A, and the inorganic material is selected and its mixture. 17. · If the photoresistive element in the 16th scope of the patent application includes oxygen cutting, nitrogen cutting, and oxynitriding, ^ # ^ (CNS) A4 «(21〇X297 ^ D8, patent application j " 18 · A method for preparing a photoresist image on a substrate, including the following sequence: (X) exposing the photoresist element in an image copying manner to form an imaged and unimaged area, wherein the photoresist element includes a substrate An anti-etching layer; and at least one photoresist layer, made from a photoresist composition, comprising: (A) a polymer selected from the group consisting of: 氟 a fluorocopolymer, which comprises a derivative derived from at least one kind of B A repeating unit of an actinic unsaturated compound, characterized in that the at least one ethylenic unsaturated compound is polycyclic; a branched polymer containing a protected acid group, the polymer containing one or more branched segments , Chemically connected along the linear main chain segment; ⑻ fluoropolymer, which has at least one fluoroalcohol group, has the following structure: -C (Rf) (Rf,) 〇H where Rf and Rf are 1 to 10. Carbon atoms of the same or different fluoroalkyl groups, or used together as (CF2) n, where n is 2 To 10; (d) an amorphous vinyl homopolymer of perfluoro (2,2-dimethyl-fluorene, 3-dioxolene) or CX2 = CY2, where X = F or CF3, and Y = _H, or perfluorinated dimethyl-1,30! Wu Zhilian) and amorphous vinyl copolymer with CX2 = CY2; and ⑷ polymer containing nitrile / fluoroalcohol, made from substituted or unsubstituted Substituted ethynyl ethers; and (B) photoactive ingredients; and -53- This paper size applies to China National Standard (CNS) A4 specifications (210X297 male cage) _ 567404 A8 B8 C8 D8, scope of patent application, ( Y) developing the exposed photoresist layer with the imaged and unimaged areas to form a relief image on the substrate. 19. The method of claim 18, wherein the polymer has an absorption coefficient of less than 5.0 microns-1 at a wavelength of 157 nm. 20. The method of claim 18, wherein the polymer has an absorption coefficient of less than 4.0 microns at a wavelength of 157 nm. 21. The method of claim 18, wherein the polymer has an absorption coefficient of less than 3.5 microns · 1 at a wavelength of 157 nm. 22. The method of claim 18, wherein the anti-etching layer is selected from the group consisting of silicon oxide, silicon nitride, silicon oxynitride, and mixtures thereof. -54- This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) Application date of case number I Bulletin s ° ^ oSpl / ^ fa for 〒 (^ ιΜ A 1 «--- ~~ C4 η Supplements the above columns to be filled by this Bureau) Chinese manual (including the scope of the patent application) replaces this version (February 1992) 567404 Episode J Chinese Patent Specification, "Multilayer components with photoresist composition in the name and its The use of shadow etching English MULTILAYER ELEMENTS CONTAINING PHOTORESIST COMPOSITIONS AND THEIR USE IN MICROLITHOGRAPHY Name Nationality 1. Larry L. Berg LARRY L. BERGER 2. Frank L. Schade, III FRANK L. SCHADT, III Inventions > All American Domicile and Residence1 · No.596 Meizhen Road, Chadsford, Penn., USA 2 · No. 2407, Delaihuai Avenue, Wilmington, Delaware, USA. Binding Name (Name) Nationality American Commerce DuPont Co., Ltd. EI DU PONT DE NEMOURS AND COMPANY US Line III. Applicant MIRIAM D. MECONNAHEY This paper ruler Du Shicai SS Family Standard (CNS) A4 specification (Can χ tear public love) 567404 _Bulletin_i VI. Application iWw range-1 ~ 1. A photoresistive element, including: (L) a substrate; (M) an anti-etching layer; and (N) at least one photoresist layer made from a photoresist composition comprising (A) at least one polymer selected from the group consisting of: (a) a fluorocopolymer, which Comprising a repeating unit derived from at least one ethylenic unsaturated compound, characterized in that the at least one ethylenic unsaturated compound is polycyclic; (b) a branched polymer containing a protected acid group, the polymer Contains one or more branched segments that are chemically connected along the linear main segment; (c) A fluoropolymer with at least one fluoroalcohol group, with the following structure: -C (Rf) (Rf,) OH where Rf and Rf are the same or different fluoroalkyl groups of 1 to 10 carbon atoms, or are used together as (CF2) n, where η is 2 to 10; (d) perfluoro (2,2-dimethyl-1 , 3-dioxolene) or amorphous vinyl homopolymer with CX2 = CY2, where X = CF3 and Y = -H, or perfluoro (2,2-dimethyl-1,3-dioxy Woodinene) and CX2 = CY2 amorphous vinyl copolymer; and (e) nitrile / fluoroalcohol-containing polymers made from substituted or unsubstituted vinyl ethers; and (B) at least one photoactive component. 2. For example, the photoresistive element in the first patent application scope, where the polymer is 157 nanometers _-46 · _ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)