KR20040062877A - Solvents and photoresist compositions for short wavelength imaging - Google Patents

Abstract

In particular, new photoresists suitable for short wavelength imaging, including sub-170 nm, such as 157 nm are provided. The resist of the present invention includes a polymer containing fluorine, a photoactive element, and a solvent. Preferred solvents for use in the resist according to the present invention can retain the resist component in solution and can include two or more solution materials (blend members). Particularly in the preferred solvent blends of the present invention, each blend element is evaporated at substantially the same rate while the resist composition maintains a substantially constant concentration of each blend member.

Description

Solvents and photoresist compositions for short wavelength imaging

Photoresist is a photosensitive film used to transfer an image onto a substrate. After the coating layer of photoresist is formed on the substrate, the photoresist layer is exposed to an activating radiation source through a photomask. The photomask has areas that are opaque to activating radiation and other areas that are transparent to activating radiation. Exposure to activating radiation results in photoinduced chemical modification of the photoresist coating, thereby transferring the photomask pattern to the photoresist-coated substrate. After exposure, the photoresist is developed to provide a relief image that allows selective processing of the substrate.

The photoresist may be positive-functional or negative-functional. For most negative-functional photoresists, portions of the coating layer exposed to activating radiation polymerize or crosslink by the reaction of the photoactive compounds with the polymerizable reagents of the photoresist composition. As a result, the exposed coating portion is less soluble in the developer than the unexposed portion. In the case of positive-functional photoresists, the exposed portions are more soluble in the developer, while the unexposed areas remain relatively less soluble in the developer. Photoresist compositions are described in Deforest, Photoresist Materials and Processes, McGraw Hill Book Company, New York, ch. 2,1975 and Moreau, Semiconductor Lithography, Principles, Practices and Materials, Plenum Press, New York, ch. 2 and 4, respectively.

Currently available photoresists are suitable for a variety of applications, but current registers are particularly suited for high performance applications such as the formation of high resolution sub-half micron and sub-quarter micron linewidths. Shows major drawbacks.

As a result, there is interest in photoresists that can be optically imaged with short wavelength radiation, including exposure radiation of about 250 nm or less, or even about 200 nm or less, such as about 193 nm. It may be possible to form smaller line widths by using such short exposure wavelengths. Thus, photoresists that provide high resolution images upon exposure to 248 nm or 193 nm can form extremely small (e.g. sub-0.25 μm) line widths, which, for example, increase circuit density and improve device performance. In order to improve, it satisfies the desire to constantly seek smaller circuit patterns of industrial size.

Has recently been considered as a route to manufacture a smaller line width fluorine F ₂ excimer laser imaging (F ₂ eximer laser imaging), i.e., radiation having a wavelength of about 157 nm. (Kunz et al. , SPIE Proceedings (Advances in Resists Technology), vol. 3678, pages 13-23 (1999))

Summary of the Invention

The novel photoresist composition is provided by consisting of a polymer comprising fluorine, a photoactive element, in particular one or more photoacid generators, and a solvent. The resist of the present invention is particularly suitable for extreme wavelength imaging such as 157 nm, sub-170 nm.

In one aspect, preferred solvents for use in the resists of the present invention are heptanone, especially 2-hetaphthalanone (methyl-n-amyl-ketone) and 3-heptanone; Ethyl-n-amyl-ketone; Ethylene glycol ethyl ether; Propylene glycol methyl ether acetate; Amyl acetate; Methyl iso-amyl ketone; Methyl ethyl ketone; Ethylene glycol methyl ether acetate; Methylamyl acetate; Ethylene glycol methyl ether acetate; Ethyl-n-butyl ketone; Iso-butyl isobutylate; 2-methyl-l-pentanol (hexanol); Ethylene glycol propyl ether; Propylene glycol t-butyl ether; Methylcaproate; Ethyl caproate (ethyl hexanoate); Cumene (isopropylbenzene); xylene; Eye brush; Cycloheptanone; Ethylene glycol ethyl ether acetate; 1-tridecanol; Cyclohexanol; Mesitylene; Hexyl acetate (2-methyl-l-pentyl acetate); Diethylene glycol dimethyl ether (diglyme); Diisobutyl ketone; Di-n-propyl carbonate; Diacetone alcohol; Ethylene glycol butyl ether; And propylene glycol butyl ether.

In another aspect, preferred solvents used in the resist of the present invention are halogenated materials, in particular fluorinated materials. Such halogenated solvents are particularly effective for dissolving the fluorinated resin of the resist of the present invention. Exemplary halogenated solvents used in the resist of the present invention include halogenated aromatic solvents such as chlorobenzene, fluorobenzene, trifluoromethylbenxion, bis (trifluoromethyl) benzene; Perfluoroalkyl solvents; And fluoroethers such as HFE-700, FC-43, and FC-3248 (all available from 3M) and other fluoroether solvents and other fluorinated solvents available from both 3M; And analogues thereof.

The resist composition also preferably consists of a blend of solvents in which one of the blend members is heptanone, preferably 2-heptanone. Other blend members include, for example, ethyl lactate, propylene glycol methyl ether acetate (PGMEA), diacetone alcohol, hexyl acetate, ethyl hexanoate, gamma-butyrolactone (GBL), diglyme, propylene glycol dimethyl ether, and Propylene glycol methyl ether is suitable.

Other solvent blends used in the resists of the present invention include blends containing other ketones or other carbonyl functional groups (eg, esters). It is known that solvents containing carbonyl groups can dissolve the fluoropolymer more effectively than solvents that do not contain carbonyl. In particular, for use in the resist composition of the present invention, as a blend member, ethyl lactate, propylene glycol methyl ether acetate (PGMEA), diacetone alcohol, hexyl acetate, ethyl hexanoate, gamma-butyrolactone (GBL), diglyme Preference is given to dialkyl-ketone and ethoxy ethyl propionate solvents such as cycloheptanone, diisobutyl ketone, including one or more other solvents such as propylene glycol dimethyl ether, and propylene glycol methyl ether. In general, ketone solvents such as heptanone or diisobutyl ketone are more preferred than ester-containing solvents such as ethyl ethoxy propionate.

The solvent blend of the resist composition of the present invention may suitably comprise two or three or more different solvents in a single blend, and more particularly may comprise two or three distinct solvents. Preferably the carbonyl solvent, such as heptanone, diisobutyl ketone, is present in an amount effective to dissolve, ie, the amount effective to dissolve the resist component.

Preferred resist solvent blends of the present invention are halogenated solvents as discussed above. In many cases the increase in solubility is realized by halogenated solvents, for example one or more halogenated solvents comprise up to about 50 volume percent or less of the total solvent of the resist composition, or one or more halogenated solvents comprises Solubility increases even when halogenated solvents are used as ancillary elements of the solvent blend, such as 40, 30, 25, 20, 15, 10, 5, 3 or even 2 volume percent or less of the total solvent of. Solvent blends of the resist composition of the present invention may also contain one or more halogenated solvents, for example, where one or more halogenated solvents are at least 55, 60, 70, 80, 90 or 95 volume percent of the total solvent of the resist composition. It may contain a large amount of solvent. One or more halogenated solvents are preferably used in solvent blends comprising carbonyl and / or hydroxy moieties such as heptanone, cyclohexanone, ethyl lactate, and the like.

Another preferred element of the resist solvent blend of the present invention is water. It is known that water can stabilize solvent blends and resist compositions, such as providing greater resistance to degradation of the photoacid generator compound during formal wear. Water present as a residual solvent after the soft-bake step may also facilitate the deprotection reaction of the photoacid-labile groups present in the resist composition. Preferably, water is present in the resist composition in a relatively small amount, for example at about 10, 8, 6, 5, 4, 3, 2, 1, 0.5 or 0.25 volume percent, relative to the total solvent of the resist composition. Generally preferably, water is present at most 3, 2, 1, 0.5 or 0.25 volume percent of the total solvent component of the resist composition. Water is preferably applied in a solvent blend comprising other solvents containing carbonyl and / or hydroxy moieties such as, for example, heptanone, cyclohexanone, ethyl lactate, and the like.

Particularly preferred solvent blends of the present invention evaporate at a substantially constant rate from the resist composition, where the blend members remain in the resist composition at substantially the same concentration. In particular, solvent blends which form room temperature azeotropes at room temperature, evaporate at the same rate from the resist liquid composition, and maintain the concentration of solvent blend members in the resist composition at substantially the same ratio are preferred. As the concentration of solvent blend member is maintained at substantially the same ratio during the coating and soft-baking process, the enhanced film forming properties of the resist, such as undesirable crystallization or precipitation of other resist elements, formation of irregular film layers The lithographic properties of the resist, which are related to the nature of avoiding undesirable separation of polymer chains and the like, are improved.

In addition to the fluorine-polymer and the photoactive component, the resists of the present invention are suitably based on additives, preferably polymers, and / or fluorinated compositions, surfactants or leveling agents; And one or more other elements such as dissolution inhibiting compounds that are plasticizers. Preferred resists of the invention may also comprise a blend of two or more resin components, wherein preferably each blend member is a fluorine-containing resin, and / or a blend of two or more photoacid generator compounds. to be.

The invention also provides a high resolution relief image, such as a line pattern (dense or isolated), with each line having a line width of 0.40 microns or less, or even about 0.25, 0.20, 0.15, or 0.10 microns or less, and essentially vertical sidewalls. method of forming a relief image). In this method, preferably the coating layer of the resist of the present invention is a short wavelength radiation, in particular sub-200 nm radiation, in particular 157 nm radiation, and high energy radiation having a wavelength below 100 nm, and EW, electron beam, ion It is imaged by other high energy radiation such as beams or x-rays. The present invention provides articles comprising substrates such as microelectronic wafer substrates, optoelectronic substrates or liquid crystal displays or other flat panel displays coated with the polymer, photoresist or resist relief images of the present invention. Another aspect of the invention is described below.

The present invention relates to novel photoresists suitable for short wavelength imaging comprising sub-200 nm, in particular sub-170 nm, such as 157 nm.

The resist of the invention consists of a polymer comprising fluorine, a photoactive element, in particular one or more photoacid generators, and a solvent.

Preferred solvents for use in the resist according to the present invention can retain the resist component in solution and can include two or more solution materials (blend members). Particularly in the preferred solvent blends of the present invention, each blend element is evaporated at substantially the same rate, while the resist composition maintains a substantially constant concentration of each blend member.

As discussed above, novel photoresist compositions are provided that include a fluorine-containing polymer, a photoactive component, in particular a photoacid generator compound, and a solvent.

The solvent element may suitably comprise a single solvent or multiple distinct liquids (solvent blends).

As discussed above, particularly preferred solvents used in the present invention are ketones or other carbonyls (e.g. heptanone, for example 2-heptatanone (methyl-n-amyl-ketone) and 3-heptanone). Ester) functional groups, generally 2-heptanone are preferred; Methyl iso-amyl ketone; C _1-12 alkyl _{(C = O) C l-} 12 alkyl various dialkyl ketones, more preferably C _2-6 alkyl such as ethyl -n- butyl ketone, and diisobutyl ketone C (= O), such as C _2-6 alkyl; And alicyclic ketone compounds such as hexanone.

As used herein, the term "ketone" is used in accordance with its recognized meaning. That is, together with functional groups of the-(C═O) -structure, in particular adjacent saturated carbons, and heteroatomic groups adjacent to the — (C═O) -structure such as esters, amides, carboxys and the like. The term "carbonyl" as used herein includes the -C (= 0)-moiety as well as adjacent carbons as well as heteroatoms. That is, the term "carbonyl" includes ketones, esters, amides, carboxy (-COOH), and analogs thereof.

The resist composition preferably comprises a blend of solvents in which one of the blend members is heptanone, preferably 2-heptanone. Other blend members are suitably, for example, ethyl lactate, propylene glycol methyl ether acetate (PGMEA), diacetone alcohol, hexyl acetate, ethyl hexanoate, gamma-butyrolactone (GBL), diglyme, propylene glycol Dimethyl ether, and propylene glycol methyl ether.

Other solvent blends used with the resist of the present invention include blends containing ketone or carbonyl functional groups (eg, esters). Solvents containing carbonyl groups can dissolve the fluoropolymer more effectively than solvents without keto. In particular, the brand members include ethyl lactate, propylene glycol methyl ether acetate (PGMEA), diacetone alcohol, hexyl acetate, ethyl hexanoate, gamma-butyrolactone (GBL), diglyme, propylene glycol dimethyl ether, and propylene glycol Various dialkyl-ketones such as cyclohexanone, diisobutyl ketone and ethoxy ethyl propionate, including one or more other solvents such as methyl ether, are the preferred solvents used in the resist composition of the present invention.

The solvent blend of the resist composition of the present invention may suitably include two, three, four or more other solvents in a single blend, more particularly two or three distinct solvents in a single resist composition. Preferably the carbonyl solvent, such as heptanone, diisobutyl ketone, is present in an amount effective to dissolve, ie, the amount effective to dissolve the resist component. The dissolution effect of the carbonyl solvent is at least 20, 30, 40, 50, 60, or 70 volumes of the solvent blend, especially for resist compositions wherein the carbonyl solvent is composed of 85 to 90 percent by weight solvent based on the weight of the total composition. It consists of percentages.

As discussed above, halogenated solvents, in particular fluorinated solvents such as, for example, organic fluoroether solvents having from 1 to about 8 or 10 carbons, are preferred solvent blend members. In addition, as discussed above, water is a preferred solvent blend member, preferably 10, 9, 8, 7, 6 of a relatively small amount relative to the total solvent component of the resist composition, eg, all solvents of the resist composition. , 5, 4, 3, 2, or 0.5 volume percent.

As discussed above, particularly preferred solvent blends of the present invention evaporate at a substantially constant rate from the resist composition, where the blend members remain in the resist composition at substantially the same concentration. In particular, solvent blends which form room temperature azeotropes at room temperature (about 25 ° C.), evaporate at the same rate from the resist liquid composition, and maintain the concentration of solvent blend members in the resist composition at substantially the same ratio are preferred. .

Room temperature solvent room temperature azeotrope for use in the resist composition of the present invention can be readily specified through a simple test. For example, two member solvents may be mixed in different proportions. For example, a first blend sample having 5 parts by volume of the first blend member to 20 parts of the second blend member; A second blend member having 5 parts by volume of the first blend member to 15 parts of the second blend member; A third blend sample having 5 parts of the first blend member to 10 parts of the second blend member; A fourth blend sample having 5 parts of the first blend member to 5 parts of the second blend member; A fifth blend sample having 10 parts of the first blend member versus 10 parts of the second blend partner; A sixth blend sample having 15 parts of the first blend member versus 5 parts of the second blend member; And a sixth blend sample having 20 parts of the first brand member versus 5 parts of the second brand member.

Each of these blend samples is included in a vessel with an open top and the pressure is reduced until the blend boils gradually at room temperature. As soon as the sample reaches boiling, it is concentrated and sequestered. During the low pressure boiling process of the blend, additional samples are concentrated and collected, for example after 50 volume percent of the blend sample is evaporated, and other samples of the blend are concentrated and isolated.

As the composition of the concentrated and isolated sample approaches the composition of the solvent blend, for example, the solvent blend member of the isolated sample is present in an amount of volume within about 30, 20, 10 or even 5 percent of the heat treated solvent blend. Solvent blends are then considered to be room temperature room azeotropes. For preferred room temperature azeotrope, for example about 50 volumes of the initial blend sample is present when the solvent blend member of the isolated sample is present in an amount of about 30, 20, 10 or even 5 percent of the heat treated solvent blend. After evaporation, the isolated and concentrated sample approximates the composition of the solvent blend. The amount of each blend member of the isolated sample can be appropriately measured by various methods such as gas chromatography.

Solvent blends of particularly preferred resist compositions of the present invention are:

1) heptanone and ethyl lactate are preferably together at least 60, 70, 80, 90 or 95 volume percent, and preferably heptanone in a much greater amount than ethyl lactate for all solvents of the resist composition, Preferably a solvent blend comprising heptanone, preferably 2-heptanone and ethyl lactate, having a volume to volume ratio of heptanone: ethyl lactate of 2: 1 or greater;

2) Heptanone and propylene glycol methyl ether acetate are preferably together at least 60, 70, 80, 90 or 95 volume percent, and preferably heptane is much higher than propylene glycol methyl ether acetate for all solvents of the resist composition. Solvent blend comprising heptanone, preferably 2-heptanone and propylene glycol methyl ether acetate, wherein the volume to volume ratio of heptanone: propylene glycol methyl ether acetate is 2: 1 or greater;

3) cyclohexanone and ethyl lactate together preferably preferably at least 60, 70, 80, 90 or 95 volume percent of all solvents in the resist composition, and preferably cyclohexanone in much greater amounts than ethyl lactate And preferably a solvent blend comprising cyclohexanone and ethyl lactate having a volume to volume ratio of cyclohexanone: ethyl lactate of 2: 1 or greater;

4) cyclohexanone and propylene glycol methyl ether acetate are preferably together at least 60, 70, 80, 90 or 95 volume percent, and preferably cyclohexanone is less than propylene glycol methyl ether acetate, for all solvents of the resist composition. In much larger amounts, preferably cyclohexanone: solvent blend comprising cyclohexanone and propylene glycol methyl ether acetate with a volume to volume ratio of 2: 1 or greater;

5) Solvents comprising both 2-heptanone and 3-heptanone, preferably at least 60, 70, 80, 90 or 95 volume percent of all solvents of the resist composition, 2-heptanone and 3-heptanone Blend;

6) Heptanone, preferably 2-heptanone, cyclohexanone, and one additional solvent, for example a solvent comprising a bicarbonyl solvent such as ketone, carbonyl or ethyl lactate or propylene glycol methyl ether acetate Blend;

7) one or more additional solvents such as water and one or more carbonyl and / or non-carbonyl solvents such as heptanone, cyclohexanone, ethyl lactate, propylene glycol methyl ether acetate, and the like A solvent blend comprising; Preferably, the water is present in ancillary elements, for example at most 5% by volume, more preferably at most 4, 3, 2, 1, 0.5 or 0.25% by volume relative to the total solvent component of the resist composition; And

8) fluorinated solvents such as halogenated solvents, especially HFE solvents (hydrofluoroethers available from 3M), and one or more carbonyl and / or heptanone, cyclohexanone, ethyl lactate, propylene glycol methyl ether Solvent blends including one or more additional solvents such as non-carbonyl solvents such as acetates, and the like;

Solvent blends that are less windy and thus excluded from the preferred aspects of the present invention are, in particular, two-component solvent blends comprising ketones such as methyl ethyl ketone and benzene solvents such as halobenzenes, in particular chlorobenzenes (ie a total of two distinctions). Resist having a solvent). Photoresists comprising PGMEA (propylene glycol methyl ether acetate), in particular PGMEA as a single solvent (without a blend partner), are also excluded from preferred aspects of the present invention.

The solvent used in the resist composition of the present invention preferably adopts high purity, for example at least 98 percent or 99 percent pure, as measured by gas chromatography. The solvent used in the present invention can also be appropriately filtered immediately before use.

As discussed above, the resists of the present invention are suitably photoactive components comprising fluorine-containing resins, preferably one or more photoacid generator compounds, and optionally basic additives, one or more dissolution inhibiting compounds, One or more other additives, such as effectors, and / or plasticizers.

Suzy

The fluorine-containing resin of the resist of the present invention suitably comprises repeating units derived from at least one unsaturated compound of ethylene. Preferably the unsaturated group is an alicyclic group such as norbornene, cyclohexene, adamantene and analogs thereof. Alicyclic unsaturated compounds preferably have one or more substituents of fluorine, perfluoroalkyl, in particular C _1-12 perfluoroalkyl. Preferably, such fluorine substituents are isolated from unsaturated carbons by at least one saturated carbon in order not to unduly impede polymerization. Also preferred are fluorinated olefinic compounds such as tetrafluoroethylene (TFE) compounds and hexafluoroisopropanol compounds and derivatives thereof. Exemplary preferred unsaturated compounds for the synthesis of fluorine-containing polymers of the present invention include the following formulas (A) to (J).

In the above formulas (A) to (J), each R is independently hydrogen or halogen, especially non-hydrogen substituents such as fluoro, C _1-12 alkyl, haloalkyl, especially C _1-12 fluoroalkyl, preferably Optionally substituted alkyl such as C _1-12 perfluoroalkyl, C _1-12 alkoxy, haloalkoxy, especially optionally substituted alkoxy, carboxyl group, C _1-14 alkyl such as C _1-12 fluoroalkyl Carboxyl, or photoacid-labile groups such as photoacid-labile esters or acetals; m is 1 to the maximum integer allowed by the valence of the monomer, and m is particularly 1, 2, 3, 4 or 5; And n is 0, 1 or 2. Some of the compounds (A) to (J) are described generally in WO 00/17712 and incorporated herein by reference.

Generally preferred monomers of the above formulas include the following formulas (K) and (L):

In the above formulas (K) and (L), X is (-CH _2- ) _p , or -OCH ₂ -or -CH ₂ 0-, wherein p is 0, 1 or 2, preferably 1 or 2; -OCH _2- ; -CH ₂ OCH _2- ; Or -CH ₂ 0-; LG is an element of a photoacid-labile moiety such as hydrogen or a quaternary carbon such as t-butyl or other quaternary carbon of optionally substituted C _4-18 alkyl; And n is 0 or 1.

In general, pendant groups incorporated into the resins of the invention from preferred monomers (such as the R groups in (A) to (F)) include the following structures:

Wherein X is as defined in formulas (K) and (L) above;

Y is a chemical bond connecting hydrogen, oxygen and group Z, (-CH _2- ) _{p with} p of 1 or 2, -CH ₂ 0-, or R is C _1-12 alkyl, preferably C _1-12 CHRO-, which is alkyl; And

Z preferably has alkyl having 1 to 20 carbon atoms and comprises tri (C _1-16 ) alkylmethyl; Di (C _1-16 ) alkylcarboxyylcarboxylmethyl; benzyl; Pensil; Tri (C _1-16 ) carboxyylcaryl; C _1-16 alkylcarbonyloxy; Formyl group; Acetate groups having 1 to 20 carbon atoms; Tetrahydropyranyl; Or tetrahydrofuranyl; And preferably X is -OCH _2- ;

Preferably Y is a bond or -CH ₂ O-; And preferably Z is t-butyl, methyl or pentyl.

Additional monomers which are polymerized to provide fluorine-containing resins of the resists of the invention include those of the formulas (M) to (0), wherein starting materials (ie, (N ') and (O')) Polymerized groups (ie, (M "), (N") and (O ")):

In the structure, M, M ", N, N'N", O, 0 'and O ", R and m are as defined in the monomers of the above formulas (A) to (J); X is p is 0 or 1 Phosphorus (-CH _2- ) p; -OCH _2- ; -CH ₂ 0CH _2- ; or -CH ₂ O-;

Y is a bond, hydrogen, -CH ₂ 0-, or -CHRO-, wherein R is C _1-16 alkyl, preferably C _1-16 alkyl; And preferably X is -OCH _2- ; And preferably Y is a bond or -CH ₂ 0-.

Particularly preferred units of the fluoropolymers of the present invention include units of the formulas 1-9:

In structures 1-9, LG is an element of a photoacid-labile moiety such as hydrogen or quaternary carbon (eg t-butyl); And

Y and Z are as defined above, ie Y is a chemical bond connecting hydrogen, oxygen and group Z, (-CH _2- ) _p with -1 or 2, -CH ₂ 0-, or R is C _{1 -12} alkyl, preferably CHRO-, which is C _1-4 alkyl; And

Z preferably has alkyl having 1 to 20 carbon atoms and comprises tri (C _1-16 ) alkylmethyl; Di (C _1-16 ) alkylcarboxyylcarboxylmethyl; benzyl; Pensil; Tri (C _1-16 ) carboxyylcaryl; C _1-16 alkylcarbonyloxy; Formyl group; Acetate groups having 1 to 20 carbon atoms; Tetrahydropyranyl; Or tetrahydrofuranyl;

And preferably X is -OCH _2- ; Preferably Y is a bond or -CH ₂ O-; And preferably Z is t-butyl, methyl or pentyl. In the above structure, the line extending from the norbornyl ring indicates a bond to the polymer backbone or there.

Particularly preferred fluorine-containing polymers used in the present invention include resins comprising repeating units selected from monomer groups of the formulas (P), (Q), (R) 'and (S):

In the above formulas (P), (Q), (R) and (S), R is hydrogen or optionally substituted alkyl such as C _1-12 alkyl, in particular butyl including methyl, ethyl, propyl, tbutyl, and Its analogs; And X is (—CH ₂ —) _p , or —OCH ₂ — or —CH ₂ O—, wherein p is 0, 1 or 2, preferably 1 or 2, as defined above.

Preferred polymers used in the present invention include 1) a combination of (P) and (Q); 2) a combination of (P), (Q ') and (R); And 3) those containing units of a combination of (P) and / or (Q '), (R) and (S).

Particularly preferred polymers used in the present invention are

(1) the molar ratio of each of (P): (Q '): 50:50; 60: 40; 70: 30; 80: 20; 90: 10; 40: 60; 30: 70; 20: 80; Or 10: a resin composed of units of (P) and (Q) which are 90;

(2) (P) is about 10 to 60 mole percent relative to the total units of polymer, preferably 20 to 50 or 30 to 40 mole percent relative to the total units of polymer; (Q) is about 1 to 50 mole percent relative to the total units of polymer, preferably 5 to 50 or 10 to 40 mole percent relative to the total units of polymer; And (R) is about 20 to 60 mole percent relative to the total units of the polymer, preferably 20 to 60 or 30 to 50 or 60 mole percent relative to the total units of the polymer (P), (Q) and (R) Resin consisting of units of; And

(3) when at least one of (P) and (Q) is present in the polymer, (P) and (Q) are each independently from about 0 to 60 mole percent relative to the total units of the polymer, preferably the total of the polymer 10 to 50 or 20 to 40 mole percent per unit; (R) is about 50 to 60 mole percent relative to the total units of polymer, preferably 10 to 60 or 10 to 30 mole percent, 40 to 50 mole percent relative to the total units of polymer; And (S) is (P) and / or (Q), (R) which is about 10 to 60 mole percent relative to the total units of the polymer, preferably 10 or 20 to 50 or 60 mole percent relative to the total units of the polymer And resins composed of units of (S).

The fluorine-containing polymer of the resist of the present invention is suitably free of aromatic units such as phenyl, naphthyl, or pyridyl.

As discussed above, the fluorine-containing polymer may have one or more other resins present in the resist composition. Such additional resin (s) may or may not contain fluorine, in particular no aromatic units.

The resin component of the resist composition of the present invention should be present in an amount sufficient to provide film-forming characteristics. See the examples below for preferred amounts of resin components.

Photoactive ingredient

Various photoactive components can be employed in the resist of the present invention. Photoacid generators (PAGs) are generally preferred. Particularly preferred PAGs to be used in the resists of the present invention are omniium salt compounds, including iodonium and sulfonium compounds; And non-ionic PAGs such as imidosulfonate compounds, N-sulfonyloxyimide compounds; Diazosulfonyl compounds and other sulfone PAGs, including α, α-methylenedisulfone and disulfonhydrazine, nitrobenzyl compounds, halogenated especially fluorinated non-ionic PAGs. It does not have a preferred PAGs aromatic substituent.

More particularly preferred Iodonium PAGs include those of Formula 1 below;

In Formula 1, R ¹ and R ² are each independently C _1-20 including an alicyclic such as optionally substituted cyclohexyl, adamantyl, isobornyl, norbornyl, penyl, dodecanyl, and the like Alkyl such as alkyl; Optionally substituted carbocyclic aryl such as phenyl, naphthyl and the like; And optionally substituted heteroaromatic or heteroalicyclic, such as a group having 1-3 heteroatoms (N, O or S) as 1 to 3 independent or fused rings and ring members; And

X is a counter anion such as a carboxylate or sulfonate counter anion, optionally substituted alkyl, preferably C _-20 alkyl, in particular one or more electron-withdrawing groups, for example F or Sulfo substituted with one or more moieties such as C _1-10 alkyl (perfluoroalkyl, particularly preferably C _1-10 perfluoroalkyl) substituted with other halo, nitro, cyano, etc. carbonate (-S0 ₃ ^-) or carboxylate (-COO ^-); Optionally substituted carboxylic aryl such as phenyl or naphthyl; Optionally substituted heteroaromatic or heteroalicyclic, such as a group having 1-3 heteroatoms (N, O or S) as 1 to 3 independent or fused rings and ring members.

Preferred imidosulfonate PAGs include compounds of formula (II):

In Formula 2, R is optionally substituted alkyl, preferably C _-20 alkyl, in particular one or more electron-withdrawing groups, for example F or other halo, nitro, cyano, or the like. It is appropriate to be substituted with substituted C _1-10 alkyl (perfluoroalkyl, particularly preferably C _1-10 perfluoroalkyl); Optionally substituted carboxylic aryl such as phenyl or naphthyl; Optionally substituted heteroaromatic or heteroalicyclic, such as a group having 1 to 3 independent or fused rings and 1-3 heteroatoms (N, O or S) as ring members; R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen or a group defined by R, wherein R ² and R ³ are combined and / or R ¹ and R ⁴ are combined to give a ring, preferably an alicy To form a ring having a click ring, eg, from 4 to about 8 ring members; And n is 1, 2, 3 or 4, preferably 1 or 2.

Preferred PAGs of Formula 2 include those having a fused alicyclic ring structure, such as PAGs of Formula 2a:

In Formula 2a, R, R ¹ , R ² , R ^3, and R ⁴ are the same as defined in Formula 2, respectively, and one (and preferably all) of R ¹ , R ² , R ^3, and R ⁴ is appropriate. Preferably hydrogen is as defined in Formula 2 above; And X is methylene (—CH ₂ —), O or S. Particularly preferred PAGs of the above formula (2a) are X is methylene and R is fluorinated C _1-12 alkyl, in particular perfluoroC _l-1 alkyl, such as —CF ₃ .

Although less preferred than iodonium salts and imidosulfonate compounds, sulfonium PAGS is also suitable for use in the present invention. For example, preferred sulfonium PAGs include compounds of Formula 3:

Wherein R ¹ , R ² and R ³ are each independently selected from the same group as defined in Formula 1; And X is as defined in Chemical Scheme 1 above.

Also preferred are sulfonium PAGs, such as those of Formula 4:

Wherein R ¹ and X are as defined in Formula 3 above, the dotted line means a ring structure comprising a sulfur cation depicted as a ring member, and the ring is suitably 5 to about 8 ring members, and one, two or At least endocyclic multiple bonds, and one or more optional ring substituents. Preferably the dotted line forms a non-aromatic ring, such as thienyl, or a fully saturated ring (without endo cyclic double bond).

In the general formula 1, 3 and 4, a preferred counter anion X is a C _l-l5 perfluoroalkyl and C _l-l5 perfluoroalkoxy, for example triflate, perfluoro as butane sulfonate, perfluoro hexane Perfluoroalkyl and perfluoroalkoxy groups such as sulfonate, perfluorooctanesulfonate, and perfluoroethoxyethylsulfonate.

Various other PAGs can be used in the resist of the present invention, including non-ionic PAGs such as substituted disulfone compounds; Sulfonate compounds such as N-oxyimino sulfonate compounds and α-cyano N-oxyimino sulfonate compounds; Cedarone hydrazine compound; Diazomethane disulfone compounds; Nitrobenzyl compounds; Substituted acylsulfonium compounds; And an oxime sulfonate compound containing a bis-N oxyimidosulfonate compound.

More particularly, preferred disulfone PAGs for use in the resists of the present invention include compounds of formula

R ¹ and R ² are the same as defined in Chemical Formula 1.

Preferred oxime sulfonate PAGs used in the resist of the present invention include those of the formula

Wherein R ¹ and R ² are as defined in formula 1 above and / or wherein at least one of R ¹ and R ² is cyano, nitro, haloalkyl, in particular C _1-12 haloalkyl, in particular -CF Electron-drawing groups such as C _1-12 perfluoroalkyl, such as ₃ , —CF ₂ CF ₃ and other perfluoroalkyl, alkanoyl, and the like;

Y is a non-hydrogen substituent, and those defined in Formula 2 above are suitable.

Preferred diazosulfone PAGS used in the resist of the present invention include those of the formula

In the above, R ¹ and R ² are the same as defined in the formula (1).

Preferred α, α-methylenedisulfone PAGs used in the resist of the present invention include those of the formula (8):

Wherein R ¹ and R ² are the same or different and are not hydrogen or as defined in Formula 1 above;

R ³ and R ⁴ are the same or different and are not hydrogen or a non-hydrogen substituent as defined for R ¹ of Formula 1 above, and preferably at least one of R ³ and R ⁴ is not hydrogen, more preferably R ³ and R ⁴ are not both hydrogen.

As mentioned above, disulfonehydrazine PAGS (i.e., the hydrazine moiety is inserted in two sulfone moieties) are also suitable, preferably here the hydrazine moiety (e.g. -N (R ³ ) -N (R ⁴ )-) is located in the middle of the sulfone moiety that is mono- or di-substituted with two non-hydrogen substituents. Preferred disulfonhydrazine PAGS for use in the resist of the present invention comprises a compound of formula

Wherein R ¹ and R ² are the same or different and are not hydrogen or as defined in Formula 1 above;

R ³ and R ⁴ are the same or different and are not hydrogen or a non-hydrogen substituent as defined for R ¹ of Formula 1 above, and preferably at least one of R ³ and R ⁴ is not hydrogen, more preferably R ³ and R ⁴ are not both hydrogen.

Suitable PAGs used in the resists of the present invention also include disulfonylamine (ie -S0 ₂ -N-SO _2- ) salts such as:

Wherein R ¹ and R ² are the same or different and are not hydrogen or as defined in Formula 1 above; And X is a counter ion.

One or more PAGS is employed in the resist in an amount sufficient to provide an image that can be developed upon exposure to active radiation, such as 157 nm radiation. One or more PAGs is suitably employed at 1 to 15 weight percent, more particularly about 2 to 12 weight percent, relative to the total solids of the resist (all components except solvent).

PAGs used in the resists of the present invention can be prepared by generally known methods. See, for example, US Pat. Nos. 4,442,197 and 4,642,912 and European Patent Application No. 0708368A1 for the synthesis of Iodonium PGAs. See WO94 / 10608 for the synthesis of N-sulfonyloxyimide PAGs. Diazosulfone PAGs can be prepared, for example, by the methods described in European patent application 0708368A1 and US Pat. No. 5,558,976. See also WO 00/10056.

Basic additives

As discussed above, the resist of the present invention may suitably include basic additives. Basic additives can be used in relatively small amounts (eg 0.1 to 1,2 or about 3 weight percent of the photoactive component) and significantly increase the lithographic action, especially the resolution of the developed resist relief image. In particular, the addition of a suitable base compound to the resist of the present invention effectively inhibits the diffusion of undesirable photoacid into the mask region in the following exposure process.

Preferred basic additives are amide compounds, in particular comprising primary, secondary, tertiary and quaternary amines. Amines that are not of high nucleophilic nature are generally preferred to avoid undesired reaction of the base additive with other resist composition elements such as PAG and / or solvents.

More particularly, secondary and tertiary amines are generally preferred, especially optionally substituted alkyls such as, for example, optionally substituted C _3-20 alkyl having at least 3 or 4 carbons; Optionally substituted alkyl having at least 3 or 4 carbons, for example optionally substituted C _3-20 alkyl comprising an alicyclic group such as optionally substituted cyclohexyl, adamantyl, isobornyl, and the like; Optionally substituted alkenyl such as, for example, optionally substituted C _3-20 alkenyl having at least 3 or 4 carbons; Optionally substituted alkynyl such as, for example, optionally substituted C _3-20 alkynyl having at least 3 or 4 carbons; Optionally substituted carbocyclic isles such as phenyl; Optionally substituted 1 to 3 independent or fused rings with heteroaryl or heteroalicyclic having heteroaryl or heteroalicyclic group having 1 to 3 heteroatoms (especially N, O or S) per ring; Secondary and tertiary amines having the same steric large substituent are preferred.

Particularly preferred basic additives used in the resist of the present invention are DBU (1, 8-diazobicyclo [5.4.0] ounde-7-ene); DBN (1,5 diazabicyclo [4.3.0] non-5-ene; N, N-bis- (2-hydroxyethyl) piperazine; N, N-bis- (2 hydroxyethyl) -2, 5-diazobicyclo [2.2.1] heptane; N-triisopropanolamine; dibutyl amine, preferably their branched isomers such as diisobutylamine and diterbutylamine; tributyl amine and again diterbutylamine and Tritertbutylamine, and their branched isomers such as analogues, optionally substituted piperidine and other optionally substituted piperazine compounds, especially hydroxy-substituted or N-ethanol piperidine and N-di Also suitable are C _1-12 alcohol-substituted piperidine and piperazine, such as ethanol piperadine, and also other basic compounds, especially compounds having one or more nitrogen ring members and having from 5 to 8 total ring members. Suitable.

Other preferred base additives are N-substituents of hydroxy-alkyl secondary and tertiary amines, for example C _2-20 alkyl having one, two, three or more hydroxy moieties, in particular one or two hydroxy moieties. Secondary and tertiary amines having at least one; At least one of the secondary or tertiary nitrogens comprises a junction or bridgeheaded alicyclic amine of a bicyclic or multicyclic compound. Also suitable are polymerpyridyl compounds thereof such as di-butyl pyridine and poly (vinylpyridine). Generally, the base additive of the polymer is suitable substituted amines having a molecular weight of, for example, about 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400 or 1500. .

Especially in resist systems, the base additives do not substantially interfere with the photoactive component, ie do not react with the PAG, especially during storage of the resist. In particular, the base additive can be used for 2, 3, 4, 5 or 6 months during storage of the resist composition, for example at reduced temperatures such as about 25 ° C. or refrigeration conditions (eg about 5, 10, 15 or 18 ° C.). In the meantime, it is desirable to select so that undesirable decomposition of the photoacid generator can be avoided. More particularly for resists comprising dicarboxylate imide PAG (described in Formulas 2 and 2a above) or iodonium compounds such as PAGs of Formula 1 above, in particular nitrogen is a ring member, e.g. DBU, DBN Hindered secondary or tertiary amines such as monocyclic, bicyclic and tricyclic amines, alkylate pyridine, for example pyridine optionally substituted with one or more C _1-18 alkyl groups Quinoline, optionally substituted piperidine, optionally substituted pyridine, and analogs thereof are preferably used. In addition to alicyclic base additives having nitrogen ring members, it is also preferred to use imidosulfonates and iodonium in combination, and PAGs have non-one or more alkyl substituents having at least 4 carbon atoms. Cyclic secondary and tertiary amines. Non _-free secondary and tertiary amine substituents substituted with one or more alkyl groups, such as C _-20 alkyl groups, are also preferred for use with iodonium PAG.

Carboxylate additives (such as carboxylate salts such as ammonium carboxylate salts) are less preferred for use with dicarboxylate imides. Carboxylate additives are also less preferred for use with iodonium PAG.

The base additive is suitably used in the resist composition using 0.01 to 5 weight percent relative to the total solid phase (all components except solvent), more preferably about 0.05 to 2 weight percent relative to the total solid phase.

Dissolution inhibitor compounds

Preferred dissolution inhibitor compounds in the resists of the invention are polymeric and / or include fluorine substituents. As described above, preferred dissolution inhibitor compounds include compounds containing photoacid-labile groups such as photoacid-labile esters or acetal moieties. Also preferred are low molecular weight materials, for example polymers or oligomers having Mw of less than 5,000, more preferably less than about 4,000, 3,000, 2,000, 1,000 or 500. Fluorinated polymers or oligomers are particularly preferred dissolution inhibitor compounds.

Dissolution inhibitors also need not be polymers (eg those containing repeat units). For example, various non-polymeric compositions, in which the material is fluorinated, are suitable dissolution inhibitors for the resists of the present invention. One or more isolated or fused compounds, including, for example, fluorinated steroid compounds, such as fluorinated cholates and lithocholates, such as cholic acid, deoxycholic acid, lithocholic acid, t-butyl deoxycholate, t-butyllitocholate, and the like. Fluorinated compounds with rings are suitable. Fluorinated steroid compounds may be suitably preferred by fluorination of known steroids, which transforms carbonyl groups into difluoromethylene. Such non-polymeric compounds may also have one photoacid-labile group, for example a photoacid-labile ester or acetal moiety.

The at least one dissolution inhibitor compound is suitably present in the resist composition in an amount of at least about 0.001 to 5% by weight, more preferably at least 0.001 to 1% by weight of the total solids of the resist, based on the total solids (all components except solvent). May exist.

Surfactants and Levelers

Surfactants and planarizing agents used in the resists of the present invention include ionic salts such as, for example, silicon-containing compounds and ammonium compounds. Silicone-containing compounds are generally preferred surfactants. Examples of preferred surfactants and planarizing agents include Silwet 7604 (siloxane copolymers from Union Carbide); FC-430 (imidosulfonate from 3M); RO8 (mixture containing fluoroalcohol); Modaflow (acrylate material). Surfactants and planarizing agents can be suitably used in the amounts described above for the dissolution inhibitor compounds.

Plasticizer compound

As described above, the resists of the present invention may also contain one or more plasticizer materials that can inhibit or prevent unwanted crazing or cracking of the deposited resist layer in addition to improving the adhesion of the resist layer to the underlying material. It may contain. Preferred plasticizers are for example materials having at least one hetero atom (particularly S or O), and preferably have a molecular weight of about 20 to 1000, more typically about 20 to about 50, 60, 70, 80, 90, 100, Materials which are 150, 200, 250, 300, 400 or 500, for example bis (2-butoxyethyl) adipate; Bis (2-butoxyethyl) sebacate; Bis (2-butoxyethyl) phthalate; 2-butoxyethyl oleate; Diisodecyl adipate; Adipates, sebacates and phthalates, such as diisodecyl glutarate; And poly (ethylene glycol) acrylate, poly (ethylene glycol) bis (2-ethylhexanoate), poly (ethylene glycol) dibenzoate, poly (ethylene glycol) dioleate, poly (ethylene glycol) monooleate Poly (ethylene glycol) such as tri (ethylene glycol) bis (2-ethylhexanoate), and the like.

The one or more plasticizer compounds may suitably be present in the resist composition in an amount of about 0.5 to 10% by weight or more, more preferably 0.5 to 3% by weight of the total solids of the resist, based on the total solids (all components except solvent). have.

As described, various portions of PAG, basic additives and resin units, and other components of the resist of the present invention may be optionally substituted, typically for example halogen (particularly F, Cl or Br); C _1-8 alkyl; C _1-8 alkoxy; C _2-8 alkenyl; C _2-8 alkynyl; Hydroxyl; C _1-6 alkanoyl, eg alkanoyl such as acyl; The 1, 2 or 3 position may be substituted by one or more suitable groups such as carbocyclic aryl such as phenyl. However, a plurality of carbon-carbon bonds and aromatic groups are not preferable because of excessive absorbance of the exposure radiation.

Preferred substituent groups are generally fluorinated C _1-12 alkyl, perfluoro C _1-12 alkyl, and perfluoro C _1-12 alkylene, fluorinated C _3-8 cycloalkyl, and fluorinated cyclic ethers and fluorinated cyclic It will contain or consist of at least one halogen atom, preferably fluorine, such as fluorinated ethers including esters (including C _1-12 alkoxy) and esters (including C _1-12 esters).

As used herein, alkyl, alkenyl and alkynyl refer to both cyclic groups unless otherwise modified. Provided that the cyclic group will contain at least three carbon ring members. The alkoxy group of the resist component suitably has 1 to about 16 carbons and 1, 2, 3 or 4 alkoxy linkages. Suitable alkanoyl groups have from 1 to about 16 carbons and at least one carbonyl group, typically 1, 2 or 3 carbonyl groups. Carbocyclic aryl used in the present invention has 1 to 3 separated or fused rings and 6 to about 18 carbon ring members and may include phenyl, naphthyl, biphenyl, acenaphthyl, phenanthracyl, and the like. Non-heteroaromatic groups. Phenyl and naphthyl are sometimes preferred. Suitable heteroaromatic or heteroaryl groups will have from 1 to 3 rings, 3 to 8 ring members and 1 to about 3 hetero atoms (N, O or S) in each ring. Particularly suitable heteroaromatic or heteroaryl groups are for example coumarinyl, quinolinyl, pyridyl, pyrimidinyl, furyl, pyrrolyl, thienyl, thiazolyl, oxazolyl, imidazolyl, indolyl, benzofuranyl And benzothiazole.

The resist of the present invention can be easily prepared by those skilled in the art. For example, the photoresist compositions of the invention can be prepared by dissolving the components of the photoresist in a combination of 2-heptanone and ethyl lactate, which is a suitable solvent described herein, for example, a preferred solvent. Typically, the solids of the composition vary from about 5 to 35 weight percent of the total weight of the photoresist composition, and more typically from 5 to about 12 or 15 weight percent of the total weight of the photoresist composition. The resin binder and photoactive component should be present in an amount sufficient to provide a film coating layer and to form a good quality latent and relief image.

The composition of the present invention is generally used according to known procedures. The liquid coating composition of the present invention is applied to the substrate by, for example, spinning, dipping, roller coating or other conventional coating technique. In spin coating, the solids of the coating solution can be adjusted to provide the desired film thickness based on the specific spinning equipment used, the viscosity of the solution, the speed of the spinner and the amount of time allowed for spinning.

The resist composition of the present invention is suitably applied to a substrate conventionally used in processes involving coating as a photoresist. For example, the composition may be applied onto a silicon wafer or a silicon wafer coated with silicon dioxide for the manufacture of microprocessors and other integrated circuit components. Aluminum-aluminum oxide, gallium azenide, ceramics, quartz, copper, glass substrates and the like are also suitably used.

The photoresist coating on the surface is then dried, preferably by heating until the photoresist coating is viscous to remove the solvent. It is then imaged through a mask in a conventional manner. The exposure is sufficient to effectively activate the photoactive component of the photoresist system to produce a patterned image in the resist coating layer, and more specifically, the exposure energy is typically from about 1 to about 1, depending on the components of the exposure apparatus and the photoresist composition. 100 mJ / cm ² range.

As described above, the coating layer of the resist composition of the present invention is preferably photoactivated by short exposure wavelengths, in particular by sub-300 and sub-200 nm, with sub-170 nm exposure wavelengths, in particular 157 nm being particularly preferred. Wavelength. However, the resist composition of the present invention can also be appropriately imaged by higher wavelengths. For example, the resins of the present invention can be imaged at higher wavelengths, such as about 193 nm or 248 nm, in combination with a suitable PAG and a photosensitizer if necessary.

Following exposure, the film layer of the composition is baked at a temperature of preferably about 70 ° C to about 160 ° C. Thereafter, the film is developed. Polar developer, preferably quaternary ammonium hydroxide solution, such as tetra-alkyl ammonium hydroxide solution; various amine solutions, preferably 0.26 N tetramethylammonium hydroxide, such as ethyl amine, n-propyl amine, diethyl Amines, di-n-propyl amines, triethyl amines, or methyldiethyl amines; Alcohol amines such as diethanol amine or triethanol amine; Positive processing is performed on the exposed resist film by using an aqueous base developer such as a cyclic amine such as pyrrole, pyridine, and the like. Plasma development can also be used. In general, the phenomenon is in accordance with the process recognized in the art.

Following the development of a photoresist coating on the substrate, for example, by chemically etching or plating the resist-free substrate region according to procedures known in the art, it can be selectively processed on the resist-free region of the developed substrate. . For the fabrication of microelectronic substrates, for example for the fabrication of silicon dioxide wafers, a suitable etchant may be applied as a gas etchant, for example a plasma stream, Cl ₂ or CH ₄ / CHF _3. Halogen plasma etchant such as chlorine or fluorine-based etchant such as etchant. After this treatment, the resist can be removed from the processed substrate using known stripping procedures.

All documents mentioned in the present invention belong to the reference in the present invention. The following examples are illustrative of the invention and are not intended to limit the invention.

Example 1 Preparation of Resist of the Invention

The resist of the present invention is prepared by mixing the following components, the amount of which is indicated as weight percent of solids (all components except solvent) and the resist is formulated as a 90% fluid formulation:

ingredient amount Resist Residual solid PAG 5 Base additive 0.5 Dissolution inhibitor 10 Surfactants 0.2 Plasticizer 0.6 menstruum Up to 10 wt% solids

In the resist, the resin is a fluorine-containing terpolymer consisting of norbornene; t-butylacrylate and tetrafluoroethylene (TFE) units are prepared by free radical polymerization of monomers; PAG is a compound of formula (IIa) wherein X is methylene and R is -CF ₃ ; The base additive is DBU; The dissolution inhibitor is fluorinated cholic acid; The surfactant is Sylwet 7604; Plasticizer is poly (ethyleneglycol) dioleate; The solvent is a 70:30 v / v combination of 2-heptanone and ethyl lactate.

The blended resist composition is spin coated onto a HMDS vapor primed 4 inch silicon wafer and softbaked at 90 ° C. for 60 seconds by vacuum hotplate. The resist coating layer is exposed through a photomask at 157 nm, and then the exposed coating layer is baked after exposure at 110 ° C. The coated wafer is then treated with 0.26N tetramethylammonium hydroxide aqueous solution to develop the imaging resist layer and provide relief images.

It is understood that the foregoing detailed description of the invention is merely illustrative, and that changes and modifications may be effective without departing from the spirit or scope of the invention as set forth in the following claims.

Claims (66)

A fluorinated resin, a photoactive component, and a solvent component, the solvent component comprising at least two different solvent mixtures, wherein one of the different solvents does not contain a ketone moiety, except that methyl ethyl ketone and chloro Photoresist composition excluding the solvent component consisting of benzene. The photoresist composition of claim 1, wherein the solvent component comprises heptanone. The photoresist composition of claim 1, wherein the solvent component comprises cyclohexanone. The photoresist composition of claim 1, wherein the solvent component comprises ethyl lactate. The photoresist composition of claim 1 wherein the solvent component comprises propylene glycol methyl ether acetate. 6. The photoresist composition of any one of claims 1 to 5, wherein the solvent component comprises at least two solvents capable of forming a room temperature azeotrope. The solvent component of claim 1, wherein the solvent component is heptanone; Ethyl-n-amyl-ketone; Methyl ethyl ketone; Ethylene glycol ethyl ether; Propylene glycol methyl ether acetate; Amyl acetate; Methyl iso-amyl ketone; Ethylene glycol methyl ether acetate; Methylamyl acetate; Ethylene glycol methyl ether acetate; Ethyl-n-butyl ketone; Iso-butyl isobutyrate; 2-methyl-1-pentanol (hexanol); Ethylene glycol propyl ether; Propylene glycol t-butyl ether; Methylcaproate; Ethyl caproate (ethyl hexanoate); Cumene (isopropylbenzene); Xylene; Anisole; Ethylene glycol ethyl ether acetate; 1-tridecanol; Cyclohexanol; Mesitylene; Hexyl acetate; Diethylene glycol dimethyl ether (diglyme); Diisobutyl ketone; Di-n-propyl carbonate; Diacetone alcohol; Ethylene glycol butyl ether; And at least two different solvents selected from the group consisting of propylene glycol butyl ether. The photoresist composition of claim 1 wherein the photoresist comprises at least three different solvents. A fluorinated resin, a photoactive component, and a solvent component, wherein the solvent component is 3-heptanone; Ethyl-n-amyl-ketone; Ethylene glycol ethyl ether; Amyl acetate; Methyl iso-amyl ketone; Ethylene glycol methyl ether acetate; Methylamyl acetate; Ethylene glycol methyl ether acetate; Ethyl-n-butyl ketone; Iso-butyl isobutyrate; 2-methyl-1-pentanol (hexanol); Ethylene glycol propyl ether; Propylene glycol t-butyl ether; Methylcaproate; Ethyl caproate (ethyl hexanoate); Cumene (isopropylbenzene); Xylene; Anisole; Ethylene glycol ethyl ether acetate; 1-tridecanol; Cyclohexanol; Mesitylene; Hexyl acetate; Diethylene glycol dimethyl ether (diglyme); Diisobutyl ketone; Di-n-propyl carbonate; Diacetone alcohol; Ethylene glycol butyl ether; And a solvent selected from the group consisting of propylene glycol butyl ether. A photoresist composition comprising a fluorinated resin, a photoactive component, and a solvent component, wherein the solvent component comprises at least three different solvent mixtures. The photoresist composition of claim 10, wherein the solvent component comprises heptanone. 12. The photoresist composition of claim 10 or 11, wherein the solvent component comprises cyclohexanone. The photoresist composition of claim 10, wherein the solvent component comprises ethyl lactate. The photoresist composition of claim 10, wherein the solvent component comprises propylene glycol methyl ether acetate. The photoresist composition of claim 10, wherein the solvent component comprises at least two solvents capable of forming a room temperature azeotropic mixture. The method of claim 10 wherein the solvent component is heptanone; Ethyl-n-amyl-ketone; Ethylene glycol ethyl ether; Propylene glycol methyl ether acetate; Amyl acetate; Methyl iso-amyl ketone; Methyl ethyl ketone; Ethylene glycol methyl ether acetate; Methylamyl acetate; Ethylene glycol methyl ether acetate; Ethyl-n-butyl ketone; Iso-butyl isobutyrate; 2-methyl-1-pentanol (hexanol); Ethylene glycol propyl ether; Propylene glycol t-butyl ether; Methylcaproate; Ethyl caproate (ethyl hexanoate); Cumene (isopropylbenzene); Xylene; Anisole; Ethylene glycol ethyl ether acetate; 1-tridecanol; Cyclohexanol; Mesitylene; Hexyl acetate; Diethylene glycol dimethyl ether (diglyme); Diisobutyl ketone; Di-n-propyl carbonate; Diacetone alcohol; Ethylene glycol butyl ether; And at least three solvents selected from the group consisting of propylene glycol butyl ether. A photoresist composition comprising a fluorinated resin, a photoactive component, and a solvent component, wherein the solvent component comprises a halogenated solvent but excludes a solvent composed of chlorobenzene and methylethyl ketone. 18. The photoresist composition of claim 17, wherein the photoresist composition comprises a fluorinated solvent. 18. The photoresist composition of claim 17, wherein the photoresist composition comprises a fluoroether solvent. 20. The photoresist composition of any one of claims 17 to 19, wherein the solvent component comprises heptanone. 21. The photoresist composition of any one of claims 17 to 20, wherein the solvent component comprises cyclohexanone. 22. The photoresist composition of any of claims 17 to 21, wherein the solvent component comprises ethyl lactate. 23. The photoresist composition of any of claims 17 to 22, wherein the solvent component comprises propylene glycol methyl ether acetate. The photoresist composition of claim 17, wherein the solvent component comprises at least two solvents capable of forming a room temperature azeotropic mixture. The photoresist composition of claim 17, wherein the solvent component comprises at least three different solvents. 26. The process of claim 17, wherein the solvent component is heptanone; Ethyl-n-amyl-ketone; Ethylene glycol ethyl ether; Propylene glycol methyl ether acetate; Amyl acetate; Methyl iso-amyl ketone; Ethylene glycol methyl ether acetate; Methylamyl acetate; Ethylene glycol methyl ether acetate; Ethyl-n-butyl ketone; Iso-butyl isobutyrate; 2-methyl-1-pentanol (hexanol); Ethylene glycol propyl ether; Propylene glycol t-butyl ether; Methylcaproate; Ethyl caproate (ethyl hexanoate); Cumene (isopropylbenzene); Xylene; Anisole; Ethylene glycol ethyl ether acetate; 1-tridecanol; Cyclohexanol; Mesitylene; Hexyl acetate; Diethylene glycol dimethyl ether (diglyme); Diisobutyl ketone; Di-n-propyl carbonate; Diacetone alcohol; Ethylene glycol butyl ether; And at least one solvent selected from the group consisting of propylene glycol butyl ether. A photoresist composition comprising a fluorinated resin, a photoactive component, and a solvent component, wherein the solvent component comprises water. 28. The photoresist composition of claim 27, wherein water comprises only about 3% of the total solvent of the composition. 29. The photoresist composition of claim 27 or 28, wherein the solvent component comprises heptanone. 30. The photoresist composition of any one of claims 27 to 29 wherein the solvent component comprises cyclohexanone. 31. The photoresist composition of any one of claims 27-30, wherein the solvent component comprises ethyl lactate. 32. The photoresist composition of any of claims 26 to 31, wherein the solvent component comprises propylene glycol methyl ether acetate. 33. The photoresist composition of any one of claims 27 to 32, wherein the solvent component comprises at least two solvents capable of forming a room temperature azeotrope. 34. The photoresist composition of any of claims 27 to 33, wherein the solvent component comprises at least three different solvents. 35. The process of any one of claims 27 to 34 wherein the solvent component is heptanone; Ethyl-n-amyl-ketone; Methyl ethyl ketone; Ethylene glycol ethyl ether; Propylene glycol methyl ether acetate; Amyl acetate; Methyl iso-amyl ketone; Ethylene glycol methyl ether acetate; Methylamyl acetate; Ethylene glycol methyl ether acetate; Ethyl-n-butyl ketone; Iso-butyl isobutyrate; 2-methyl-1-pentanol (hexanol); Ethylene glycol propyl ether; Propylene glycol t-butyl ether; Methylcaproate; Ethyl caproate (ethyl hexanoate); Cumene (isopropylbenzene); Xylene; Anisole; Ethylene glycol ethyl ether acetate; 1-tridecanol; Cyclohexanol; Mesitylene; Hexyl acetate; Diethylene glycol dimethyl ether (diglyme); Diisobutyl ketone; Di-n-propyl carbonate; Diacetone alcohol; Ethylene glycol butyl ether; And at least one solvent selected from the group consisting of propylene glycol butyl ether. A photoresist composition comprising a fluorinated resin, a photoactive component, and a solvent component, wherein the solvent component comprises ethyl lactate. 37. The photoresist composition of claim 36, wherein the solvent component comprises heptanone. 38. The photoresist composition of claim 36 or 37, wherein the solvent component comprises cyclohexanone. 39. The photoresist composition of any of claims 36 to 38, wherein the solvent component comprises propylene glycol methyl ether acetate. A photoresist composition comprising a fluorinated resin, a photoactive component, and a solvent component, wherein the solvent component comprises a fluorinated solvent. A photoresist composition comprising a fluorinated resin, a photoactive component, and a solvent component, wherein the solvent component comprises at least two solvents capable of forming a room temperature azeotropic mixture. 42. The photoresist composition of claim 41, wherein the solvent component comprises at least three different solvents. 42. The photoresist composition of claim 41, wherein the solvent component comprises at least four solvents. The photoresist composition of claim 1, wherein the photoactive component comprises one or more iodonium compounds. The photoresist composition of claim 1, wherein the photoactive component comprises one or more sulfonium compounds. 46. The photoactive component of claim 1, wherein the photoactive component is imidosulfonate, N-sulfonyloxyimide, diazosulfonyl, α, α-methylenedisulfone, disulfonhydrazine, nitrobenzyl, and disulfonyl amine Photoresist composition comprising a. The photoresist composition of claim 1, wherein the photoresist further comprises one or more materials selected from the group of basic additives, dissolution inhibitor compounds, surfactants, and plasticizers. 48. The photoresist composition of any one of claims 1 to 47 wherein the fluorinated resin comprises at least one polymerized unit corresponding to the structures of formulas (A) to (S) as defined above. The photoresist composition of claim 1, wherein the resin comprises a group of the formula: Where X is (CH _2- ) _p , where p is 0 or 1; -OCH _2- ; -CH ₂ OCH _2- ; Or -CH ₂ O-; Y is hydrogen, a chemical bond connecting oxygen and group Z, (-CH _2- ) _p (where p is 1 or 2), -CH ₂ O-, or CHRO- where R is C _1-16 alkyl )ego; Z is alkyl; Di (C _1-16 ) alkylcarboxylicarylmethyl; benzyl; Fenchyl; Tri (C _1-16 ) carbocyclicaryl; C _1-16 alkylcarbonyloxy; Formyl group; Acetate groups; Tetrahydropyranyl; Or tetrahydrofuranyl. The photo of claim 1, wherein the fluorinated resin comprises at least one polymerized unit corresponding to the structures of formulas (P), (Q), (R) and / or (S) as defined above. Resist composition. 51. The photoresist of claim 1 wherein the photoresist is DBU; DBN; N, N-bis- (2-hydroxyethyl) piperazine; N, N-bis- (2-hydroxyethyl) -2,5-diazobicyclo [2.2.1] heptane; N-triisopropanolamine; Dibutyl amine; Tributyl amine; Optionally substituted piperidine; And a basic additive that is any other piperazine. The photoresist composition of claim 1, wherein the photoresist comprises hydroxy-alkyl secondary and tertiary amines. 53. The photoresist composition of any of claims 1-52, wherein the photoresist comprises a polymeric amine. 55. The photoresist composition of any one of claims 1 to 53, wherein the photoresist comprises a fluorination dissolution inhibitor. 55. The photoresist composition of claim 54, wherein the dissolution inhibitor is a steroid. The photoresist composition of claim 1, wherein the photoresist comprises a polymer dissolution inhibitor. The photoresist composition of claim 1, wherein the photoresist comprises a plasticizer material. 58. The photoresist composition of claim 57, wherein the plasticizer comprises one or more oxygen or sulfur atoms. 59. The photoresist composition of claim 57 or 58 wherein the plasticizer is an adipate, sebacate, phthalate or poly (ethylene glycol). Applying a coating layer of the photoresist composition of claim 1 to the substrate; Exposing the photoresist coating layer to active radiation and then developing the exposed resist layer to form a photoresist relief image. 61. The method of claim 60, wherein the photoresist coating layer is exposed to radiation having a wavelength of less than about 200 nm. 61. The method of claim 60, wherein the photoresist coating layer is exposed to radiation having a wavelength of less than about 170 nm. 61. The method of claim 60, wherein the photoresist coating layer is exposed to radiation having a wavelength of about 157 nm. An article comprising a substrate having a coating layer of the photoresist composition of claim 1 on the substrate. 65. The article of claim 64, wherein the substrate is a microelectronic wafer substrate. 65. The article of claim 64, wherein the substrate is an opto-electronic device substrate.