KR20040004403A - Compositions for microlithography - Google Patents

Abstract

The present invention comprises at least one spacer group selected from the group consisting of ethylene, alpha-olefins, 1,1'-disubstituted olefins, vinyl alcohol, vinyl ethers, and 1,3-dienes; And the formula -C (R _f ) (R _{f '} ) OR _b , wherein R _f and R _f' are the same or different fluoroalkyl groups having 1 to about 10 carbon atoms or taken together (CF ₂ ) Provides a fluorine-containing polymer prepared from a norbornyl radical containing a functional group containing _n (where n is an integer from 2 to about 10) and R _b is a hydrogen atom or an acid- or base-reactive protecting group. . The fluorine-containing polymer has an absorption coefficient of less than 4.0 μm ⁻¹ at a wavelength of 157 nm. These polymers are useful in photoresist compositions for microlithography. They exhibit high transparency at these short wavelengths and also have other important properties including good plasma etch resistance and adhesion properties.

Description

Composition for microlithography {COMPOSITIONS FOR MICROLITHOGRAPHY}

Polymer products may be used in imaging and photosensitive systems and in particular in Introduction to Microlithography, Second Edition by L. F. Thompson, C.G. Willson, and M.J. Bowden, American Chemical Society, Washington, DC, 1994, as a component of a photoimaging system. In such systems, ultraviolet (UV) light or other electron beams impinge on the material containing the photoactive component to induce physical or chemical changes of the material. This results in a useful image or latent image that can be processed into useful images for semiconductor device fabrication.

Although the polymer product itself may be photoactive, the photosensitive composition generally contains one or more photoactive components in addition to the polymer product. Upon exposure to an electron beam (e.g., UV light), the photoactive component is determined by the rheological state, solubility, surface properties, refractive index, color, electromagnetic properties of the photosensitive composition as described in the publication of Thompson et al. (See above). Acts to change properties or other physical or chemical properties.

In order to image very fine features at sub-micron levels in semiconductor devices, electron beams of far or extreme ultraviolet (UV) light are required. Positive resists are generally used in semiconductor manufacturing. Lithography at 365 nm (I-ray) UV using novolac polymer and diazonaptoquinone as dissolution inhibitor is a currently established chip technology with a resolution limit of about 0.35-0.30 microns. Lithography at 248 nm original UV using p-hydroxystyrene polymer is known and has a resolution limit of 0.35-0.18 nm. Next-generation at even shorter wavelengths is due to lower resolution limits that decrease as the wavelength decreases (ie, resolution limits of 0.18-0.12 microns for 193 nm imaging and about 0.07 microns for 157 nm imaging). Photolithography is strongly desired. Photolithography using a 193 nm exposure wavelength (obtained from an argon fluorine (ArF) excimer laser) is a leading candidate for next generation microelectronic fabrication using 0.18 and 0.13 μm design rules. If a suitable material with sufficient transparency and other necessary properties can be found at this very short wavelength, photolithography using a 157 nm exposure wavelength (obtained from a fluorine excimer laser) is superior to next-generation microlithography (193 nm) that accelerates the planning period. ) Is the leading candidate for The opacity of traditional near UV and far UV organic photoresists at 193 nm or shorter wavelengths precludes their use in single layer designs at these short wavelengths.

Some resist compositions suitable for imaging at 193 nm are known. For example, photoresist compositions comprising cycloolefin-maleic anhydride alternating copolymers have been found to be useful for imaging of semiconductors at 193 nm [F.M. Houlihan et al., Macromolecules, 30, pages 6517-6534 (1997); T. Wallow et al., SPIE, Vol. 2724, pages 355-364; and F.M. Houlihan et al., Journal of Photopolymer Science and Technology, 10, No. 3, pages 511-520 (1997). Some literature [ie, U. Okoroanyanwu et al, SPIE, Vol. 3049, pages 92-103; R. Allen et al., SPIE, Vol. 2724, pages 334-343; and Semiconductor International, Sept. 1997, pages 74-80, are concentrated in 193 nm resists. Compositions comprising addition polymers of functionalized norbornene and / or ROMP (opening metathesis polymerization) are disclosed in PCT WO 97/33198. Homopolymers and maleic anhydride copolymers of norbornadiene and their use in 193 nm lithography are described in J. Niu and J. Frechet, Angew. Chem. Int. Ed., 37, No. 5, (1998), pages 667-670. Copolymers of fluorinated alcohol substituted polycyclic ethylenically unsaturated comonomers and sulfur dioxide have been reported suitable for 193 nm lithography [H. Ito et al., "Synthesis and Evaluation of Alicyclic Backbone Polymers for 193 nm Lithography", Chapter 16, ACS Symposium Series 706 (Micro- and Nanopatterning Polymers) pages 208-223 (1998), and H. Ito et al., Abstract in Polymeric Materials Science and Engineering Division, American Chemical Society Meeting, Volume 77, Fall Meeting, September 8-11, 1997, held in Las Vegas, NV. Because of the presence of repeating units derived from sulfur dioxide in such alternating copolymers, such polymers are not suitable for 157 nm lithography due to the excessively high absorption coefficient at 157 nm.

Photoresists containing fluorinated alcohol functional groups attached to aromatic moieties are disclosed [K.J. Przybilla et al., "Hexafluoroacetone in Resist Chemistry: A Versatile New Concept for Materials for Deep UV Lithography", SPIE Vol. 1672, (1992), pages 500-512]. Although this resist is suitable for 248 nm lithography, lithography at 193 or 157 nm is not suitable because of the aromatic functionality contained therein (due to the excessively high absorption coefficient of the aromatic resist component at these wavelengths).

Copolymers of fluoroolefin monomers and cyclic unsaturated monomers are disclosed in US Pat. Nos. 5,177,166 and 5,229,473, which do not disclose photosensitive compositions. Copolymers of certain fluorinated olefins with certain vinyl esters are known. For example, copolymers of trifluoroethylene (TFE), cyclohexanecarboxylate, and vinyl esters are disclosed in Japanese Patent Application JP 03281664. Copolymers of TFE and vinyl esters such as vinyl acetate and the use of these copolymers in photosensitive compositions for refractive imaging (eg holography) are disclosed in US Pat. No. 4,963,471 to DuPont.

Copolymers of norbornene-type monomers with functional groups and ethylene are disclosed in WO 98/56837. Copolymers of norbornene-type monomers containing functional groups with vinyl ethers, dienes and isobutylene are described in US Pat. No. 5,677,405. Is disclosed. Norbornene / ethylene copolymerization catalyzed by a nickel catalyst is disclosed in US Pat. No. 5,929,181.

Certain copolymers of fluorinated alcohol comonomers with other comonomers are disclosed in US Pat. No. 3,444,148 and JP 62186907 A2. These patents relate to membranes or other non-photosensitive films or fibers, none of which teach the use of fluorinated alcohol comonomers in photosensitive layers (eg resists).

U.S. Patent 5,655,627 discloses a negative tone resist by coating a silicon wafer with a solution of a copolymer resist of pentafluoropropyl methacrylate-t-butyl methacrylate in a solvent, followed by exposure at 193 nm and development with a carbon dioxide critical fluid. A method of generating an image is disclosed.

There is still a need for resist compositions that meet many of the requirements for single layer photoresists, including optical transparency at 193 nm and / or 157 nm, plasma etch resistance, and solubility in aqueous base developers.

In a method of forming a patterned microelectronic structure by lithography, one or more antireflective coatings (ARCs) or layers are referred to underneath the photoresist layer (BARC) or above the photoresist layer (TARC) (or sometimes simply referred to as ARC). ) Or both are common in the industry. The antireflective coating layer reduces the harmful effects of variations in film thickness, and thus standing waves caused by interference of light reflected at various interfaces within the photoresist structure, and changes in exposure dose in the photoresist layer due to the loss of reflected light. It turned out to be. The use of these antireflective coatings improves the patterning and resolution characteristics of the photoresist material as they suppress reflection related effects.

There is also a need for an antireflective coating having optical transparency at 193 nm and / or 157 nm.

Summary of the Invention

The present invention relates to (A) a spacer group and (B) a norbornyl radical and

-C (R _f ) (R _{f '} ) OR _b

Wherein R _f and R _{f ′} are the same or different fluoroalkyl groups having 1 to about 10 carbon atoms or are taken together (CF ₂ ) _n where n is an integer from 2 to about 10 , R _b relates to a fluorine-containing polymer comprising a reaction product of repeating units derived from a monomer containing a functional group containing a hydrogen atom or an acid- or base-reactive protecting group.

In a first aspect, the invention provides a composition comprising at least (A) a spacer group selected from the group consisting of ethylene, alpha-olefins, 1,1'-disubstituted olefins, vinyl alcohol, vinyl ethers, and 1,3-dienes; And

(B) the following structural formula

{Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 10 carbon atoms, a substituted hydrocarbon group, an alkoxy group, a carboxylic acid, a carboxylic acid Ester or the following structural formula

-C (R _f ) (R _{f '} ) OR _b

Wherein R _f and R _{f ′} are the same or different fluoroalkyl groups having 1 to about 10 carbon atoms or when taken together (CF ₂ ) _n where n is an integer from 2 to about 10 , R _b is a hydrogen atom or an acid- or base-reactive protecting group]; r is a repeating unit derived from a monomer having 0-4, in which at least one of R ₁ , R ₂ , R ₃ and R ₄ is a structural formula C (R _f ) (R _{f ′} ) OR Provided is a fluorine-containing polymer produced from a repeating unit having a structure containing _b .

In a second aspect, the invention provides a composition of (a) (A) a spacer group and (B) a norbornyl radical and

-C (R _f ) (R _{f '} ) OR _b

Wherein R _f and R _{f ′} are the same or different fluoroalkyl groups having 1 to about 10 carbon atoms or are taken together (CF ₂ ) _n where n is an integer from 2 to about 10 , R _b is a fluorine-containing polymer comprising a reaction product of repeating units derived from a monomer containing a functional group containing a hydrogen atom or an acid- or base-reactive protecting group; And

(b) one or more photoactive components

Wherein the fluorine-containing polymer has an absorption coefficient of less than 4.0 μm ⁻¹ at a wavelength of 157 nm.

In a third aspect, the invention provides (X) (a) at least (A) spacer groups and (B) norbornyl radicals and

-C (R _f ) (R _{f '} ) OR _b

Wherein R _f and R _{f ′} are the same or different fluoroalkyl groups having 1 to about 10 carbon atoms or are taken together (CF ₂ ) _n where n is an integer from 2 to about 10 , R _b is a fluorine-containing polymer prepared from a fluorine-containing polymer comprising a reaction product of a monomer containing a functional group containing a hydrogen atom or an acid- or base-reactive protecting group; And

(b) photoactive components

Wherein the fluorine-containing polymer is subjected to image-by-image exposure of a photoresist layer prepared from a photoresist composition having an absorption coefficient of less than 4.0 μm ⁻¹ at a wavelength of 157 nm to form an image forming and image non-forming surface

(Y) developing an exposed photoresist layer having an image forming and an image forming surface to form a relief image on the substrate;

It provides a method for forming a photoresist image on a substrate, which in turn comprises.

In a fourth aspect, the invention comprises a support and at least an antireflective layer, wherein the antireflective layer comprises at least (A) a spacer group and (B) a norbornyl radical and

-C (R _f ) (R _{f '} ) OR _b

Wherein R _f and R _{f ′} are the same or different fluoroalkyl groups having 1 to about 10 carbon atoms or are taken together (CF ₂ ) _n where n is an integer from 2 to about 10 , R _b provides a member made from a composition comprising at least one fluorine-containing polymer prepared from a fluorine-containing reaction product of a monomer containing a functional group containing a hydrogen atom or an acid- or base-reactive protecting group.

The member may further comprise a photoresist layer.

In a fifth aspect, the present invention has (Y) a support, a photoresist layer and an antireflective layer, wherein the antireflective layer comprises at least (A) spacer groups and (B) norbornyl radicals and the following structural formula:

-C (R _f ) (R _{f '} ) OR _b

Wherein R _f and R _{f ′} are the same or different fluoroalkyl groups having 1 to about 10 carbon atoms or are taken together (CF ₂ ) _n where n is an integer from 2 to about 10 , R _b is a hydrogen atom or an acid-or base-reactive protecting group) containing a photoresist is prepared from a composition comprising one or more fluorine-containing polymers prepared from a fluorine-containing polymer comprising the reaction product of a monomer containing a functional group The member is exposed for each image to form an image forming and image non-forming surface,

(Z) developing an exposed photoresist member having image forming and image non-forming surfaces to form a relief image on the substrate;

An improved lithographic patterning method of a photoresist member having a support, a photoresist layer and an antireflective layer, is provided.

FIELD OF THE INVENTION The present invention relates to the use of photoresists (positive and / or negative) for photoimaging and in particular for image formation in semiconductor device fabrication. The present invention also relates to novel fluorine-containing polymer compositions having high UV transparency (especially at short wavelengths, for example at 157 nm) useful for photoresist compositions and antireflective coatings.

The fluorine-containing polymer of the present invention has at least (A) a spacer group and (B) a norbornyl radical and

-C (R _f ) (R _{f '} ) OR _b

Wherein R _f and R _{f ′} are the same or different fluoroalkyl groups having 1 to about 10 carbon atoms or when taken together (CF ₂ ) _n where n is an integer from 2 to about 10 , R _b is prepared from a fluorine-containing polymer comprising a reaction product of a monomer containing a functional group containing a hydrogen atom or an acid- or base-reactive protecting group.

Fluorine-containing polymer

The fluorine-containing polymer is prepared from at least the spacer group (A) and the monomer (B).

Spacer groups are hydrocarbon compounds containing vinylic unsaturation and optionally containing one or more heteroatoms, such as oxygen atoms or nitrogen atoms. Hydrocarbon compounds envisaged as spacer groups typically contain 2 to 10, more typically 2 to 6 carbon atoms. The hydrocarbon may be straight or branched chain. Specific examples of suitable spacer groups are selected from the group consisting of ethylene, alpha-olefins, 1,1'-disubstituted olefins, vinyl alcohol, vinyl ethers and 1,3-dienes. Typically, when the spacer group is an alpha olefin, it is selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene. Typically, when the spacer group is vinyl ether, it is selected from the group consisting of methyl vinyl ether and ethyl vinyl ether. Typically, the vinyl alcohol can be obtained by post polymerization hydrolysis of the functional groups already contained in the polymer backbone, for example the acetate groups of vinyl acetate. Typically, when the spacer group is 1,3-diene it is butadiene. Typically, when the spacer group is a 1,1'-disubstituted olefin it is isobutylene or isopentene.

Monomer (B) is an ethylenically unsaturated compound containing a norbornyl radical and a fluoroalcohol functional group.

The fluoroalkyl groups designated as R _f and R _{f ′} may be partially fluorinated alkyl groups or fully fluorinated alkyl groups (ie perfluoroalkyl groups).

Broadly, R _f and R _{f ′} are the same or different fluoroalkyl groups having 1 to about 10 carbon atoms or when taken together (CF ₂ ) _n where n is an integer from 2 to about 10.

The term "taken together" means that R _f and R _{f '} are not separate fluorinated alkyl groups, but rather that they together form a ring structure of 3 to about 11 carbon atoms as illustrated below in the case of a 5-membered ring. it means:

When R _f and R _{f ′} are partially fluorinated alkyl groups, the hydroxyl (—OH) group of the fluoroalcohol functional group is such that the hydroxyl protons are substantially removed from the base medium such as aqueous sodium hydroxide solution or tetraalkylammonium hydroxide solution. Sufficient degree of fluorination must be present to impart acidity. Typically, there will be sufficient fluorine substitution in the fluorinated alkyl group of the fluoroalcohol functional group such that the hydroxyl group has a pKa value as follows: 5 <pKa <11.

Preferably, R _f and R _{f ′} are independently a perfluoroalkyl group having 1 to about 5 carbon atoms, most preferably R _f and R _{f ′} are both trifluoromethyl (CF ₃ ).

Structural formula

In the repeating unit derived from the monomer having a substituent, the substituents R ₁ , R ₂ , R ₃ and R ₄ may each independently be a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to about 10 carbon atoms or a substituted hydrocarbon group. When one or more substituents R ₁ , R ₂ , R ₃ and R ₄ are hydrocarbon groups, the carbon atoms are generally straight or branched chain. Typical examples include alkyl groups (methyl ("Me"), ethyl ("Et"), propyl ("Pr")), carboxylic acids or esters, alkoxy (-OMe, OEt, OPr), halogens (F, Cl, Br). When one or more substituents R ₁ , R ₂ , R ₃ and R ₄ are substituted hydrocarbon groups, the substituents are typically heteroatoms selected from the group consisting of oxygen atoms which form alkoxy groups, carboxylic acid groups or carboxylic ester groups.

Ethylene and the following structural formula

Copolymers of monomers of may contain "more than" branches (see, eg, International Patent Application 96/23010, incorporated herein by reference, for description of "more than" branches). These polymers may typically contain more than 5 methyl terminal branches, more typically more than 10 methyl terminal branches, most typically more than 20 methyl terminal branches in the polyethylene segment of the polymer. Branching can impart improved solubility to ethylene copolymers that can be beneficial for making photoresists or for other purposes. Branching can also be confirmed by NMR spectroscopy, see International Patent Application 96/23010 and other known literature for identifying branches in polyolefins. Methyl terminal branching refers to the number of methyl groups corrected for methyl groups present as terminal groups in the polymer. Groups bonded as side chain groups to norbornane ring systems, such as methyl attached directly to carbon atoms bonded to ring atoms of norbornane ring systems, are not included as methyl terminal branches. Such corrections are known in the art. Typically, the polymers herein contain at least 1 mol% (based on the total number of all repeat units in the copolymer), more typically at least 2 mol%, most typically at least 5 mol% of the norbornene monomers described above. do. Repeating units derived from one or more other copolymerizable monomers, such as alpha-olefins and vinyl ethers, may optionally be present.

The free radical polymerization or metal catalyzed vinyl addition polymerization process used to prepare the polymerization products of the present invention is accomplished by such polymerization mechanisms known in the art to obtain polymers having repeating units derived from ethylenically unsaturated compounds. Specifically, the following structural formula

The ethylenically unsaturated compound having a free radical polymerization is a repeating unit

In the above formula, P, Q, S and T may be independently the same or different, and may be a polymer having fluorine, hydrogen, chlorine and trifluoromethyl.

If only one ethylenically unsaturated compound is polymerized, the resulting polymer is a homopolymer. If two or more other ethylenically unsaturated compounds are polymerized, the resulting polymer is a copolymer.

Some representative examples of ethylenically unsaturated compounds and their corresponding repeating units are shown below:

In the case of metal catalyzed vinyl addition polymerization, a useful catalyst is a nickel containing complex. Neutral Ni catalysts are described in WO patent application 9830609. Salicylidin based neutral nickel catalysts are described in other documents [WO Patent Application 9842664]. Wang, C .; Friedrich, S .; Younkin, T. R .; Li, R. T .; Grubbs, R. H .; Bansleben, D. A .; Day, M.W. Organometallics 1998, 17 (15), 314 and Younkin, T .; Connor, E. G .; Henderson, J. I .; Friedrich, S.K .; Grubbs, R. H .; Bansleben, D.A. Science 2000, 287, 460-462. Another catalyst is also disclosed [Ittel, S.D .; Johnson, L. K .; Brookhart, M. Chem. Rev. 2000, 100, 1169-1203 and Boffa, L. S .; Novak, B.M. Chem. Rev. 2000, 100, 1479-1493. WO 0050470 to Moody, L.S .; MacKenzie, P. B .; Killian, C. M .; Lavoie, G. G .; Ponasik, J. A .; Barrett, A.G.M .; Smith, T. W .; Pearson, JC] has 2,6-orthos which are mostly both an existing ligand and some new ligands for later metal catalysts, for example ligands derived from pyrrole amines instead of aniline and ortho substituents are both aryl groups or any aromatic groups. Disclosed is an improvement or change in an aniline based ligand having a substituent. Specific examples would be alpha-diimine based nickel catalysts derived from pyrrole amines and ortho aromatic substituted anilines and salicylidinine based nickel catalysts. Some of these derivatives exhibit improved lifespan / activity / productivity / hydrogen reactions / potential functional group resistance and the like. Another useful catalyst is a late metal catalyst of functional group resistance, generally based on Ni (II) or Pd (II). Useful catalysts are disclosed in WO 98/56837 and US Pat. No. 5,677,405.

A process for preparing copolymers from norbornene-type monomers and cationic polymerizable monomers using Group VIII transition metal ion sources for these monomers at temperatures from -100 ° C to 120 ° C is disclosed in US Pat. No. 5,677,405. "Cationically polymerizable monomer" generally means monomers such as olefins, isoolefins, branched α-olefins, vinyl ethers, cyclic ethers and lactones which are cationicly polymerized. Copolymers formed from norbornene-type monomers and cationic polymerizable monomers have a relatively high norbornene content (˜80 mol% in the copolymer characterized). Copolymers may be formed using esters derived from functionalized norbornene comonomers such as 5-norbornene-2-methanol and 5-norbornene-2-methanol. The catalysts and methods disclosed in this application are expected to be suitable for the synthesis of copolymers of norbornene fluoroalcohol and 1,3-diene, 1,1'-disubstituted olefins and vinyl ethers of the present invention. In addition, these copolymers can suitably control the monomer feed ratio and contain more than about 1 mole percent, more typically more than about 25 mole percent, most typically more than about 50 mole percent of norbornene fluoroalcohol. It is expected to be. Examples of suitable catalysts useful for the preparation of such copolymers are norbornadienepalladium dichloride / silver hexafluoroantimonate, methoxynorbornenylpalladium chloride dimer / silver hexafluoroantimonate and [(η- Crotyl) (cycloocta-1,5-diene) nickel] -hexafluorophosphate.

In photoresist applications, it is expected that the copolymer may contain acidic groups that may or may not be protected with acid reactive protecting groups. In addition, monomeric units containing these acidic groups are expected to comprise more than about 1 mol%, more typically more than about 25 mol%, and most typically more than about 50 mol% of the polymer. Examples of acidic groups include carboxylic acids, phenols and fluoroalcohols having a pKa value of about 9 or less.

Copolymers of ethylene and protected norbornene fluoroalcohols can be synthesized using Ziegler-Natta and metallocene catalysts based on early transition metals. Suitable protecting groups for fluoroalcohols include alpha-alkoxy ethers. Examples of suitable catalysts are described in W. Kaminsky J. Chem. Soc., Dalton Trans. 1988, 1413 and W. Kaminsky Catalysis Today 1994, 20, 257.

Any suitable polymerization condition can be used in the method of making the polymer. Typically, when metal catalyzed vinyl addition polymerization is used, the temperature is maintained below about 200 ° C, typically 0 to 160 ° C. Suitable known solvents such as trichlorobenzene or p-xylene can be used.

Each fluorine-containing copolymer according to the invention is less than 4.0 μm ⁻¹ at a wavelength of 157 nm, preferably less than 3.5 μm ⁻¹ at this wavelength, more preferably less than 3.0 μm ⁻¹ , even more preferably at this wavelength Has an absorption coefficient of less than 2.5 μm ⁻¹ at this wavelength.

Some illustrative non-limiting examples of representative comonomers containing fluoroalcohol functional groups within the scope of the present invention are as follows:

The fluorine-containing polymer may be photoactive, ie the photoactive component may be chemically bonded to the fluorine-containing polymer. This can be done by chemically bonding the photoactive component to the monomer and then copolymerizing the monomers (A) and (B) of the invention, so that a separate photoactive component is not necessary.

The ratio of A and B can be important. Typical ranges for each are about 30% to about 70%.

One or more additional monomers (C) may be used in the preparation of the fluorine-containing polymers of the invention. In general, it is expected that acrylate monomers may be suitable as monomers (C) in the preparation of the polymers of the invention. Typical additional monomers include olefins, acrylates containing electron withdrawing groups (other than fluorine) attached directly to the double bond. These polymers, typically terpolymers, can be prepared, for example, by free radical polymerization of acrylonitrile, vinyl chloride, vinylidene chloride. Alternatively, olefins containing aromatic groups attached directly to double bonds, such as styrene and alpha-methyl styrene, which are, in arguably, alpha- and 1,1'-disubstituted olefins, are also useful. Vinyl acetate is also useful as additional monomer.

These fluorine-containing polymers are useful for preparing photoresist compositions comprising fluorine-containing polymers, one or more photoactive components and optionally dissolution inhibitors. The photoactive component can be chemically bonded to the fluorine-containing polymer or it can be a separate component used with the fluorine-containing polymer.

Photoactive Ingredients (PAC)

If the fluorine-containing polymer is not photoactive, the composition of the present invention may contain a photoactive component (PAC) that is not chemically bonded to the fluorine-containing polymer, ie the photoactive component is a separate component in the composition. Photoactive components are generally compounds which generate acids or bases upon exposure to actinic radiation. If acid is produced upon exposure to actinic radiation, the PAC is called a photoacid generator (PAG). If a base is produced upon exposure to actinic radiation, the PAC is called a photobase generator (PBG).

Photoacid generators suitable for the present invention include, but are not limited to, 1) sulfonium salts (formula I), 2) iodonium salts (formula II), and 3) hydroxamic acid esters (formula III).

In structures I-II, R ₅ -R ₇ are independently substituted or unsubstituted aryl or substituted or unsubstituted C ₁ -C ₂₀ alkylaryl (aralkyl). Representative aryl groups include, but are not limited to, phenyl and naphthyl. Suitable substituents include, but are not limited to, hydroxyl (—OH) and C ₁ -C ₂₀ alkyloxy (eg, C ₁₀ H ₂₁ O). The anion X ⁻ in formula I-II is, but is not limited to SbF _6- (hexafluoroantimonate), CF ₃ SO _3- (trifluoromethylsulfonate = triflate) and C ₄ F ₉ SO _3- (Perfluorobutylsulfonate).

Dissolution inhibitor

Various dissolution inhibitors can be used in the present invention. Ideally, dissolution inhibitors (DI) for raw and extreme UV resists (e.g., 193 nm resists) are suitable for multifunctional needs, including dissolution inhibition, plasma etch resistance and adhesion behavior of resist compositions comprising certain DI additives. Can be designed / selected to meet. Some dissolution inhibiting compounds also act as plasticizers in resist compositions.

Various bile esters (ie cholate esters) are particularly useful as DI in the compositions of the present invention. Bile acid esters were studied in 1983 by Reichmanis et al. And are known to be effective dissolution inhibitors for seam UV resists [E. Reichmanis et al., "The Effect of Substituents on the Photosensitivity of 2-Nitrobenzyl Ester Deep UV Resists", J. Electrochem. Soc. 1983, 130, 1433-1437. Bile salt esters have several reasons, including their availability in natural sources, their high alicyclic carbon content and their transparency especially in the shim and vacuum UV regions of the electromagnetic spectrum (eg, they typically have high transparency at 193 nm). It's kind of interesting DI. In addition, bile esters are also of interest to DI because they can be designed to have a wide range of hydrophobic to hydrophilic compatibility depending on hydroxyl substitution and functionalization.

Representative bile acids and bile acid derivatives suitable as additives and / or dissolution inhibitors in the present invention include, but are not limited to, those exemplified below: choline acid (IV), deoxycholine acid (V), lysocholine Acids (VI), t-butyl deoxycholate (VII), t-butyl lysocholate (VIII) and t-butyl-3-α-acetyl lysocholate (IX). Bile acid esters, including compounds VII-IX, are preferred dissolution inhibitors in the present invention.

The amount of dissolution inhibitor can vary depending on the choice of polymer. When there is a lack of sufficient protected acid groups to form suitable images in the polymer, dissolution inhibitors may be used to improve the image forming properties of the photoresist composition.

Other ingredients

The composition of the present invention may contain any additional component. Examples of additional components that may be added include, but are not limited to, resolution enhancers, fixers, residue diluents, coating aids, plasticizers, solvents, and Tg (glass transition temperature) modifiers. Crosslinking agents may also be present in the negative resist composition. Some crosslinkers typical include bis-azides such as 4,4'-diazidodiphenyl sulfide and 3,3'-diazidodiphenyl sulfone. Typically, negative compositions containing one or more crosslinkers also contain suitable functional groups (eg, unsaturated C═C bonds) that can react with reactive species (eg, nitrates) generated upon UV exposure. To form a crosslinked polymer that does not dissolve, disperse or substantially swell in the developer. Examples of suitable solvents are 2-heptanone, trichlorobenzene, methanol, 1,1,2,2-tetrachloroethane, d ₂ ethyl ether and p-xylene.

Formation method of photoresist image

The method of forming a photoresist image on a substrate is

(X) (a) the fluorine-containing polymer of the present invention; And

(b) one or more photoactive components

Image-wise exposing the photoresist layer prepared from the photoresist composition comprising an image forming and image non-forming surface,

(Y) sequentially developing an exposed photoresist layer having image forming and image non-forming surfaces to form a relief image on the substrate.

Image-specific exposure

The photoresist layer is prepared by applying a photoresist composition onto a substrate and drying to remove the solvent. The photoresist layer thus formed is sensitive to light in the ultraviolet region of the electromagnetic spectrum, in particular at wavelengths below 365 nm. Image-specific exposure of the resist composition of the present invention can be done at many different UV wavelengths including, but not limited to, 365 nm, 248 nm, 193 nm, 157 nm and lower wavelengths. Image-by-image exposure is preferably at 248 nm, 193 nm, 157 nm or lower wavelengths of ultraviolet light, more preferably at 193 nm, 157 nm or lower wavelengths of ultraviolet light, most preferably at 157 nm or lower wavelengths. UV light is carried out. Image-by-image exposure can be done digitally with a laser or equivalent device or non-digitally using a photomask. Digital imaging with a laser is preferred. Laser devices suitable for digital imaging of the compositions of the present invention include, but are not limited to, argon-fluorine excimer lasers UV output at 193 nm, krypton-fluorine excimer lasers UV output at 248 nm and fluorine outputs at 157 nm. F ₂ ) laser. As discussed above, the use of lower wavelength UV light for image-by-image exposure results in higher resolution (lower resolution limit) and the use of lower wavelengths (eg, 193 nm or 157 nm or less). It is generally preferred over the use of higher wavelengths (eg 248 nm or greater).

phenomenon

The fluorine-containing component in the resist composition of the present invention should have sufficient functional groups for development after image-by-image exposure to UV light. Preferably, the functional group is an acid or protected acid that allows aqueous development to be possible using basic developer such as sodium hydroxide solution, potassium hydroxide solution or ammonium hydroxide solution.

Fluorine-containing polymers in the resist composition of the present invention typically comprise the following structural units

-C (R _f ) (R _{f '} ) OH

Wherein R _f and R _{f ′} are as defined above, an acid containing material consisting of at least one fluoroalcohol-containing monomer. The degree of acidic fluoroalcohol groups is determined for the desired composition by optimizing the amount necessary for good development in an aqueous alkaline developer.

When an aqueous processable photoresist is coated or otherwise applied to a substrate and image-by-image exposed to UV light, development of the photoresist composition results in the binder material being at least partially deprotected upon exposure to form a photoresist (or other photoimageable form). It is necessary to contain sufficient acid groups (eg fluoroalcohol groups) and / or protected acid groups to render the coating composition) processable in an aqueous alkaline developer. In the case of the portage-type photoresist layer, the photoresist layer will be removed at the portion exposed to UV rays during development, but developed by an aqueous alkaline liquid such as a total aqueous solution containing 0.262 N tetramethylammonium hydroxide (generally 120 at 25 ° C.). Substantially unaffected in unexposed portions during seconds or less, typically less than 90 seconds, in some instances less than 5 seconds). In the case of a negative photoresist layer, the photoresist layer will be removed in the portion not exposed to UV rays during development but will be substantially unaffected in the portion exposed during development using a critical fluid or organic solvent.

As used herein, a critical fluid is one or more materials that are heated to temperatures near or above their critical temperature and compressed to pressures near or above their critical pressure. The critical fluid in the present invention is at least 15 ° C. below the critical temperature of the fluid and at least 5 atm below the critical pressure of the fluid. Carbon dioxide may be used for the critical fluid in the present invention. Various organic solvents can also be used as a developing solution in this invention. These include, but are not limited to, halogenated solvents and non-halogenated solvents. Halogenated solvents are typical and fluorinated solvents are more typical.

Board

The substrate used in the present invention may be silicon, silicon oxide, silicon nitride, or various other materials used for the manufacture of semiconductors.

Other applications

Many of the polymers discussed in this application can be used as antireflective layers for semiconductor lithography. In particular, since low light absorption at 157 nm is the most important property of the materials considered here, they should be particularly useful at this wavelength.

Such layers can be applied using many other techniques such as spin coating, chemical vapor deposition, and aerosol deposition. Formulations of compositions for use as antireflective layers are known to those skilled in the art. The main optical properties to be considered for the materials used in the antireflective coatings are light absorption and refractive index, and the fluorine-containing polymer of the present invention has such properties.

For this application, the present invention comprises a support and at least an antireflective layer, wherein the antireflective layer comprises (a) the fluorine-containing polymer of the present invention; And (b) at least one photoactive component.

The member may further comprise a photoresist layer.

The present invention also has a (Y) support, a photoresist layer and an antireflective layer, wherein the antireflective layer is image-formed and non-image-formed by subjecting the photoresist member prepared from the composition comprising the fluorine-containing polymer of the present invention image by image. Form the

(Z) developing an exposed photoresist member having image forming and image non-forming surfaces to form a relief image on the substrate;

An improved lithographic patterning method of a photoresist member having a support, a photoresist layer and an antireflective layer, is provided.

The image forming and developing steps are done as previously described. The antireflective layer may be removed during the development of the photoresist having the image forming and non-image forming sides or it may be removed separately using aqueous or solvent development or by conventional dry etching methods as known in the art. . The photoresist layer can be any photoresist layer known in the art if it has an absorption coefficient of less than 4.0 μm ⁻¹ at a wavelength of 157 nm. Fluorine-containing polymers are described above in detail herein. The antireflective layer may be present between the support and the photoresist layer or it may be present on the photoresist layer surface remote from the support.

All copolymers herein are also useful as molding resins (in the case of thermoplastic resins) or as elastomers (in the case of elastomers). Structural formula

Polymers containing monomers of will also have modified surface properties, for example will be relatively hydrophobic because of fluorine atoms present on norbornene-type monomers, or if a hydrophilic group such as hydroxyl is present in the first monomer, May be relatively hydrophilic. These copolymers are useful in polymer blends, in particular as compatibilizers between different types of polymers, for example the ethylene copolymers of the present invention can be used in polyolefins such as polyethylene and poly (meth) acrylates, polyesters or polyamides such as Blends of more polar polymers can be commercialized.

Abbreviation:

Me: methyl

Et: ethyl

Hex: Hexyl

Am: Amy

Bu: Butyl

Eoc: chain ends

p: para

M.W .: Molecular Weight

Total Me: total number of methyl groups per 1000 methylene groups identified by ¹ H or ¹³ C NMR analysis

Cmpd: Compound

mL: milliliters

Press: Pressure

Temp: temperature

Incorp: Incorporated

BAF = B (3,5-C ₆ H _3- (CF ₃ ) ₂ ) _4-

Nd: not verified

GPC: Gel Permeation Chromatography

TCB: 1,2,4-trichlorobenzene

THF: tetrahydrofuran

Rt: room temperature

Equiv: equivalent

MI: melt index

RI: refractive index

UV: UV

M _w : weight average molecular weight

M _n : Number average molecular weight

M _p : peak average molecular weight

PDI: polydispersity; Divide M _w by M _n

NMR: nuclear magnetic resonance

E: ethylene

g: grams

h: hour

mol: mol

mmol: mmol

Et ₂ O: diethyl ether

General information on catalytic synthesis:

The process for the synthesis of catalysts A to D used in Examples 1-6 is described in WO 98/30609.

Procedures for Examples 1, 2 and 3

In a nitrogen purged drybox, the glass insert with the gas inlet was filled with 0.02 mmol of nickel complex A, B or C and 40 equivalents (0.4095 g) of B (C ₆ F ₅ ) ₃ . Trichlorobenzene (9 mL) was added to the glass insert, which was then cooled to -30 ° C in a dry box freezer. Norbornene-HFIP (1.52 g) was dissolved in 1 mL of Et ₂ O and the resulting solution was added over frozen trichlorobenzene. The insert was immediately cooled again in a -30 ° C. dry box freezer. The gas inlet of the cold insert was covered with an electrical tape and the insert was sealed with a greased cap and removed from the dry box atmosphere. Outside the drying box, the tubes were placed in plastic bags. The bag was sealed, placed in a bucket and surrounded by dry ice. After removing the electrical tape, the glass insert was transferred to a pressure tube. The pressure tube was sealed, evacuated, placed under ethylene (300 psi) and mechanically shaken at room temperature (rt) for about 18 hours. After completion of the reaction, methanol (˜20 mL) was added to the glass insert to precipitate the polymer. The copolymer was isolated and dried in vacuo. ¹ H NMR spectra were obtained at 113 ° C. in TCE-d ₂ (1,1,2,2-tetrachloroethane-d2) using a Bruker 500 MHz spectrometer. ¹³ C NMR spectra of 60 mg CrAcAc (chromium (III) acetylacetonate) and 310 mg in a total volume of 3.1 mL TCB (trichlorobenzene) using a Varian Unity 400 NMR spectrometer equipped with a 10 mm probe A sample was obtained at 140 ° C. GPC molecular weights were reported against polystyrene standards; Conditions: Water 150 ° C, Trichlorobenzene at 150 ° C, Shodex column at -806MS 4G 734/602005, RI detector.

Example 1

Nickel complex A (0.0102 g) was used to follow the above general procedure. The copolymer of ethylene and norbornene-HFIP was isolated as 2.77 g of white powder. ¹ H NMR: 1.5 mol% norbornene-HFIP incorporated; M _n ˜ 3,120; 33.3 total methyl terminal branch per 1000 CH ₂ . ¹³ C NMR: 1.4 mol% norbornene-HFIP incorporated. GPC: Bimodal distribution with small amount of high molecular weight material: M _p = 1,581; M _w = 19,873; M _n = 1,118 and M _p = 64,787; M _w = 94,613 and M _n = 55,595.

Example 2

Nickel complex B (0.0106 g) was used to follow the above general procedure. The copolymer of ethylene and norbornene-HFIP was isolated as 3.11 g of white powder. ¹ H NMR: 0.8 mol% norbornene-HFIP incorporated; M _n ˜ 18,040; 42.9 total methyl terminal branches per 1000 CH ₂ . ¹³ C NMR: 0.92 mol% norbornene-HFIP incorporated.

Example 3

Nickel complex C (0.0094 g) was used to follow the above general procedure. Copolymers of ethylene and norbornene-HFIP were isolated as 1.01 g of white powder. ¹ H NMR: 0.3 mol% norbornene-HFIP incorporated; M _n ˜ 9,240; 29.1 total methyl terminal branch per 1000 CH ₂ . ¹³ C NMR: 0.33 mol% norbornene-HFIP incorporated.

Procedures for Examples 4 and 5:

In a nitrogen purged drybox, the glass insert with the gas inlet was filled with 0.04 mmol of nickel complex A or D and 20 equivalents (0.4095 g) of B (C ₆ F ₅ ) ₃ . Trichlorobenzene (9 mL) was added to the glass insert, which was then cooled to -30 ° C in a dry box freezer. Norbornene-HFIP (1 mL) was dissolved in 1 mL of Et ₂ O and the resulting solution was added over frozen trichlorobenzene. The insert was immediately cooled again in a -30 ° C. dry box freezer. The gas inlet of the cold insert was covered with an electrical tape and the insert was sealed with a greased cap and removed from the dry box atmosphere. Outside the drying box, the tubes were placed in plastic bags. The bag was sealed, placed in a bucket and surrounded by dry ice. After removing the electrical tape, the glass insert was transferred to a pressure tube. The pressure tube was sealed, evacuated, placed under ethylene (150 psi) and mechanically shaken for about 18 hours at room temperature (rt). After completion of the reaction, methanol (˜20 mL) was added to the glass insert to precipitate the polymer. The copolymer was isolated and dried in vacuo. ¹³ C NMR spectra were obtained at 140 ° C. using 60 mg CrAcAc and 310 mg samples in a total volume of 3.1 mL TCB using a Varian Unity 400 NMR spectrometer equipped with a 10 mm probe.

Example 4

Nickel complex A (0.0211 g) was used to follow the above general procedure. Branched copolymers of ethylene and norbornene-HFIP were isolated as 2.60 g of white powder. ¹³ C NMR: 0.83 mol% norbornene-HFIP incorporated.

Example 5

Nickel complex D (0.0204 g) was used to follow the above general procedure. Branched copolymers of ethylene and norbornene-HFIP were isolated as 3.58 g of white powder. ¹³ C NMR: 0.59 mol% norbornene-HFIP incorporated.

Example 6

In a nitrogen purged drybox, the glass insert with the gas inlet was filled with 0.04 mmol of nickel complex B (0.0205 g) and 20 equivalents (0.4095 g) of B (C ₆ F ₅ ) ₃ . p-xylene (8 mL) was added to the glass insert, which was then cooled to -30 ° C in a dry box freezer. Norbornene-HFIP (2 mL) was dissolved in 1 mL of Et ₂ O and the resulting solution was added over frozen p-xylene. The insert was immediately cooled again in a -30 ° C. dry box freezer. The gas inlet of the cold insert was covered with an electrical tape and the insert was sealed with a greased cap and removed from the dry box atmosphere. Outside the drying box, the tubes were placed in plastic bags. The bag was sealed, placed in a bucket and surrounded by dry ice. After removing the electrical tape, the glass insert was transferred to a pressure tube. The pressure tube was sealed, evacuated, placed under ethylene (150 psi) and mechanically shaken for about 18 hours at room temperature (rt). After completion of the reaction, methanol (˜20 mL) was added to the glass insert to precipitate the polymer. The copolymer was isolated and dried in vacuo to yield 1.75 g of a white powder. ¹³ C NMR spectra were obtained at 140 ° C. using 60 mg CrAcAc and 310 mg samples in a total volume of 3.1 mL TCB using a Varian Unity 400 NMR spectrometer equipped with a 10 mm probe.

Example 7-17

The following catalysts, identified as N-1 to N-4, were prepared according to the synthesis described in Examples 22-25.

Procedure for Examples 7-17:

In a nitrogen purged drybox, the glass inserts were filled with nickel compound and B (C ₆ F ₅ ) ₃ and optionally NaBAF. Next, p-xylene was added to the glass insert followed by NRBF or NBFOH. The inserts were gripped and capped. The glass insert was then filled into the pressure tube inside the drying box. Thereafter, the pressure tube was sealed, taken out of the dry box, connected to a pressure reactor, placed under a predetermined ethylene pressure and mechanically shaken. After the defined reaction time, the ethylene pressure was released and the glass insert was removed from the pressure tube. The polymer was separated into methanol-soluble and insoluble fractions by addition of MeOH (-20 mL). Insoluble fractions were collected on frit and rinsed with MeOH. MeOH was removed in vacuo to give a MeOH-soluble fraction. The polymer was transferred to pre-weighed vials and dried overnight under vacuum. Thereafter, it was characterized and the polymer yield was obtained.

NMR Characterization: ¹ H NMR spectra were obtained at 113 ° C. in TCE-d ₂ using a Bruker 500 MHz spectrometer. ¹³ C NMR spectra using a Varian Unity 400 NMR spectrometer with a 10 mm probe or a Bruker Evans 500 MHz NMR spectrometer using 60 mg CrAcAc and 310 mg samples in a total volume of 3.1 mL TCB Obtained at 140 ° C. ^The total methyl per 1000 CH ₂ was measured using different NMR resonances in the ¹ H and ¹³ C NMR spectra. Because of the peak overlap and other calculation correction methods, the values measured by the ¹ H and ¹³ C NMR spectra are not exactly the same, but they will generally approximate within 10-20% at low comonomer incorporation levels. ¹³ in C NMR spectra, 1000 CH total methyl per 1000 CH ₂ was ₂ per 1B _1, 1B _2, 1B ₃ and 1B _4+, EOC is the sum of the resonance. Total methyl as determined by ¹³ C NMR spectroscopy does not include traces of methyl from the methyl vinyl terminus. ^{In the 1} H NMR spectrum, total methyl is determined from the integration of resonances from 0.6 to 1.08 ppm and CH ₂ 's is determined from the integration of the region from 1.08 to 2.49 ppm. Assuming that there is 1 methine for all methyl groups, one third of the methyl integral is subtracted from the methylene integration to not include methine.

Molecular Weight Characterization: GPC molecular weights are reported against polystyrene standards. Unless otherwise specified, GPC's were run with RI detection at a flow rate of 1 mL / min at 135 ° C. with a run time of 30 minutes. Two columns, AT-806MS and WA / P / N 34200, were used. A Waters RI detector was used and the solvent was TCB with 5 g of BHT per gallon. In addition to GPC, molecular weight information was sometimes obtained by ¹ H NMR spectroscopy (olefin end group analysis) and also by melt index measurement (g / 10 min at 190 ° C.).

Ethylene / NRBF copolymerization (total volume NRBF + p-xylene = 10 mL; 150 psi ethylene; 205 mg B (C ₆ F ₅ ) ₃ ; 18 h) Example Compound (mmol) Temperature (℃) NRBF (mL) Yield ^a (g) NRBF incorporation mol% M.W. Total Me 7 N-1 (0.04) 60 4 2.64 3.08 ( ¹³ C) M _p = 16,574; M _w = 17,428; M _n = 4,796; PDI = 3.63 24.0 ( ¹³ C) 8 N-1 (0.04) 60 2 4.12 1.57 ( ¹³ C) M _p = 12,408; M _w = 14,206; M _n = 5,798; PDI = 2.45 16.3 ( ¹³ C) 9 N-1 (0.04) 90 4 3.72 2.34 ( ¹³ C) M _p = 7,045; M _w = 7,850; M _n = 2,452; PDI = 3.20 20.0 ( ¹³ C) 10 N-1 (0.04) 90 2 9.19 2.15 ( ¹³ C) M _p = 7,599; M _w = 8,085; M _n = 3,313; PDI = 2.44 19.2 ( ¹³ C) 11 N-1 (0.04) 120 4 14.69 4.80 ( ¹³ C) 32.0 ( ¹³ C) 12 N-1 (0.04) 120 2 17.96 0.79 ( ¹³ C) M _p = 4,673; M _w = 5,037; M _n = 1,937; PDI = 2.60 15.8 ( ¹³ C) ^a Yield of MeOH insoluble polymer fraction (g). MeOH soluble polymer fraction was also isolated for the polymerization of Examples 7-12. The ¹ H NMR spectrum and solubility of these fractions indicate that they have a high NRBF incorporation rate (> 50 mol% by ¹ H NMR analysis). Homopolymers of NRBF are typically white powders as in the homopolymers of ethylene produced by catalyst N-1. Therefore, the appearance of these polymers as viscous oils and their methanol solubility are consistent with the copolymers of NRBF and ethylene. Yield and appearance of the MeOH-soluble fraction are as follows: Example 7. 2.50 g viscous yellow oil; Example 8. 2.11 g viscous yellow oil; Example 9. 1 g viscous yellow oil; Example 10. 0.34 g Viscous yellow oil; Example 11. 1.18 g viscous yellow oil; Example 12. 0.44 g viscous yellow oil.

Ethylene / NBFOH copolymerization (total volume NBFOH + p-xylene = 10 mL; 50 psi ethylene; 90 ° C .; 205 mg B (C ₆ F ₅ ) ₃ ; 177 mg NaBAF; 18 hours) Example Compound (mmol) NBFOH (mL) Yield ^a (g) NBFOH incorporation mol% M.W. Total Me 13 N-2 (0.04) 2 0.431 0.56 ( ¹³ C) M _n ( ¹ H) = 4,370 12.1 ( ¹³ C) 14 N-3 (0.04) 2 0.301 0.05 ⁽¹ H) M _n ( ¹ H) = 2,942 12.7 15 N-4 (0.04) 2 0.119 A very small amount ⁽¹ H) 16 N-1 (0.04) 2 1.07 0.75 ( ¹³ C) M _n ( ¹ H) = 2,560 14.4 ( ¹³ C) 17 N-1 (0.04) 4 1.46 0.85 ( ¹³ C) 130.4 ( ¹³ C) ^a Yield of MeOH insoluble polymer fraction (g). MeOH soluble polymer fraction was also isolated for the polymerization of Examples 13-17. The solubility of these fractions indicates that they have a high NBFOH incorporation rate. Homopolymers of NBFOH are typically white powders as in the homopolymers of ethylene produced by catalysts N-1 to N-4. Therefore, the appearance of these polymers as viscous oils / amorphous solids and their methanol solubility are consistent with the copolymers of NBFOH and ethylene. The yield and appearance of the MeOH-soluble fraction are as follows: Example 13. 1.12 g brown oil / Solid; Example 14. 0.98 g yellow oil / solid; Example 15. 1 g tan oil / solid; Example 16. 1.03 g tan oil / solid; Example 17. 1.27 g brown oil / solid.

¹³ C NMR branching analysis of some ethylene copolymers (MeOH-insoluble fractions) of NRBF and NBFOH Example Total Me Me Et Pr Bu Hex + & eoc Am + & eoc Bu + & eoc One 23.3 13.1 3.2 0.6 0.9 5.3 5.6 6.4 2 39.3 31.3 2.8 1.3 0.8 1.4 2.3 3.9 4 50.5 37.2 5.0 1.5 1.4 4.1 5.2 6.8 5 50.5 18.5 6.3 0.8 2.6 16.8 21.2 24.9 6 30.7 12.3 4.0 0.7 1.2 9.1 11.6 13.8 7 24.0 17.2 2.1 0.2 0.6 2.5 4.4 4.4 8 16.3 10.2 2.2 0.3 0.5 2.7 4.3 3.6 9 20.0 10.8 1.7 0.4 0.8 4.5 6.6 7.1 10 19.2 9.8 1.1 0.1 0.6 5.3 7.1 8.2 11 32.0 20.6 0.0 0.5 0.8 7.0 10.1 11.0 12 15.8 3.7 0.0 0.4 0.9 8.6 8.8 11.7 13 12.1 6.8 0.3 0.1 1.8 4.5 4.4 4.9 16 14.4 5.6 0.8 0.1 1.2 5.9 5.3 7.8 17 130.4 110.4 7.3 1.2 35.6 9.2 13.1 11.5

GPC Data for the Ethylene / NRBF Copolymers of Examples 5 and 6 Example M _w M _n M _p PDI 5 4,892 427 364 11.47 6 111,129 915 495 121.41

Example 18

Example 6 was repeated except following the procedures and methods used in Examples 7-17. That is, the methanol soluble polymer fraction as well as the methanol insoluble polymer fraction were isolated. NRBF was used as comonomer.

The yield of methanol insoluble fraction was 0.19 g. Yield and characterization of the methanol insoluble fraction is as follows; 0.75 g; 29.61 mol% NRBF incorporated; 44.7 Me / 1000 CH ₂ ; Mn: no olefin.

Example 19

The following solution was prepared and magnetically stirred overnight.

ingredient Weight (gm)

Methanol Soluble Fraction of Copolymer in Example 9 0.192

2-heptanone 2.134

t-butyl lysocholate 0.050

Dissolved in 2-heptanone filtered through a 0.45 μ PTFE syringe filter

6.25 wt% solution of triphenylsulfonium nonaplate 0.125

Spin coating was performed using a Brewer Science Inc. Model-100CB mixed spin coater / hotplate on a 4 inch diameter “P” type, <100> orientation, silicon wafer. Risso Tech Japan nose. The development was performed with a resist development analyzer (Litho Tech Japan Co. Resist Development Analyzer) (model-790).

6 mL of hexamethyldisilazane (HMDS) primer was deposited and spun at 5000 rpm for 10 seconds to prepare a wafer. After filtration through a 0.45 μm PTFE syringe filter, about 1 mL of the solution was added, rotated at 2500 rpm for 60 seconds and heated at 120 ° C. for 60 seconds.

Exposing the wafer coated with light obtained by passing broadband UV radiation from an ORIEL Model-82421 Solar Simulator (1000 watts) through a 248 nm interference filter passing about 30% of energy at 248 nm. 248 nm image formation was achieved. The exposure time was 30 seconds and the undamaged dose was 20.5 mJ / cm ² . Various exposure doses were generated by using a mask with a variable neutral optical density of 18 positions. After exposure, the exposed wafer was heated at 100 ° C. for 60 seconds.

The wafer was developed in tetramethylammonium hydroxide (TMAH) aqueous solution (OHKA NMD-W, 2.38% TMAH solution) for about 2 seconds. As a result of this test, a positive image was formed at a full dose of 2.7 mJ / cm ² .

Example 20

The following solution was prepared and magnetically stirred overnight.

ingredient Weight (gm)

Methanol Soluble Fraction of Copolymer in Example 9 0.142

2-heptanone 2.134

t-butyl lysocholate 0.100

Dissolved in 2-heptanone filtered through a 0.45 μ PTFE syringe filter

6.25 wt% solution of triphenylsulfonium nonaplate 0.125

A wafer coating, imaging and developing procedure as described in Example 19 was followed except that the development time was 60 seconds. As a result of this test, a positive image was formed at a full dose of 8.3 mJ / cm ² .

Example 21

The following solution was prepared and magnetically stirred overnight.

ingredient Weight (gm)

Methanol Soluble Fraction of Copolymer in Example 18 0.142

2-heptanone 2.134

t-butyl lysocholate 0.100

Dissolved in 2-heptanone filtered through a 0.45 μ PTFE syringe filter

6.25 wt% solution of triphenylsulfonium nonaplate 0.125

The wafer coating procedure described in Example 19 was followed. A photoresist film of suitable quality was formed on the substrate. However, the amount of polymer was insufficient to confirm the proper setting for imaging.

General Methods and Information of Ligand Precursor and Catalyst Synthesis for Examples 22-25

All work related to catalyst synthesis was carried out in a nitrogen purged drying box. Anhydrous, deoxygenated solvents were used in all cases and used as purchased from Aldrich or purified by standard methods. The solvent was stored on 4 mm molecular sieves in a dry box. NaBAF was purchased from Boulder Scientific and Ni [II] allyl halide precursors were prepared according to standard literature methods. (Tert-butyl) ₂ PCH ₂ Li was synthesized by reacting (Tert-butyl) ₂ PCH ₃ (purchased from Strem) with an equimolar amount of Tert-butyl lithium (purchased from Aldrich) for several hours in heptane at 109 ° C. It was. The product was collected on frit and washed with pentane. NMR spectra were recorded using a Brooker 500 MHz spectrometer or a Brooker 300 MHz spectrometer.

Example 22

Synthesis of N-1. A 500 mL round bottom flask was charged with 536 mg (5.40 mmol) of t-butylisocyanate dissolved in about 30 mL of THF. Then (t-Bu) ₂ PCH ₂ Li (898 mg, 5.40 mmol) dissolved in about 30 mL of THF was added. The reaction mixture was stirred for 1 hour. Next, a solution of [Ni (C ₃ H ₅ ) (μ-Cl)] ₂ (730 mg, 2.70 mmol) in THF (about 30 mL) was added and the reaction mixture was stirred for an additional 1 hour, after which The solvent was removed in vacuo. The residue was washed with hexane and dried in vacuo to give 1.80 g (83%) of a purple powder. ¹ H NMR (CD ₂ Cl ₂ , 23 ° C., 300 MHz): δ 6.0-4.0 (broad signal), 4.0-2.0 (broad signal), 1.0-0.0 (broad signal, t-Bu); ³¹ P NMR (CD ₂ Cl ₂ , 23 ° C., 300 MHz): δ 46.7 (s)

Example 23

Synthesis of N-2. 2,4-dimethoxyphenylisocyanate (1.078 g) and (t-Bu) ₂ PCH ₂ Li (1.00 g) were weighed in a separate vial. About 5 mL of THF was added to each vial and the vial was capped and cooled to −30 ° C. in a dry box freezer. A cold (t-Bu) ₂ PCH ₂ Li solution was added to the cold 2,4-dimethoxyphenylisocyanate solution and the reaction mixture was stirred overnight. The solution was filtered and THF was removed in vacuo. The product was washed with toluene to leave the ligand lithium salt as 0.67 g of a creamy powder. ³¹ P NMR (C ₆ D ₆ ) δ 6.69 and 0.00. These ligand lithium salts (0.43 g), [(H ₂ CC (CO ₂ Me) CH ₂ ) Ni (μ-Br)] ₂ (0.27 g) and NaBAF (1.00 g) were placed in a round bottom flask and placed in about Et ₂ O Dissolved in 20 mL. The reaction mixture was stirred overnight. The product was filtered through dry diatomaceous earth and frit. The solvent was removed and the product dried in vacuo to give 1.46 g of N-2 as an orange-brown powder with 1 equivalent of (Li / Na) BAF. ³¹ P NMR (CD ₂ Cl ₂ ) 60.1 (major); 62.1 (Minor).

Example 24

Synthesis of N-3. 0.30 g of phenyl isocyanate (0.22 g) and (t-Bu) ₂ PCH ₂ Li were weighed in a separate vial. About 3 mL of THF was added to each vial. Phenyl isocyanate solution was added to the (t-Bu) ₂ PCH ₂ Li solution and the reaction mixture was stirred overnight. The next day, [(H ₂ CC (CO ₂ Me) CH ₂ ) Ni (μ-Br)] ₂ (0.43 g) was weighed in a separate vial and dissolved in a few mL of THF. The resulting solution was added to the reaction mixture and stirred again overnight. The solvent was removed in vacuo. The product was dissolved in toluene and filtered. The solvent was removed and the product dried in vacuo to give 0.53 g of red powder: ³¹ P NMR (C ₆ D ₆ ) δ 54.1 (major).

Example 25

Synthesis of N-4. 2,6-dimethylphenyl isocyanate (0.27 g) and (t-Bu) ₂ PCH ₂ Li (0.30 g) were weighed in a separate vial. About 3 mL of THF was added to each vial and 2,6-dimethylphenyl isocyanate solution was added to a solution of (t-Bu) ₂ PCH ₂ Li and the reaction mixture was stirred overnight. The next day, [(H ₂ CC (CO ₂ Me) CH ₂ ) Ni (μ-Br)] ₂ (0.43 g) was weighed in a separate vial and dissolved in several mL of THF. The resulting solution was added to the reaction mixture, which was then stirred again overnight. The solvent was removed in vacuo. The product was dissolved in Et ₂ O and filtered through diatomaceous earth and frit. The solvent was removed and the product dried in vacuo to yield 0.75 g of a reddish brown powder. ³¹ P NMR (C ₆ D ₆ ) δ 51.7 (major).

Claims (33)

At least (A) a spacer group selected from the group consisting of ethylene, alpha-olefin, 1,1'-disubstituted olefin, vinyl alcohol, vinyl ether and 1,3-diene; And (B) the following structural formula {Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 10 carbon atoms, a substituted hydrocarbon group, an alkoxy group, a carboxylic acid, a carboxylic acid Ester or the following structural formula -C (R _f ) (R _{f '} ) OR _b [Wherein, R _f and R _{f ′} are the same or different fluoroalkyl groups having 1 to 10 carbon atoms or taken together (CF ₂ ) _n (where n is 2 to 10) and R _b Is a hydrogen atom or an acid- or base-reactive protecting group]; r is a repeating unit derived from a monomer having 0-4, in which at least one of R ₁ , R ₂ , R ₃ and R ₄ is a structural formula C (R _f ) (R _{f ′} ) OR repeating units having a structure containing _b Fluorine-containing polymers prepared from. The fluorine-containing polymer of claim 1, wherein the absorption coefficient is less than 4 μm ⁻¹ at a wavelength of 157 nm. The fluorine-containing polymer of claim 1, wherein the absorption coefficient is less than 3.5 μm ⁻¹ at a wavelength of 157 nm. The fluorine-containing polymer of claim 1, wherein R _f and R _{f ′} are independently a perfluoroalkyl group having 1 to 5 carbon atoms. The fluorine-containing polymer of claim 4 wherein R _f and R _{f ′} are trifluoromethyl. The fluorine-containing polymer of claim 1, wherein the spacer group is selected from the group consisting of ethylene, propylene, isobutylene, ethyl vinyl ether and butadiene. (a) at least (A) a spacer group selected from the group consisting of ethylene, alpha-olefins, 1,1'-disubstituted olefins, vinyl alcohol, vinyl ethers and 1,3-dienes; And (B) the following structural formula {Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 10 carbon atoms, a substituted hydrocarbon group, an alkoxy group, a carboxylic acid, a carboxylic acid Ester or the following structural formula -C (R _f ) (R _{f '} ) OR _b [Wherein, R _f and R _{f ′} are the same or different fluoroalkyl groups having 1 to 10 carbon atoms or taken together (CF ₂ ) _n (where n is 2 to 10) and R _b Is a hydrogen atom or an acid- or base-reactive protecting group]; r is a repeating unit derived from a monomer having 0-4, in which at least one of R ₁ , R ₂ , R ₃ and R ₄ is a structural formula C (R _f ) (R _{f ′} ) OR repeating units having a structure containing _b Fluorine-containing polymers prepared from; And (b) one or more photoactive components And a fluorine-containing polymer having an absorption coefficient of less than 4.0 μm ⁻¹ at a wavelength of 157 nm. The photoresist composition of claim 7, wherein the fluorine-containing polymer has an absorption coefficient of less than 3.5 μm ⁻¹ at a wavelength of 157 nm. The photoresist composition of claim 7, wherein the fluorine-containing polymer has an absorption coefficient of less than 3.0 μm ⁻¹ at a wavelength of 157 nm. The photoresist composition of claim 7, wherein R _f and R _{f ′} are independently a perfluoroalkyl group having 1 to 5 carbon atoms. The photoresist composition of claim 10, wherein R _f and R _{f ′} are trifluoromethyl. 8. The photoresist composition of claim 7, wherein the spacer group is selected from the group consisting of ethylene, propylene, isobutylene, ethyl vinyl ether and butadiene. 8. The photoresist composition of claim 7, wherein the monomer containing a fluoroalcohol functional group is selected from the group consisting of: The photoresist composition of claim 7 further comprising a solvent. The photoresist composition of claim 14, wherein the solvent is selected from the group consisting of trichlorobenzene, methanol, 1,1,2,2-tetrachloroethane-d ₂ , ethyl ether, p-xylene and 2-heptanone. 8. The photoresist composition of claim 7, wherein the photoactive component is chemically bonded to the fluorine-containing polymer. 8. The photoresist composition of claim 7, wherein the photoactive component is not chemically bonded to the fluorine-containing polymer. The photoresist composition of claim 7 further comprising a dissolution inhibitor. (X) (a) at least (A) a spacer group selected from the group consisting of ethylene, alpha-olefins, 1,1'-disubstituted olefins, vinyl alcohol, vinyl ethers and 1,3-dienes; And (B) the following structural formula {Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 10 carbon atoms, a substituted hydrocarbon group, an alkoxy group, a carboxylic acid, a carboxylic acid Ester or the following structural formula -C (R _f ) (R _{f '} ) OR _b [Wherein, R _f and R _{f ′} are the same or different fluoroalkyl groups having 1 to 10 carbon atoms or taken together (CF ₂ ) _n (where n is 2 to 10) and R _b Is a hydrogen atom or an acid- or base-reactive protecting group]; r is a repeating unit derived from a monomer having 0-4, in which at least one of R ₁ , R ₂ , R ₃ and R ₄ is a structural formula C (R _f ) (R _{f ′} ) OR repeating units having a structure containing _b Fluorine-containing polymers prepared from; And (b) one or more photoactive components Wherein the fluorine-containing polymer is subjected to image-by-image exposure of a photoresist layer prepared from a photoresist composition having an absorption coefficient of less than 4.0 μm ⁻¹ at a wavelength of 157 nm to form an image forming and image non-forming surface (Y) developing an exposed photoresist layer having an image forming and an image forming surface to form a relief image on the substrate; Forming a photoresist image on a substrate. The method of claim 19, wherein the fluorine-containing polymer has an absorption coefficient of less than 3.5 μm ⁻¹ at a wavelength of 157 nm. The method of claim 19, wherein the fluorine-containing polymer has an absorption coefficient of less than 3.0 μm ⁻¹ at a wavelength of 157 nm. The method of claim 19, wherein the photoactive component is chemically bonded to the fluorine-containing polymer. The method of claim 19, wherein the photoactive component is not chemically bound to the fluorine-containing polymer. The method of claim 19, wherein the developing step is less than about 5 seconds. The method of claim 19 further comprising a solvent. The method of claim 25, wherein the solvent is selected from the group consisting of trichlorobenzene, methanol, 1,1,2,2-tetrachloroethane-d ₂ , ethyl ether, p-xylene and 2-heptanone. Ethylene and the following structural formula {Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 10 carbon atoms, a substituted hydrocarbon group, an alkoxy group, a carboxylic acid, a carboxylic acid Ester or the following structural formula -C (R _f ) (R _{f '} ) OR _b [Wherein, R _f and R _{f ′} are the same or different fluoroalkyl groups having 1 to 10 carbon atoms or taken together (CF ₂ ) _n (where n is 2 to 10) and R _b Is a hydrogen atom or an acid- or base-reactive protecting group]; r is a repeating unit derived from a monomer of 0-4, at least one of which is one or more of R ₁ , R ₂ , R _3, and R ₄ is a structural formula C (R _f ) (R _{f ′} ) OR _b A copolymer comprising 5 or more methyl terminal branches per 1000 methylene groups, consisting of repeating units having a structure containing. The copolymer of claim 27 comprising at least 10 methyl terminal branches per 1000 methylene groups. The copolymer of claim 27 wherein the monomer is selected from the group consisting of: The copolymer of claim 27, wherein at least 1 mol% of repeating units derived from one or more monomers are present in the copolymer. The copolymer of claim 27 wherein repeating units derived from one or more additional monomers are also present in the copolymer. A process for producing the fluorine-containing polymer of claim 1 comprising contacting a spacer group comprising an alpha-olefin and a repeating unit and a catalytically effective amount of a transition metal catalyst under polymerization conditions to form a fluorine-containing polymer. 32. The process of claim 31 wherein the alpha-olefin is ethylene, the transition metal catalyst comprises nickel and the polymerization conditions comprise a temperature of less than 200 ° C.