A polymer comprising units of formulas (1) and (2) and having a Mw of 1,000-500,000 is provided. R1 is H, CH3 or CH2CO2R3, R2 is H, CH3 or CO2R3, R3 is alkyl, R4 is halogen or acyloxy, alkoxycarbonyloxy or alkylsulfonyloxy group which may be substituted with halogen, R5 is H or alkyl, R6 is an acid labile group, Z is a single bond or a divalent hydrocarbon group, k is 0 or 1, and W is xe2x80x94Oxe2x80x94 or xe2x80x94(NR)xe2x80x94 wherein R is H or alkyl. A resist composition comprising the polymer as a base resin is sensitive to high-energy radiation, has excellent sensitivity, resolution, and etching resistance, and lends itself to micropatterning with electron beams or deep-UV rays.

1. Field of the Invention
The present invention relates to (i) a polymer comprising units having an electron attractive group at a specific position, (ii) a resist composition comprising the polymer, having improved transparency and hence, a high resolution, and in particular, suitable as micropatterning material for VLSI fabrication, and (iii) a patterning process using the resist composition.
2. Prior Art
While a number of recent efforts are being made to achieve a finer pattern rule in the drive for higher integration and operating speeds in LSI devices, deep-ultraviolet lithography is thought to hold particular promise as the next generation in microfabrication technology. In particular, photolithography using a KrF or ArF excimer laser as the light source is strongly desired to reach the practical level as the micropatterning technique capable of achieving a feature size of 0.3 xcexcm or less.
The resist materials for use in photolithography using light of an excimer laser, especially ArF excimer laser having a wavelength of 193 nm, are, of course, required to have a high transmittance to light of that wavelength. In addition, they are required to have an etching resistance sufficient to allow for film thickness reduction, a high sensitivity sufficient to eliminate any extra burden on the expensive optical material, and especially, a high resolution sufficient to form a precise micropattern. To meet these requirements, it is crucial to develop a base resin having a high transparency, robustness and reactivity. None of the currently available polymers satisfy all of these requirements. Practically acceptable resist materials are not yet available.
Known high transparency resins include copolymers of acrylic or methacrylic acid derivatives and polymers containing in the backbone an alicyclic compound derived from a norbornene derivative. All these resins are unsatisfactory. For example, copolymers of acrylic or methacrylic acid derivatives are relatively easy to increase reactivity in that highly reactive monomers can be introduced and acid labile units can be increased as desired, but difficult to increase robustness because of their backbone structure. On the other hand, the polymers containing an alicyclic compound in the backbone have robustness within the acceptable range, but are less reactive with acid than poly(meth)acrylate because of their backbone structure, and difficult to increase reactivity because of the low freedom of polymerization. Additionally, since these resins are less transparent than poly(meth)acrylates, they tend to further exaggerate the shortage of reactivity. Therefore, for both poly(meth)acrylates and polymers containing an alicyclic compound in the backbone, some resist compositions which are formulated using these polymers as the base resin fail to withstand etching although they have satisfactory sensitivity and resolution. Some other resist compositions are highly resistant to etching, but have low sensitivity and low resolution below the practically acceptable level.
An object of the invention is to provide (i) a polymer featuring both robustness and transparency, (ii) a resist composition comprising the polymer, having a significantly higher sensitivity, resolution, and etching resistance than prior art resist compositions, and (iii) a patterning process using the resist composition.
It has been found that a polymer comprising units of formulas (1) and (2) to be defined below and having a weight average molecular weight of 1,000 to 500,000 has very high transparency owing to the inclusion of an electron attractive group at a specific position, and that a resist composition comprising the polymer has a significantly high sensitivity, resolution, and etching resistance and is thus quite useful in precise micropatterning.
In a first aspect, the invention provides a polymer comprising units of the following general formula (1) and units of the following general formula (2) and having a weight average molecular weight of 1,000 to 500,000.
Herein R1 is hydrogen, methyl or CH2CO2R3, R2 is hydrogen, methyl or CO2R3, R3 is a straight, branched or cyclic alkyl group of 1 to 15 carbon atoms, R4 is a halogen atom or an acyloxy, alkoxycarbonyloxy or alkylsulfonyloxy group of 1 to 15 carbon atoms in which some or all of the hydrogen atoms on the constituent carbon atoms may be substituted with halogen atoms, R5 is hydrogen or a straight, branched or cyclic alkyl group of 1 to 10 carbon atoms, R6 is an acid labile group, Z is a single bond or a divalent straight, branched or cyclic hydrocarbon group of 1 to 10 carbon atoms, and k is 0 or 1. W is xe2x80x94Oxe2x80x94 or xe2x80x94(NR)xe2x80x94 wherein R is hydrogen or a straight, branched or cyclic alkyl group of 1 to 15 carbon atoms.
Typical of the units of formula (1) are units of the following general formula (3) or (4).
Herein R1 to R5, Z, and k are as defined above. R7 to R10 are independently selected from straight, branched or cyclic alkyl groups of 1 to 8 carbon atoms and substituted or unsubstituted aryl groups of 6 to 20 carbon atoms, and Y is a divalent hydrocarbon group of 4 to 15 carbon atoms which may contain a hetero atom and which forms a ring with the carbon atom to which it is connected at opposite ends.
The polymer may further include units of at least one of the following formulas (5) to (8).
Herein R1, R2 and k are as defined above. At least one of R11 to R14 is a carboxyl or hydroxyl-containing monovalent hydrocarbon group of 1 to 15 carbon atoms, and the remainders are independently hydrogen or a straight, branched or cyclic alkyl group of 1 to 15 carbon atoms, or R11 to R14, taken together, may form a ring, and when they form a ring, at least one of R11 to R14 is a carboxyl or hydroxyl-containing divalent hydrocarbon group of 1 to 15 carbon atoms, and the remainders are independently a single bond or a straight, branched or cyclic alkylene group of 1 to 15 carbon atoms. At least one of R15 to R18 is a monovalent hydrocarbon group of 2 to 15 carbon atoms containing a xe2x80x94CO2xe2x80x94 partial structure, and the remainders are independently hydrogen or a straight, branched or cyclic alkyl group of 1 to 15 carbon atoms, or R15 to R18, taken together, may form a ring, and when they form a ring, at least one of R15 to R18 is a divalent hydrocarbon group of 1 to 15 carbon atoms containing a xe2x80x94CO2xe2x80x94 partial structure, and the remainders are independently a single bond or a straight, branched or cyclic alkylene group of 1 to 15 carbon atoms. R19 is a polycyclic hydrocarbon group of 7 to 15 carbon atoms or an alkyl group containing such a polycyclic hydrocarbon group. R20 is an acid labile group. X is xe2x80x94CH2xe2x80x94 or xe2x80x94Oxe2x80x94.
In a second aspect, the invention provides a resist composition comprising the polymer defined above.
In a third aspect, the invention provides a process for forming a resist pattern comprising the steps of applying the resist composition onto a substrate to form a coating; heat treating the coating and then exposing it to high-energy radiation or electron beams through a photo mask; and optionally heat treating the exposed coating and developing it with a developer.
In the units of formula (1), an electron attractive group has been introduced on the carbon atom adjoining the aliphatic ring that constitutes the backbone. The electron attractive group introduced alters the overall electron distribution and steric structure of the polymer and as a consequence, remarkably improves transparency for the reason which is unknown, and especially at the wavelength of 193 nm, to an equivalent level to poly(meth)acrylate. Accordingly, a resist composition using the polymer as a base resin eliminates the drawbacks of forward tapered shape and short-dissolution as found in prior art resist compositions, without detracting from the etching resistance and other advantages of a polymer containing an alicyclic compound in the backbone.
The polymer or high molecular weight compound of the invention is defined as comprising units of the following general formulas (1) and (2) and having a weight average molecular weight of 1,000 to 500,000.
In formula (1), k is equal to 0 or 1. Then formula (1) can be represented by the following formulas (1-1) and (1-2).
Herein, R1 is hydrogen, methyl or CH2CO2R3. R2 is hydrogen, methyl or CO2R3. R3 stands for straight, branched or cyclic alkyl groups of 1 to 15 carbon atoms, such as, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl, ethylcyclopentyl, butylcyclopentyl, ethylcyclohexyl, butylcyclohexyl, adamantyl, ethyladamantyl and butyladamantyl. R4 stands for halogen atoms or acyloxy, alkoxycarbonyloxy or alkylsulfonyloxy groups of 1 to 15 carbon atoms in which some or all of the hydrogen atoms on the constituent carbon atoms may be substituted with halogen atoms, such as, for example, fluorine, chlorine, bromine, formyloxy, acetoxy, ethylcarbonyloxy, pivaloyloxy, methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy, methanesulfonyloxy, ethanesulfonyloxy, n-butanesulfonyloxy, trifluoroacetoxy, trichloroacetoxy, and 2,2,2-trifluoroethylcarbonyloxy. R5 stands for hydrogen or straight, branched or cyclic alkyl groups of 1 to 10 carbon atoms, such as, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylethyl and cyclohexylbutyl. R6 is an acid labile group. Z is a single bond or a divalent straight, branched or cyclic hydrocarbon group of 1 to 10 carbon atoms, such as methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, and cyclohexane-1,4-diyl.
W is xe2x80x94Oxe2x80x94 or xe2x80x94(NR)xe2x80x94 wherein R is hydrogen or a straight, branched or cyclic alkyl group of 1 to 15 carbon atoms, examples of which are the same as exemplified for R3.
Exemplary acid labile groups represented by R6 are the same as will be exemplified for R20 although acid labile groups of the following formulas are preferred.
Accordingly, units of the following general formula (3) or (4) are preferred among the units of formula (1).
Herein R1 to R5, Z, and k are as defined above. R7 to R10 are independently selected from straight, branched or cyclic alkyl groups of 1 to 8 carbon atoms and substituted or unsubstituted aryl groups of 6 to 20 carbon atoms. Examples of the straight, branched or cyclic alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, and cyclohexylethyl. Examples of the optionally substituted aryl group include phenyl, methylphenyl, naphthyl, anthryl, phenanthryl and pyrenyl. Y is a divalent hydrocarbon group of 4 to 15 carbon atoms which may contain a hetero atom and which forms a ring with the carbon atom to which it is connected at opposite ends. Examples of the rings that Y forms include cyclopentane, cyclopentene, cyclohexane, cyclohexene, bicyclo[2.2.1]heptane, bicyclo[4.4.0]decane, tricyclo[5.2.1.02,6]decane, tetracyclo[184.108.40.206,5.17,10]dodecane, and adamantane.
Illustrative, non-limiting, examples of the units of formula (1) and the units of formula (3) or (4) are given below.
The polymer of the invention may further comprise units of at least one type selected from units of the following formulas (5) to (8).
In the above formulae, X is xe2x80x94CH2xe2x80x94 or xe2x80x94Oxe2x80x94; and k is equal to 0 or 1. Then formulae (5) to (8) may also be represented by the following formulae (5-1) to (8-2).
Herein R1, R2, k and X are as defined above.
At least one of R11 to R14 is a monovalent hydrocarbon group of 1 to 15 carbon atoms (preferably straight, branched or cyclic alkyl) which contains a carboxyl or hydroxyl group, and the remaining R""s are independently hydrogen or a straight, branched or cyclic alkyl group of 1 to 15 carbon atoms. Examples of the carboxyl or hydroxyl-bearing monovalent hydrocarbon group of 1 to 15 carbon atoms include carboxy, carboxymethyl, carboxyethyl, carboxybutyl, hydroxymethyl, hydroxyethyl, hydroxybutyl, 2-carboxyethoxycarbonyl, 4-carboxybutoxycarbonyl, 2-hydroxyethoxycarbonyl, 4-hydroxybutoxycarbonyl, carboxycyclopentyloxycarbonyl, carboxycyclohexyloxycarbonyl, carboxynorbornyloxycarbonyl, carboxyadamantyloxycarbonyl, hydroxycyclopentyloxycarbonyl, hydroxycyclohexyloxycarbonyl, hydroxynorbornyloxycarbonyl, and hydroxyadamantyloxycarbonyl. Examples of the straight, branched or cyclic alkyl group of 1 to 15 carbon atoms are the same as exemplified for R3. R11 to R14, taken together, may form a ring, and in that event, at least one of R11 to R14 is a divalent hydrocarbon group of 1 to 15 carbon atoms (preferably straight, branched or cyclic alkylene) having a carboxyl or hydroxyl group, while the remaining R""s are independently single bonds or straight, branched or cyclic alkylene groups of 1 to 15 carbon atoms. Examples of the carboxyl or hydroxyl-bearing divalent hydrocarbon group of 1 to 15 carbon atoms include the groups exemplified as the carboxyl or hydroxyl-bearing monovalent hydrocarbon group, with one hydrogen atom eliminated therefrom. Examples of the straight, branched or cyclic alkylene groups of 1 to 15 carbon atoms include the groups exemplified for R3, with one hydrogen atom eliminated therefrom.
At least one of R15 to R18 is a monovalent hydrocarbon group of 2 to 15 carbon atoms containing a xe2x80x94CO2xe2x80x94 partial structure, while the remaining R""s are independently hydrogen or straight, branched or cyclic alkyl groups of 1 to 15 carbon atoms. Examples of the monovalent hydrocarbon group of 2 to 15 carbon atoms containing a xe2x80x94CO2xe2x80x94 partial structure include 2-oxooxolan-3-yloxycarbonyl, 4,4-dimethyl-2-oxooxolan-3-yloxycarbonyl, 4-methyl-2-oxooxan-4-yloxycarbonyl, 2-oxo-1,3-dioxolan-4-ylmethyloxycarbonyl, and 5-methyl-2-oxooxolan-5-yloxycarbonyl. Examples of the straight, branched or cyclic alkyl groups of 1 to 15 carbon atoms are the same as exemplified for R3. R15 to R18, taken together, may form a ring, and in that event, at least one of R15 to R18 is a divalent hydrocarbon group of 1 to 15 carbon atoms containing a xe2x80x94CO2xe2x80x94 partial structure, while the remaining R""s are independently single bonds or straight, branched or cyclic alkylene groups of 1 to 15 carbon atoms. Examples of the divalent hydrocarbon group of 1 to 15 carbon atoms containing a xe2x80x94CO2xe2x80x94 partial structure include 1-oxo-2-oxapropane-1,3-diyl, 1,3-dioxo-2-oxapropane-1,3-diyl, 1-oxo-2-oxabutane-1,4-diyl, and 1,3-dioxo-2-oxabutane-1,4-diyl, as well as the groups exemplified as the monovalent hydrocarbon group containing a xe2x80x94CO2xe2x80x94 partial structure, with one hydrogen atom eliminated therefrom. Examples of the straight, branched or cyclic alkylene groups of 1 to 15 carbon atoms include the groups exemplified for R3, with one hydrogen atom eliminated therefrom.
R19 is a polycyclic hydrocarbon group having 7 to 15 carbon atoms or an alkyl group containing a polycyclic hydrocarbon group, for example, norbornyl, bicyclo[3.3.1]nonyl, tricyclo[5.2.1.02,6]decyl, adamantyl, ethyladamantyl, butyladamantyl, norbornylmethyl, and adamantylmethyl.
R20 is an acid labile group. The acid labile groups represented by R20 may be selected from a variety of such groups. Examples of the acid labile group are groups of the following general formulae (L1) to (L4), tertiary alkyl groups of 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, trialkylsilyl groups in which each alkyl moiety has 1 to 6 carbon atoms, and oxoalkyl groups of 4 to 20 carbon atoms.
In these formulas and throughout the specification, the broken line denotes a valence bond.
RL01 and RL02 are hydrogen or straight, branched or cyclic alkyl groups of 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. Exemplary alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, cyclopentyl, cyclohexyl, 2-ethylhexyl, and n-octyl. RL03 is a monovalent hydrocarbon group of 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, which may contain a hetero atom such as oxygen, examples of which include unsubstituted straight, branched or cyclic alkyl groups and straight, branched or cyclic alkyl groups in which some hydrogen atoms are replaced by hydroxyl, alkoxy, oxo, amino, alkylamino or the like. Illustrative examples are the substituted alkyl groups shown below.
A pair of RL01 and RL02, RL01 and RL03, or RL02 and RL03 may form a ring. Each of RL01, RL02 and RL03 is a straight or branched alkylene group of 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms when they form a ring.
RL04 is a tertiary alkyl group of 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, a trialkylsilyl group in which each alkyl moiety has 1 to 6 carbon atoms, an oxoalkyl group of 4 to 20 carbon atoms, or a group of formula (L1). Exemplary tertiary alkyl groups are tert-butyl, tert-amyl, 1,1-diethylpropyl, 1-ethylcyclopentyl, 1-butylcyclopentyl, 1-ethylcyclohexyl, 1-butylcyclohexyl, 1-ethyl-2-cyclopentenyl, 1-ethyl-2-cyclohexenyl, and 2-methyl-2-adamantyl. Exemplary trialkylsilyl groups are trimethylsilyl, triethylsilyl, and dimethyl-tert-butylsilyl. Exemplary oxoalkyl groups are 3-oxocyclohexyl, 4-methyl-2-oxooxan-4-yl, and 5-methyl-5-oxooxolan-4-yl. Letter y is an integer of 0 to 6.
RL05 is a straight or branched alkyl group of 1 to 8 carbon atoms or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms. Examples of the straight, branched or cyclic alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-pentyl and n-hexyl. Exemplary aryl groups are phenyl, methylphenyl, naphthyl, anthryl, phenanthryl, and pyrenyl. Letter m is equal to 0 or 1, n is equal to 0, 1, 2 or 3, and 2m+n is equal to 2 or 3.
RL06 is a straight, branched or cyclic alkyl group of 1 to 8 carbon atoms or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms. Examples of these groups are the same as exemplified for RL05.
RL07 to RL16 independently represent hydrogen or monovalent hydrocarbon groups of 1 to 15 carbon atoms which may contain a hetero atom. Exemplary hydrocarbon groups are straight, branched or cyclic alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl and cyclohexylbutyl, and substituted ones of these groups in which some hydrogen atoms are replaced by hydroxyl, alkoxy, carboxy, alkoxycarbonyl, oxo, amino, alkylamino, cyano, mercapto, alkylthio, sulfo or other groups. Alternatively, RL07 to RL16, taken together, form a ring (for example, a pair of RL07 and RL08, RL07 and RL09, RL08 and RL10, RL09 and RL10, RL11 and RL12, RL13 and RL14, or a similar pair form a ring). Each of RL07 to RL16 represents a divalent C1-C15 hydrocarbon group which may contain a hetero atom, when they form a ring, examples of which are the ones exemplified above for the monovalent hydrocarbon groups, with one hydrogen atom being eliminated. Two of RL07 to RL16 which are attached to adjoining carbon atoms (for example, a pair of RL07 and RL09, RL09 and RL15, RL13 and RL15, or a similar pair) may bond together directly to form a double bond.
Of the acid labile groups of formula (L1), the straight and branched ones are exemplified by the following groups.
Of the acid labile groups of formula (L1), the cyclic ones are, for example, tetrahydrofuran-2-yl, 2-methyltetrahydrofuran-2-yl, tetrahydropyran-2-yl, and 2-methyltetrahydropyran-2-yl.
Examples of the acid labile groups of formula (L2) include tert-butoxycarbonyl, tert-butoxycarbonylmethyl, tert-amyloxycarbonyl, tert-amyloxycarbonylmethyl, 1,1-diethylpropyloxycarbonyl, 1,1-diethylpropyloxycarbonylmethyl, 1-ethylcyclopentyloxycarbonyl, 1-ethylcyclopentyloxycarbonylmethyl, 1-ethyl-2-cyclopentenyloxycarbonyl, 1-ethyl-2-cyclopentenyloxycarbonylmethyl, 1-ethoxyethoxycarbonylmethyl, 2-tetrahydropyranyloxycarbonylmethyl, and 2-tetrahydrofuranyloxycarbonylmethyl groups.
Examples of the acid labile groups of formula (L3) include 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl, 1-isopropylcyclopentyl, 1-n-butyl-cyclopentyl, 1-sec-butylcyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 3-methyl-1-cyclopenten-3-yl, 3-ethyl-1-cyclopenten-3-yl, 3-methyl-1-cyclohexen-3-yl, and 3-ethyl-1-cyclohexen-3-yl groups.
The acid labile groups of formula (L4) are exemplified by the following groups.
Examples of the tertiary alkyl groups, trialkylsilyl groups, and oxoalkyl groups included in the acid labile groups represented by R20 are as previously exemplified.
As the acid labile group represented by R20, there may be used one type or a combination of two or more types. The use of acid labile groups of different types allows for fine adjustment of a pattern profile.
The polymer of the invention may be prepared by copolymerizing a compound of formula (1a) as a first monomer, a compound of formula (2a) as a second monomer and optionally, at least one member selected from compounds of formulas (5a) to (8a) as a third monomer (and subsequent monomers).
Herein, R1 to R20, W, X, Y, Z and k are as defined above.
In addition to (i) the monomer of formula (1a), (ii) the monomer of formula (2a) and (iii) the optional monomer or monomers of formulas (5a) to (8a), the polymer of the invention may have copolymerized therewith (iv) another monomer having a carbon-to-carbon double bond other than (i) to (iii), if desired. Examples of the additional monomer (iv) include substituted acrylic acid esters such as methyl methacrylate, methyl crotonate, dimethyl maleate, and dimethyl itaconate, unsaturated carboxylic acids such as maleic acid, fumaric acid and itaconic acid, substituted or unsubstituted norbornenes such as norbornene and methyl norbornene-5-carboxylate, and unsaturated acid anhydrides such as itaconic anhydride.
Copolymerization reaction is effected by mixing the monomers (i) to (iv) in a suitable proportion which is determined by taking into account the reactivity of the respective monomers, or dissolving the monomers in a solvent if desired, adding a suitable polymerization initiator or catalyst, and holding the reaction mixture at a suitable temperature for a suitable time. Copolymerization reaction may be effected in various modes although radical polymerization reaction is preferred.
For radical polymerization, preferred reaction conditions include (a) a solvent selected from among hydrocarbons such as benzene, ethers such as tetrahydrofuran, alcohols such as ethanol, and ketones such as methyl isobutyl ketone, (b) a polymerization initiator selected from azo compounds such as 2,2xe2x80x2-azobisisobutyronitrile and peroxides such as benzoyl peroxide and lauroyl peroxide, (c) a temperature of about 0xc2x0 C. to about 100xc2x0 C., and (d) a time of about xc2xd hour to about 48 hours. Reaction conditions outside the described range may be employed if desired.
By properly adjusting the proportion of the respective monomers used in the copolymerization reaction, the polymer can be tailored so that it may exert the preferred performance when blended in resist compositions.
The polymers of the invention may contain
(I) more than 0 mol % to 50 mol %, preferably 20 to 50 mol %, more preferably 30 to 50 mol % of units of formula (1) originating from the monomer of formula (1a),
(II) more than 0 mol % to 50 mol %, preferably 20 to 50 mol %, more preferably 30 to 50 mol % of units of formula (2) originating from the monomer of formula (2a), and optionally,
(III) 0 mol % to 50 mol %, preferably 0 to 30 mol %, more preferably 0 to 20 mol % of units of one or more types of formulae (5) to (8) originating from the monomers of formulae (5a) to (8a), and further optionally,
(IV) 0 to 50 mol %, preferably 0 to 30 mol %, more preferably 0 to 20 mol % of units of one or more types originating from the additional monomers (iv). It is noted that compositions outside the above range are not excluded from the invention.
The inventive polymers comprising units of formulas (1) and (2) have a weight average molecular weight of 1,000 to 500,000, preferably 3,000 to 100,000. Outside the range, the etching resistance may become extremely low and the resolution may become low because a substantial difference in rate of dissolution before and after exposure is lost.
Resist Composition
The polymer of the invention is useful as the base polymer of a resist composition, and the other aspect of the invention provides a resist composition comprising the polymer. Preferably, the resist composition is defined as comprising the polymer, a photoacid generator, and an organic solvent.
Photoacid Generator
The photoacid generator is a compound capable of generating an acid upon exposure to high energy radiation or electron beams and includes the following:
(i) onium salts of the formula (P1a-1), (P1a-2) or (P1b),
(ii) diazomethane derivatives of the formula (P2),
(iii) glyoxime derivatives of the formula (P3),
(iv) bissulfone derivatives of the formula (P4),
(v) sulfonic acid esters of N-hydroxyimide compounds of the formula (P5),
(vi) xcex2-ketosulfonic acid derivatives,
(vii) disulfone derivatives,
(viii) nitrobenzylsulfonate derivatives, and
(ix) sulfonate derivatives.
These photoacid generators are described in detail.
(i) Onium Salts of Formula (P1a-1), (P1a-2) or (P1b):
Herein, R101a, R101b, and R101c independently represent straight, branched or cyclic alkyl, alkenyl, oxoalkyl or oxoalkenyl groups of 1 to 12 carbon atoms, aryl groups of 6 to 20 carbon atoms, or aralkyl or aryloxoalkyl groups of 7 to 12 carbon atoms, wherein some or all of the hydrogen atoms may be replaced by alkoxy or other groups. Also, R101b and R101c, taken together, may form a ring. R101b and R101c each are alkylene groups of 1 to 6 carbon atoms when they form a ring. Kxe2x88x92 is a non-nucleophilic counter ion.
R101a, R101b, and R101c may be the same or different and are illustrated below. Exemplary alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl. Exemplary alkenyl groups include vinyl, allyl, propenyl, butenyl, hexenyl, and cyclohexenyl. Exemplary oxoalkyl groups include 2-oxocyclopentyl and 2-oxocyclohexyl as well as 2-oxopropyl, 2-cyclopentyl-2-oxoethyl, 2-cyclohexyl-2-oxoethyl, and 2-(4-methylcyclohexyl)-2-oxoethyl. Exemplary aryl groups include phenyl and naphthyl; alkoxyphenyl groups such as p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p-tert-butoxyphenyl, and m-tert-butoxyphenyl; alkylphenyl groups such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, and dimethylphenyl; alkylnaphthyl groups such as methylnaphthyl and ethylnaphthyl; alkoxynaphthyl groups such as methoxynaphthyl and ethoxynaphthyl; dialkylnaphthyl groups such as dimethylnaphthyl and diethylnaphthyl; and dialkoxynaphthyl groups such as dimethoxynaphthyl and diethoxynaphthyl. Exemplary aralkyl groups include benzyl, phenylethyl, and phenethyl. Exemplary aryloxoalkyl groups are 2-aryl-2-oxoethyl groups such as 2-phenyl-2-oxoethyl, 2-(1-naphthyl)-2-oxoethyl, and 2-(2-naphthyl)-2-oxoethyl. Examples of the non-nucleophilic counter ion represented by Kxe2x88x92 include halide ions such as chloride and bromide ions, fluoroalkylsulfonate ions such as triflate, 1,1,1-trifluoroethanesulfonate, and nonafluorobutanesulfonate, arylsulfonate ions such as tosylate, benzenesulfonate, 4-fluorobenzenesulfonate, and 1,2,3,4,5-pentafluorobenzenesulfonate, and alkylsulfonate ions such as mesylate and butanesulfonate.
Herein, R102a and R102b independently represent straight, branched or cyclic alkyl groups of 1 to 8 carbon atoms. R103 represents a straight, branched or cyclic alkylene groups of 1 to 10 carbon atoms. R104a and R104b independently represent 2-oxoalkyl groups of 3 to 7 carbon atoms. Kxe2x88x92 is a non-nucleophilic counter ion.
Illustrative of the groups represented by R102a and R102b are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, and cyclohexylmethyl. Illustrative of the groups represented by R103 are methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, 1,4-cyclohexylene, 1,2-cyclohexylene, 1,3-cyclopentylene, 1,4-cyclooctylene, and 1,4-cyclohexanedimethylene. Illustrative of the groups represented by R104a and R104b are 2-oxopropyl, 2-oxocyclopentyl, 2-oxocyclohexyl, and 2-oxocycloheptyl. Illustrative examples of the counter ion represented by Kxe2x88x92 are the same as exemplified for formulae (P1a-1) and (P1a-2).
(ii) Diazomethane Derivatives of Formula (P2)
Herein, R105 and R106 independently represent straight, branched or cyclic alkyl or halogenated alkyl groups of 1 to 12 carbon atoms, aryl or halogenated aryl groups of 6 to 20 carbon atoms, or aralkyl groups of 7 to 12 carbon atoms.
Of the groups represented by R105 and R106, exemplary alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, amyl, cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, and adamantyl. Exemplary halogenated alkyl groups include trifluoromethyl, 1,1,1-trifluoroethyl, 1,1,1-trichloroethyl, and nonafluorobutyl. Exemplary aryl groups include phenyl; alkoxyphenyl groups such as p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p-tert-butoxyphenyl, and m-tert-butoxyphenyl; and alkylphenyl groups such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, and dimethylphenyl. Exemplary halogenated aryl groups include fluorophenyl, chlorophenyl, and 1,2,3,4,5-pentafluorophenyl. Exemplary aralkyl groups include benzyl and phenethyl.
(iii) Glyoxime Derivatives of Formula (P3)
Herein, R107, R108, and R109 independently represent straight, branched or cyclic alkyl or halogenated alkyl groups of 1 to 12 carbon atoms, aryl or halogenated aryl groups of 6 to 20 carbon atoms, or aralkyl groups of 7 to 12 carbon atoms. Also, R108 and R109, taken together, may form a ring. R108 and R109 each are straight or branched alkylene groups of 1 to 6 carbon atoms when they form a ring.
Illustrative examples of the alkyl, halogenated alkyl, aryl, halogenated aryl, and aralkyl groups represented by R107, R108, and R109 are the same as exemplified for R105 and R106. Examples of the alkylene groups represented by R108 and R109 include methylene, ethylene, propylene, butylene, and hexylene.
(iv) Bissulfone Derivatives of Formula (P4)
Herein, R101a and R101b are as defined above.
(v) Sulfonic Acid Esters of N-hydroxyimide Compounds of Formula (P5)
Herein, R110 is an arylene group of 6 to 10 carbon atoms, alkylene group of 1 to 6 carbon atoms, or alkenylene group of 2 to 6 carbon atoms wherein some or all of the hydrogen atoms may be replaced by straight or branched alkyl or alkoxy groups of 1 to 4 carbon atoms, nitro, acetyl, or phenyl groups. R111 is a straight, branched or cyclic alkyl group of 1 to 8 carbon atoms, alkenyl, alkoxyalkyl, phenyl or naphthyl group wherein some or all of the hydrogen atoms may be replaced by alkyl or alkoxy groups of 1 to 4 carbon atoms, phenyl groups (which may have substituted thereon an alkyl or alkoxy of 1 to 4 carbon atoms, nitro, or acetyl group), hetero-aromatic groups of 3 to 5 carbon atoms, or chlorine or fluorine atoms.
Of the groups represented by R110, exemplary arylene groups include 1,2-phenylene and 1,8-naphthylene; exemplary alkylene groups include methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1-phenyl-1,2-ethylene, and norbornane-2,3-diyl; and exemplary alkenylene groups include 1,2-vinylene, 1-phenyl-1,2-vinylene, and 5-norbornene-2,3-diyl. Of the groups represented by R111, exemplary alkyl groups are as exemplified for R101a and R101c; exemplary alkenyl groups include vinyl, 1-propenyl, allyl, 1-butenyl, 3-butenyl, isoprenyl, 1-pentenyl, 3-pentenyl, 4-pentenyl, dimethylallyl, 1-hexenyl, 3-hexenyl, 5-hexenyl, 1-heptenyl, 3-heptenyl, 6-heptenyl, and 7-octenyl; and exemplary alkoxyalkyl groups include methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, pentyloxymethyl, hexyloxymethyl, heptyloxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, pentyloxyethyl, hexyloxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, butoxypropyl, methoxybutyl, ethoxybutyl, propoxybutyl, methoxypentyl, ethoxypentyl, methoxyhexyl, and methoxyheptyl.
Of the substituents on these groups, the alkyl groups of 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl and tert-butyl; the alkoxy groups of 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, and tert-butoxy; the phenyl groups which may have substituted thereon an alkyl or alkoxy of 1 to 4 carbon atoms, nitro, or acetyl group include phenyl, tolyl, p-tert-butoxyphenyl, p-acetylphenyl and p-nitrophenyl; the hetero-aromatic groups of 3 to 5 carbon atoms include pyridyl and furyl.
Illustrative examples of the photoacid generator include:
onium salts such as diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, (p-tert-butoxyphenyl)phenyliodonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate, tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, (2-norbornyl)methyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, ethylenebis[methyl(2-oxocyclopentyl)sulfonium trifluoromethanesulfonate], and 1,2xe2x80x2-naphthylcarbonylmethyltetrahydrothiophenium triflate;
diazomethane derivatives such as bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(cyclopentylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(sec-butylsulfonyl)diazomethane, bis(n-propylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, bis(tert-butylsulfonyl)diazomethane, bis(n-amylsulfonyl)diazomethane, bis(isoamylsulfonyl)diazomethane, bis(sec-amylsulfonyl)diazomethane, bis(tert-amylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-butylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-amylsulfonyl)diazomethane, and 1-tert-amylsulfonyl-1-(tert-butylsulfonyl)diazomethane;
glyoxime derivatives such as bis-o-(p-toluenesulfonyl)-xcex1-dimethylglyoxime, bis-o-(p-toluenesulfonyl)-xcex1-diphenylglyoxime, bis-o-(p-toluenesulfonyl)-xcex1-dicyclohexylglyoxime, bis-o-(p-toluenesulfonyl)-2,3-pentanedioneglyoxime, bis-o-(p-toluenesulfonyl)-2-methyl-3,4-pentanedioneglyoxime, bis-o-(n-butanesulfonyl)-xcex1-dimethylglyoxime, bis-o-(n-butanesulfonyl)-xcex1-diphenylglyoxime, bis-o-(n-butanesulfonyl)-xcex1-dicyclohexylglyoxime, bis-o-(n-butanesulfonyl)-2,3-pentanedioneglyoxime, bis-o-(n-butanesulfonyl)-2-methyl-3,4-pentanedioneglyoxime, bis-o-(methanesulfonyl)-xcex1-dimethylglyoxime, bis-o-(trifluoroethanesulfonyl)-xcex1-dimethylglyoxime, bis-o-(1,1,1-trifluorothanesulfonyl)-xcex1-dimethylglyoxime, bis-o-(tert-butanesulfonyl)-xcex1-dimethylglyoxime, bis-o-(perfluorooctanesulfonyl)-xcex1-dimethylglyoxime, bis-o-(cyclohexanesulfonyl)-xcex1-dimethylglyoxime, bis-o-(benzenesulfonyl)-(xcex1-dimethylglyoxime, bis-o-(p-fluorobenzenesulfonyl)-xcex1-dimethylglyoxime, bis-o-(p-tert-butylbenzenesulfonyl)-xcex1-dimethylglyoxime, bis-o-(xylenesulfonyl)-xcex1-dimethylglyoxime, and bis-o-(camphorsulfonyl)-xcex1-dimethylglyoxime;
bissulfone derivatives such as bisnaphthylsulfonylmethane, bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfonylmethane, bisisopropylsulfonylmethane, bis-p-toluenesulfonylmethane, and bisbenzenesulfonylmethane;
xcex2-ketosulfone derivatives such as 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane and 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane;
disulfone derivatives such as diphenyl disulfone and dicyclohexyl disulfone;
nitrobenzyl sulfonate derivatives such as 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate;
sulfonic acid ester derivatives such as 1,2,3-tris-(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene; and
sulfonic acid esters of N-hydroxyimides such as N-hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide ethanesulfonate, N-hydroxysuccinimide 1-propanesulfonate, N-hydroxysuccinimide 2-propanesulfonate, N-hydroxysuccinimide 1-pentanesulfonate, N-hydroxysuccinimide 1-octanesulfonate, N-hydroxysuccinimide p-toluenesulfonate, N-hydroxysuccinimide p-methoxybenzenesulfonate, N-hydroxysuccinimide 2-chloroethanesulfonate, N-hydroxysuccinimide benzenesulfonate, N-hydroxysuccinimide 2,4,6-trimethylbenzenesulfonate, N-hydroxysuccinimide 1-naphthalenesulfonate, N-hydroxysuccinimide 2-naphthalenesulfonate, N-hydroxy-2-phenylsuccinimide methanesulfonate, N-hydroxymaleimide methanesulfonate, N-hydroxymaleimide ethanesulfonate, N-hydroxy-2-phenylmaleimide methanesulfonate, N-hydroxyglutarimide methanesulfonate, N-hydroxyglutarimide benzenesulfonate, N-hydroxyphthalimide methanesulfonate, N-hydroxyphthalimide benzenesulfonate, N-hydroxyphthalimide trifluoromethanesulfonate, N-hydroxyphthalimide p-toluenesulfonate, N-hydroxynaphthalimide methanesulfonate, N-hydroxynaphthalimide benzenesulfonate, N-hydroxy-5-norbornene-2,3-dicarboxyimide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboxyimide trifluoromethanesulfonate, and N-hydroxy-5-norbornene-2,3-dicarboxyimide p-toluenesulfonate.
Preferred among these photoacid generators are onium salts such as triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, (2-norbornyl)methyl(2-oxocylohexyl)sulfonium trifluoromethanesulfonate, and 1,2xe2x80x2-naphthylcarbonylmethyltetrahydrothiophenium triflate; diazomethane derivatives such as bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(sec-butylsulfonyl)diazomethane, bis(n-propylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, and bis(tert-butylsulfonyl)diazomethane; glyoxime derivatives such as bis-o-(p-toluenesulfonyl)-xcex1-dimethylglyoxime and bis-o-(n-butanesulfonyl)-xcex1-dimethylglyoxime; bissulfone derivatives such as bisnaphthylsulfonylmethane; and sulfonic acid esters of N-hydroxyimide compounds such as N-hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide 1-propanesulfonate, N-hydroxysuccinimide 2-propanesulfonate, N-hydroxysuccinimide 1-pentanesulfonate, N-hydroxysuccinimide p-toluenesulfonate, N-hydroxynaphthalimide methanesulfonate, and N-hydroxynaphthalimide benzenesulfonate.
These photoacid generators may be used singly or in combinations of two or more thereof. Onium salts are effective for improving rectangularity, while diazomethane derivatives and glyoxime derivatives are effective for reducing standing waves. The combination of an onium salt with a diazomethane or a glyoxime derivative allows for fine adjustment of the profile.
The photoacid generator is added in an amount of 0.1 to 15 parts, and especially 0.5 to 8 parts by weight, per 100 parts by weight of the base resin (all parts are by weight, hereinafter). Less than 0.1 part of the photoacid generator would provide a poor sensitivity whereas more than 15 parts of the photoacid generator would adversely affect transparency and resolution.
Organic Solvent
The organic solvent used herein may be any organic solvent in which the base resin, photoacid generator, and other components are soluble. Illustrative, non-limiting, examples of the organic solvent include ketones such as cyclohexanone and methyl-2-n-amylketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol mono-tert-butyl ether acetate. These solvents may be used alone or in combinations of two or more thereof. Of the above organic solvents, it is recommended to use diethylene glycol dimethyl ether and 1-ethoxy-2-propanol because the photoacid generator serving as one of the resist components is most soluble therein, propylene glycol monomethyl ether acetate because it is a safe solvent, or a mixture thereof.
An appropriate amount of the organic solvent used is about 200 to 1,000 parts, especially about 400 to 800 parts by weight per 100 parts by weight of the base resin.
Other Polymer
To the resist composition of the invention, another polymer other than the inventive polymer comprising units of formulas (1) and (2) may also be added. The other polymers that can be added to the resist composition are, for example, those polymers comprising units of the following formula (R1) and/or (R2) and having a weight average molecular weight of about 1,000 to about 500,000, especially about 5,000 to about 100,000 although the other polymers are not limited thereto.
Herein, R001 is hydrogen, methyl or CH2CO2R003. R002 is hydrogen, methyl or CO2R003. R003 is a straight, branched or cyclic alkyl group of 1 to 15 carbon atoms. R004 is hydrogen or a monovalent hydrocarbon group of 1 to 15 carbon atoms having a carboxyl or hydroxyl group. At least one of R005 to R008 represents a monovalent hydrocarbon group of 1 to 15 carbon atoms having a carboxyl or hydroxyl group while the remaining R""s independently represent hydrogen or a straight, branched or cyclic alkyl group of 1 to 15 carbon atoms. Alternatively, R005 to R008, taken together, may form a ring, and in that event, at least one of R005 to R008 is a divalent hydrocarbon group of 1 to 15 carbon atoms having a carboxyl or hydroxyl group, while the remaining R""s are independently single bonds or straight, branched or cyclic alkylene groups of 1 to 15 carbon atoms. R009 is a monovalent hydrocarbon group of 3 to 15 carbon atoms containing a xe2x80x94CO2xe2x80x94 partial structure. At least one of R010 to R013 is a monovalent hydrocarbon group of 2 to 15 carbon atoms containing a xe2x80x94CO2xe2x80x94 partial structure, while the remaining R""s are independently hydrogen or straight, branched or cyclic alkyl groups of 1 to 15 carbon atoms. R010 to R013, taken together, may form a ring, and in that event, at least one of R010 to R013 is a divalent hydrocarbon group of 1 to 15 carbon atoms containing a xe2x80x94CO2xe2x80x94 partial structure, while the remaining R""s are independently single bonds or straight, branched or cyclic alkylene groups of 1 to 15 carbon atoms. R014 is a polycyclic hydrocarbon group having 7 to 15 carbon atoms or an alkyl group containing a polycyclic hydrocarbon group. R015 is an acid labile group. R016 is hydrogen or methyl. R017 is a straight, branched or cyclic alkyl group of 1 to 8 carbon atoms. Letter kxe2x80x2 is equal to 0 or 1; a1xe2x80x2, a2xe2x80x2, a3xe2x80x2, b1xe2x80x2, b2xe2x80x2, b3xe2x80x2, c1xe2x80x2, c2xe2x80x2, c3xe2x80x2, d1xe2x80x2, d2xe2x80x2, d3xe2x80x2, and exe2x80x2 are numbers from 0 to less than 1, satisfying a1xe2x80x2+a2xe2x80x2+a3xe2x80x2+b1xe2x80x2+b2xe2x80x2+b3xe2x80x2+c1xe2x80x2+c2xe2x80x2+c3xe2x80x2+d1xe2x80x2+d2xe2x80x2+d3xe2x80x2+exe2x80x2=1; fxe2x80x2, gxe2x80x2, hxe2x80x2, ixe2x80x2, and jxe2x80x2 are numbers from 0 to less than 1, satisfying fxe2x80x2+gxe2x80x2+hxe2x80x2+ixe2x80x2+jxe2x80x2=1.
Exemplary groups of these R""s are as exemplified above for R1 to R20.
The inventive polymer (comprising units of formulas (1) and (2)) and the other polymer are preferably blended in a weight ratio from 10:90 to 90:10, more preferably from 20:80 to 80:20. If the blend ratio of the inventive polymer is below this range, the resist composition would become poor in some of the desired properties. The properties of the resist composition can be adjusted by properly changing the blend ratio of the inventive polymer.
The other polymer is not limited to one type and a mixture of two or more other polymers may be added. The use of plural polymers allows for easy adjustment of resist properties.
Dissolution Regulator
To the resist composition, a dissolution regulator may be added. The dissolution regulator is a compound having on the molecule at least two phenolic hydroxyl groups, in which an average of from 0 to 100 mol % of all the hydrogen atoms on the phenolic hydroxyl groups are replaced with acid labile groups or a compound having on the molecule at least one carboxyl group, in which an average of 50 to 100 mol % of all the hydrogen atoms on the carboxyl groups are replaced with acid labile groups, both the compounds having an average molecular weight within a range of 100 to 1,000, and preferably 150 to 800.
The degree of substitution of the hydrogen atoms on the phenolic hydroxyl groups with acid labile groups is on average at least 0 mol %, and preferably at least 30 mol %, of all the phenolic hydroxyl groups. The upper limit is 100 mol %, and preferably 80 mol %. The degree of substitution of the hydrogen atoms on the carboxyl groups with acid labile groups is on average at least 50 mol %, and preferably at least 70 mol %, of all the carboxyl groups, with the upper limit being 100 mol %.
Preferable examples of such compounds having two or more phenolic hydroxyl groups or compounds having at least one carboxyl group include those of formulas (D1) to (D14) below.
In these formulas, R201 and R202 are each hydrogen or a straight or branched alkyl or alkenyl of 1 to 8 carbon atoms; R203 is hydrogen, a straight or branched alkyl or alkenyl of 1 to 8 carbon atoms, or xe2x80x94(R207)hxe2x80x94COOH; R204 is xe2x80x94(CH2)ixe2x80x94 (where i=2 to 10), an arylene of 6 to 10 carbon atoms, carbonyl, sulfonyl, an oxygen atom, or a sulfur atom; R205 is an alkylene of 1 to 10 carbon atoms, an arylene of 6 to 10 carbon atoms, carbonyl, sulfonyl, an oxygen atom, or a sulfur atom; R206 is hydrogen, a straight or branched alkyl or alkenyl of 1 to 8 carbon atoms, or a hydroxyl-substituted phenyl or naphthyl; R207 is a straight or branched alkylene of 1 to 10 carbon atoms; R208 is hydrogen or hydroxyl; the letter j is an integer from 0 to 5; u and h are each 0 or 1; s, t, sxe2x80x2, txe2x80x2, sxe2x80x3, and txe2x80x3 are each numbers which satisfy s+t=8, sxe2x80x2+txe2x80x2=5, and sxe2x80x3+txe2x80x3=4, and are such that each phenyl skeleton has at least one hydroxyl group; and xcex1 is a number such that the compounds of formula (D8) or (D9) have a molecular weight of from 100 to 1,000.
In the above formulas, suitable examples of R201 and R202 include hydrogen, methyl, ethyl, butyl, propyl, ethynyl, and cyclohexyl; suitable examples of R203 include the same groups as for R201 and R202, as well as xe2x80x94COOH and xe2x80x94CH2COOH; suitable examples of R204 include ethylene, phenylene, carbonyl, sulfonyl, oxygen, and sulfur; suitable examples of R205 include methylene as well as the same groups as for R204; and suitable examples of R206 include hydrogen, methyl, ethyl, butyl, propyl, ethynyl, cyclohexyl, and hydroxyl-substituted phenyl or naphthyl.
Exemplary acid labile groups on the dissolution regulator include groups of the following general formulae (L1) to (L4), tertiary alkyl groups of 4 to 20 carbon atoms, trialkylsilyl groups in which each of the alkyls has 1 to 6 carbon atoms, and oxoalkyl groups of 4 to 20 carbon atoms.
In these formulas, RL01 and RL02 are each hydrogen or a straight, branched or cyclic alkyl having 1 to 18 carbon atoms; and RL03 is a monovalent hydrocarbon group of 1 to 18 carbon atoms which may contain a heteroatom (e.g., oxygen). A pair of RL01 and RL02, a pair of RL01 and RL03, or a pair of RL02 and RL03 may together form a ring, with the proviso that RL01, RL02, and RL03 are each a straight or branched alkylene of 1 to 18 carbon atoms when they form a ring. RL04 is a tertiary alkyl group of 4 to 20 carbon atoms, a trialkysilyl group in which each of the alkyls has 1 to 6 carbon atoms, an oxoalkyl group of 4 to 20 carbon atoms, or a group of the formula (L1). RL05 is a straight, branched or cyclic alkyl group of 1 to 8 carbon atoms or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms. RL06 is a straight, branched or cyclic alkyl group of 1 to 8 carbon atoms or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms. RL07 to RL16 independently represent hydrogen or monovalent hydrocarbon groups of 1 to 15 carbon atoms which may contain a hetero atom. Alternatively, RL07 to RL16, taken together, may form a ring. Each of RL07 to RL16 represents a divalent C1-C15 hydrocarbon group which may contain a hetero atom, when they form a ring. Two of RL07 to RL16 which are attached to adjoining carbon atoms may bond together directly to form a double bond. Letter y is an integer of 0 to 6. Letter m is equal to 0 or 1, n is equal to 0, 1, 2 or 3, and 2m+n is equal to 2 or 3.
The dissolution regulator may be formulated in an amount of 0 to 50 parts, preferably 5 to 50 parts, and more preferably 10 to 30 parts, per 100 parts of the base resin, and may be used singly or as a mixture of two or more thereof. Less than 5 parts of the dissolution regulator may fail to yield an improved resolution, whereas the use of more than 50 parts would lead to slimming of the patterned film, and thus a decline in resolution.
The dissolution regulator can be synthesized by introducing acid labile groups into a compound having phenolic hydroxyl or carboxyl groups in accordance with an organic chemical formulation.
Basic Compound
In the resist composition of the invention, a basic compound may be blended. A suitable basic compound used herein is a compound capable of suppressing the rate of diffusion when the acid generated by the photoacid generator diffuses within the resist film. The inclusion of this type of basic compound holds down the rate of acid diffusion within the resist film, resulting in better resolution. In addition, it suppresses changes in sensitivity following exposure, thus reducing substrate and environment dependence, as well as improving the exposure latitude and the pattern profile.
Examples of basic compounds include primary, secondary, and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, carboxyl group-bearing nitrogenous compounds, sulfonyl group-bearing nitrogenous compounds, hydroxyl group-bearing nitrogenous compounds, hydroxyphenyl group-bearing nitrogenous compounds, alcoholic nitrogenous compounds, amide derivatives, and imide derivatives.
Examples of suitable primary aliphatic amines include ammonia, methylamine, ethylamine, n-propylamine, isopropyl-amine, n-butylamine, iso-butylamine, sec-butylamine, tert-butylamine, pentylamine, tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, and tetraethylenepentamine. Examples of suitable secondary aliphatic amines include dimethylamine, diethylamine, di-n-propylamine, di-iso-propylamine, di-n-butylamine, di-iso-butylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N,N-dimethylmethylenediamine, N,N-dimethylethylenediamine, and N,N-dimethyltetraethylenepentamine. Examples of suitable tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, tri-iso-propylamine, tri-n-butylamine, tri-iso-butylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N,N,Nxe2x80x2,Nxe2x80x2-tetramethylmethylenediamine, N,N,Nxe2x80x2,Nxe2x80x2-tetramethylethylenediamine, and N,N,Nxe2x80x2,Nxe2x80x2-tetramethyltetraethylenepentamine.
Examples of suitable mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, and benzyldimethylamine. Examples of suitable aromatic and heterocyclic amines include aniline derivatives (e.g., aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, and N,N-dimethyltoluidine), diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, and N-methylpyrrole), oxazole derivatives (e.g., oxazole and isooxazole), thiazole derivatives (e.g., thiazole and isothiazole), imidazole derivatives (e.g., imidazole, 4-methylimidazole, and 4-methyl-2-phenylimidazole), pyrazole derivatives, furazan derivatives, pyrroline derivatives (e.g., pyrroline and 2-methyl-1-pyrroline), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrrolidine, pyrrolidinone, and N-methylpyrrolidone), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (e.g., pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridine, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, and dimethylaminopyridine), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (e.g., quinoline and 3-quinolinecarbonitrile), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, and uridine derivatives.
Examples of suitable carboxyl group-bearing nitrogenous compounds include aminobenzoic acid, indolecarboxylic acid, and amino acid derivatives (e.g. nicotinic acid, alanine, alginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, and methoxyalanine). Examples of suitable sulfonyl group-bearing nitrogenous compounds include 3-pyridinesulfonic acid and pyridinium p-toluenesulfonate. Examples of suitable hydroxyl group-bearing nitrogenous compounds, hydroxyphenyl group-bearing nitrogenous compounds, and alcoholic nitrogenous compounds include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indolemethanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N,N-diethylethanolamine, triisopropanolamine, 2,2xe2x80x2-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 4-(2-hydroxyethyl)morpholine, 2-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)piperazine, 1-[2-(2-hydroxyethoxy)ethyl]piperazine, piperidine ethanol, 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)-2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyjulolidine, 3-quinuclidinol, 3-tropanol, 1-methyl-2-pyrrolidine ethanol, 1-aziridine ethanol, N-(2-hydroxyethyl)phthalimide, and N-(2-hydroxyethyl)isonicotinamide. Examples of suitable amide derivatives include formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, and benzamide. Suitable imide derivatives include phthalimide, succinimide, and maleimide.
In addition, basic compounds of the following general formula (B1) may also be included alone or in admixture.
N(X)n(Y)3-nxe2x80x83xe2x80x83B1
In the formula, n is equal to 1, 2 or 3; Y is independently hydrogen or a straight, branched or cyclic alkyl group of 1 to 20 carbon atoms which may contain a hydroxyl group or ether; and X is independently selected from groups of the following general formulas (X1) to (X3), and two or three X""s may bond together to form a ring.
In the formulas, R300, R302 and R305 are independently straight or branched alkylene groups of 1 to 4 carbon atoms; R301 and R304 are independently hydrogen, straight, branched or cyclic alkyl groups of 1 to 20 carbon atoms, which may contain at least one hydroxyl group, ether, ester or lactone ring; and R303 is a single bond or a straight or branched alkylene group of 1 to 4 carbon atoms.
Illustrative examples of the compounds of formula (B1) include tris(2-methoxymethoxyethyl)amine, tris{2-(methoxyethoxy)ethyl}amine, tris{2-(2-methoxyethoxymethoxy)ethyl}amine, tris{2-(1-methoxyethoxy)ethyl}amine, tris{2-(1-ethoxyethoxy)ethyl}amine, tris{2-(1-ethoxypropoxy)ethyl}amine, tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo-[8.8.8]hexacosane, 4,7,13,18-tetraoxa-1,10-diazabicyclo-[8.5.5]eicosane, 1,4,10,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4,1-aza-15-crown-5,1-aza-18-crown-6, tris(2-formyloxyethyl)amine, tris(2-acetoxyethyl)amine, tris(2-propionyloxyethyl)amine, tris(2-butyryloxyethyl)amine, tris(2-isobutyryloxyethyl)amine, tris(2-valeryloxyethyl)amine, tris(2-pivaloyloxyethyl)amine, N,N-bis(2-acetoxyethyl)-2-(acetoxyacetoxy)ethylamine, tris(2-methoxycarbonyloxyethyl)amine, tris(2-tert-butoxycarbonyloxyethyl)amine, tris[2-(2-oxopropoxy)ethyl]amine, tris[2-(methoxycarbonylmethyl)oxyethyl]amine, tris[2-(tert-butoxycarbonylmethyloxy)ethyl]amine, tris[2-(cyclohexyloxycarbonylmethyloxy)ethyl]amine, tris(2-methoxycarbonylethyl)amine, tris(2-ethoxycarbonylethyl)amine, N,N-bis(2-hydroxyethyl)-2-(methoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(methoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-(ethoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(ethoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-(2-methoxyethoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(2-methoxyethoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-(2-hydroxyethoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(2-acetoxyethoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-[(methoxycarbonyl)methoxycarbonyl]ethylamine, N,N-bis(2-acetoxyethyl)-2-[(methoxycarbonyl)methoxycarbonyl]ethylamine, N,N-bis(2-hydroxyethyl)-2-(2-oxopropoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(2-oxopropoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-(tetrahydrofurfuryloxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(tetrahydrofurfuryloxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-[(2-oxotetrahydrofuran-3-yl)oxycarbonyl]ethylamine, N,N-bis(2-acetoxyethyl)-2-[(2-oxotetrahydrofuran-3-yl)oxycarbonyl]ethylamine, N,N-bis(2-hydroxyethyl)-2-(4-hydroxybutoxycarbonyl)ethylamine, N,N-bis(2-formyloxyethyl)-2-(4-formyloxybutoxycarbonyl)ethylamine, N,N-bis(2-formyloxyethyl)-2-(2-formyloxyethoxycarbonyl)ethylamine, N,N-bis(2-methoxyethyl)-2-(methoxycarbonyl)ethylamine, N-(2-hydroxyethyl)-bis[2-(methoxycarbonyl)ethyl]amine, N-(2-acetoxyethyl)-bis[2-(methoxycarbonyl)ethyl]amine, N-(2-hydroxyethyl)-bis[2-(ethoxycarbonyl)ethyl]amine, N-(2-acetoxyethyl)-bis[2-(ethoxycarbonyl)ethyl]amine, N-(3-hydroxy-1-propyl)-bis[2-(methoxycarbonyl)ethyl]amine, N-(3-acetoxy-1-propyl)-bis[2-(methoxycarbonyl)ethyl]amine, N-(2-methoxyethyl)-bis[2-(methoxycarbonyl)ethyl]amine, N-butyl-bis[2-(methoxycarbonyl)ethyl]amine, N-butyl-bis[2-(2-methoxyethoxycarbonyl)ethyl]amine, N-methyl-bis(2-acetoxyethyl)amine, N-ethyl-bis(2-acetoxyethyl)amine, N-methyl-bis(2-pivaloyloxyethyl)amine, N-ethyl-bis[2-(methoxycarbonyloxy)ethyl]amine, N-ethyl-bis[2-(tert-butoxycarbonyloxy)ethyl]amine, tris(methoxycarbonylmethyl)amine, tris(ethoxycarbonylmethyl)amine, N-butyl-bis(methoxycarbonylmethyl)amine, N-hexyl-bis(methoxycarbonylmethyl)amine, and xcex2-(diethylamino)-xcex4-valerolactone.
The basic compound is preferably formulated in an amount of 0.001 to 10 parts, and especially 0.01 to 1 part, per part of the photoacid generator. Less than 0.001 part of the basic compound fails to achieve the desired effects thereof, while the use of more than 10 parts would result in too low a sensitivity and resolution.
Other Components
In the resist composition, a compound bearing a xe2x89xa1Cxe2x80x94COOH group in a molecule may be blended. Exemplary, non-limiting compounds bearing a xe2x89xa1Cxe2x80x94COOH group include one or more compounds selected from Groups I and II below. Including this compound improves the PED stability of the resist and ameliorates edge roughness on nitride film substrates.
Group I:
Compounds in which some or all of the hydrogen atoms on the phenolic hydroxyl groups of the compounds of general formulas (A1) to (A10) below have been replaced with xe2x80x94R401xe2x80x94COOH (wherein R401 is a straight or branched alkylene of 1 to 10 carbon atoms), and in which the molar ratio C/(C+D) of phenolic hydroxyl groups (C) to xe2x89xa1Cxe2x80x94COOH groups (D) in the molecule is from 0.1 to 1.0.
In these formulas, R408 is hydrogen or methyl; R402 and R403 are each hydrogen or a straight or branched alkyl or alkenyl of 1 to 8 carbon atoms; R404 is hydrogen, a straight or branched alkyl or alkenyl of 1 to 8 carbon atoms, or a xe2x80x94(R409)hxe2x80x94COORxe2x80x2 group (Rxe2x80x2 being hydrogen or xe2x80x94R409xe2x80x94COOH); R405 is xe2x80x94(CH2)ixe2x80x94 (wherein i is 2 to 10), an arylene of 6 to 10 carbon atoms, carbonyl, sulfonyl, an oxygen atom, or a sulfur atom; R406 is an alkylene of 1 to 10 carbon atoms, an arylene of 6 to 10 carbon atoms, carbonyl, sulfonyl, an oxygen atom, or a sulfur atom; R407 is hydrogen, a straight or branched alkyl or alkenyl of 1 to 8 carbon atoms, or a hydroxyl-substituted phenyl or naphthyl; R409 is a straight or branched alkylene of 1 to 10 carbon atoms; R410 is hydrogen, a straight or branched alkyl or alkenyl of 1 to 8 carbon atoms, or a xe2x80x94R411xe2x80x94 COOH group; R411 is a straight or branched alkylene of 1 to 10 carbon atoms; the letter j is an integer from 0 to 5; u and h are each 0 or 1; s1, t1, s2, t2, s3, t3, s4, and t4 are each numbers which satisfy s1+t1=8, s2+t2=5, s3+t3=4, and s4+t4=6, and are such that each phenyl skeleton has at least one hydroxyl group; xcexa is a number such that the compound of formula (A6) may have a weight average molecular weight of 1,000 to 5,000; and xcex is a number such that the compound of formula (A7) may have a weight average molecular weight of 1,000 to 10,000.
Group II:
Compounds of general formulas (A11) to (A15) below.
In these formulas, R402, R403, and R411 are as defined above; R412 is hydrogen or hydroxyl; s5 and t5 are numbers which satisfy s5xe2x89xa70, t5xe2x89xa70, and s5+t5=5; and hxe2x80x2 is equal to 0 or 1.
Illustrative, non-limiting examples of the compound bearing a xe2x89xa1Cxe2x80x94COOH group include compounds of the general formulas AI-1 to AI-14 and AII-1 to AII-10 below.
In the above formulas, Rxe2x80x3 is hydrogen or a CH2COOH group such that the CH2COOH group accounts for 10 to 100 mol % of Rxe2x80x3 in each compound, xcex1 and xcexa are as defined above.
The compound bearing a xe2x89xa1Cxe2x80x94COOH group within the molecule may be used singly or as combinations of two or more thereof.
The compound bearing a xe2x89xa1Cxe2x80x94COOH group within the molecule is added in an amount ranging from 0 to 5 parts, preferably 0.1 to 5 parts, more preferably 0.1 to 3 parts, further preferably 0.1 to 2 parts, per 100 parts of the base resin. More than 5 parts of the compound can reduce the resolution of the resist composition.
The resist composition of the invention may additionally include an acetylene alcohol derivative for the purpose of enhancing the shelf stability. Preferred acetylene alcohol derivatives are those having the general formula (S1) or (S2) below.
In the formulas, R501, R502, R503, R504, and R505 are each hydrogen or a straight, branched, or cyclic alkyl of 1 to 8 carbon atoms; and X and Y are each 0 or a positive number, satisfying 0xe2x89xa6Xxe2x89xa630, 0xe2x89xa6Yxe2x89xa630, and 0xe2x89xa6X+Yxe2x89xa640.
Preferable examples of the acetylene alcohol derivative include Surfynol 61, Surfynol 82, Surfynol 104, Surfynol 104E, Surfynol 104H, Surfynol 104A, Surfynol TG, Surfynol PC, Surfynol 440, Surfynol 465, and Surfynol 485 from Air Products and Chemicals Inc., and Surfynol E1004 from Nisshin Chemical Industry K.K.
The acetylene alcohol derivative is preferably added in an amount of 0.01 to 2% by weight, and more preferably 0.02 to 1% by weight, per 100% by weight of the resist composition. Less than 0.01% by weight would be ineffective for improving coating characteristics and shelf stability, whereas more than 2% by weight would result in a resist having a low resolution.
The resist composition of the invention may include, as an optional ingredient, a surfactant which is commonly used for improving the coating characteristics. Optional ingredients may be added in conventional amounts so long as this does not compromise the objects of the invention.
Nonionic surfactants are preferred, examples of which include perfluoroalkylpolyoxyethylene ethanols, fluorinated alkyl esters, perfluoroalkylamine oxides, perfluoroalkyl EO-addition products, and fluorinated organosiloxane compounds. Useful surfactants are commercially available under the trade names Florade FC-430 and FC-431 from Sumitomo 3M K.K., Surflon S-141 and S-145 from Asahi Glass K.K., Unidine DS-401, DS-403 and DS-451 from Daikin Industry K.K., Megaface F-8151 from Dai-Nippon Ink and Chemicals K.K., and X-70-092 and X-70-093 from Shin-Etsu Chemical Co., Ltd. Preferred surfactants are Florade FC-430 from Sumitomo 3M K.K. and X-70-093 from Shin-Etsu Chemical Co., Ltd.
Pattern formation using the resist composition of the invention may be carried out by a known lithographic technique. For example, the resist composition is applied onto a substrate such as a silicon wafer by spin coating or the like to form a resist film having a thickness of 0.3 to 2.0 xcexcm, which is then pre-baked on a hot plate at 60 to 150xc2x0 C. for 1 to 10 minutes, and preferably at 80 to 130xc2x0 C. for 1 to 5 minutes. A patterning mask having the desired pattern is then placed over the resist film, and the film exposed through the mask to an electron beam or to high-energy radiation such as deep-UV rays, excimer laser light, or x-rays in a dose of about 1 to 200 mJ/cm2, and preferably about 10 to 100 mJ/cm2, then post-exposure baked (PEB) on a hot plate at 60 to 150xc2x0 C. for 1 to 5 minutes, and preferably at 80 to 130xc2x0 C. for 1 to 3 minutes. Finally, development is carried out using as the developer an aqueous alkali solution, such as a 0.1 to 5% (preferably 2 to 3%) aqueous solution of tetramethylammonium hydroxide (TMAH), this being done by a conventional method such as dipping, puddling, or spraying for a period of 0.1 to 3 minutes, and preferably 0.5 to 2 minutes. These steps result in the formation of the desired pattern on the substrate. Of the various types of high-energy radiation that may be used, the resist composition of the invention is best suited to fine pattern formation with, in particular, deep-UV rays having a wavelength of 248 to 193 nm, excimer laser light, x-rays, or an electron beam. The desired pattern may not be obtainable outside the upper and lower limits of the above range.
The resist composition comprising the polymer as a base resin lends itself to micropatterning with electron beams or deep-UV rays since it is sensitive to high-energy radiation and has excellent sensitivity, resolution, and etching resistance. Especially because of the minimized absorption at the exposure wavelength of an ArF or KrF excimer laser, a finely defined pattern having sidewalls perpendicular to the substrate can easily be formed.

Polymers, resist compositions and patterning process


The present invention is a multiple reaction set for the production of chemicals by equilibrium limited reactions utilizing plate-type or extended surface heat exchangers. The heat exchangers effectively cool the reaction products in order to condense the methanol contained within the reaction products for separation, and also to warm incoming feed reactants prior to entrance of the reactants into a reactor utilized for the production of methanol. The various reactors, heat exchangers, and separators can be formed as separated zones within the enclosed vessels, thereby eliminating the need for separately constructed reactors, heat exchangers, and separators. Multi-stream plate-type of extended surface heat exchangers can be utilized to allow efficient cooling and methanol separation. The multiple reaction set can also be used for the recovery of methanol from a waste or purge gas stream utilizing multiple reactors, multiple plate-type or extended surface heat exchangers and multiple separators as a substitute for or in conjunction with a conventional methanol synthesis loop.

It is rare in a chemical process that the process uses stoichiometric amounts of reactants with essentially complete conversion in a simple reactor. Hence, where the reagents constitute a significant cost of the process, the unreacted material is often recycled to the reactor, usually after some physical separation of the desired product from the un-reacted material. Sometimes this separation can be achieved internally within the reactor, for example, where the reactants are gaseous, the product is in liquid form at reaction conditions and is withdrawn continuously, and a stirred tank reactor with gas induction impellers is utilized. In this particular situation, the physical separation and the recycle occurs within the reactor vessel.
Alternatively, the separation and recycle of reactant can take place external to the reactor. One example of this configuration would be a plug flow gas phase reactor where the product can be condensed from the gas phase by cooling. The unreacted gases may then be re-compressed, and at least partially returned to the inlet of the reactor, perhaps after other conditioning, such as purification or chemical separation.
There are several reasons why the amounts of reactants utilized in the reactor to form the desired end product are rarely stoichiometric. It could be that vapor pressure limitations require a non-stoichiometric reaction. For example, in high-pressure, gas-phase hydrogenations of a high boiling organic the hydrogen will be present in large excess even though a high single pass conversion of the reactant is theoretically possible. An alternate reason would be that the reaction is equilibrium limited. For example in acid catalysed esterifications the alcohol is frequently in excess to achieve high conversion of the acid.
While it may be possible to achieve high conversion of the reactants in an equilibrium limited reaction to the desired end product economically utilizing a large excess of reactants, an alternate possibility is the removal of one of the reaction products. For example, gas stripping could remove the water from an esterification reaction to continually move the conditions in the reactor out of or away from equilibrium and thereby drive the reaction toward full conversion.
However, where a product cannot be removed in-situ to drive the equilibrium toward full conversion, then a high overall conversion is likely to be achieved only by separation of the product from the reactant mixture and subsequent recycle of the un-reacted material to the reactor.
Additionally, even where an equilibrium reaction has certain conditions or aspects that are favorable for high conversion to the desired end product, the kinetics of the reaction may suggest that a higher overall production rate or better process economics can be achieved by running a reactor at conditions favoring a relatively low conversion of the reactants and then recycling the un-reacted material after physical separation of the product. Some exemplary reactions or processes of this type where conversion of the reactants to the desired product is only partial, and in which significant quantities of un-reacted material remain that can be recycled to the reactor after physical separation of the product include the reaction of synthesis gas to methanol, di-methyl ether, mixtures thereof, Fischer-Tropsch waxes, and ammonia.
Using the equilibrium limited reaction for the production of methanol as an example, because methanol is one of the largest by volume chemicals produced in the world today, the conversion to methanol is typically carried out in a two-step process. In a first step, methane is reformed with water or partially oxidized with oxygen to produce carbon monoxide and hydrogen, with some carbon dioxide and residual methane, (i.e., synthesis gas or syn-gas). In a second step, the syn-gas is converted into methanol.
The second step of converting the syn-gas into methanol is a well-known process. It typically involves a catalytic process using a copper-based catalyst, such as a catalyst comprising a reduced zinc oxide/copper oxide mixture, among others. To provide the optimum production of methanol from this reaction, the reaction is typically carried out at pressures within the range of 40-100 bars and at temperatures in excess of 200 degrees C. and below 320 degrees C., with a temperature range of between 220 and 280 degrees C. being most common. The production of the syn-gas itself is typically carried out at pressures within the range of 20-40 bars depending on the reformer technology that is utilized.
Due to the particular mechanism of the reaction for the production of methanol, the reaction does not go to completion, as the concentration of produced methanol is limited by equilibrium. Specifically, the amount of methanol contained in the product gas exiting the reactor comprises about 6-8 mol % of the total gas, although it can be higher. This methanol is removed from this product gas stream by condensing it through cooling the product gas stream to below 110 degrees C., and most commonly below 60 degrees C. The cooled methanol can then be removed from the gas stream while the excess syn-gas is sent back to the reactor in order to further react the excess syn-gas. This enables additional methanol to be obtained from the syn-gas recycled back to the reactor in combination with an amount of fresh syn-gas that is also charged to the reactor.
In performing this recycle step, one well-known process involves the use of a recycle compressor which receives the excess syn-gas from the separator and compresses it in order to overcome the pressure drop that occurs within the reactor and separator. This type of reactor is commonly referred to as a recycle loop reactor and is schematically shown in FIG. 1. In this reactor, the concentration of methanol in the syn-gas leaving the reactor is low enough that the volumetric flow rate of the excess syn-gas through the recycle compressor is typically two (2) to ten (10) times the volumetric flow rate of the fresh syn-gas being introduced into the reactor separately from the syn-gas charged to the reactor from the recycle compressor. A purge gas stream of approximately 4 to 8 percent of the recycled syn-gas stream is also expelled from the recycle loop, prior to re-compression to control the concentration of inert material that builds up in the reactor as a result of the recycle.
One significant drawback to the recycle loop reactor described above is the cost of the recycle compressor. Often the recycle function is incorporated into a single drive train compressor that compresses the syn-gas up to the pressure of the recycle loop and also provides for re-compression of the recycle gases. The compression train is an expensive item of equipment and may be the single most expensive purchased component in the construction of a methanol producing facility. As stated previously, a high recycle flow is utilized to enable high overall conversion of syn-gas to be achieved. The recycle compressor also becomes significantly cheaper per unit volume compressed as the scale of the plant is increased. Thus, the use of a process using a recycle compressor is, as a practical matter, preferential for those facilities producing a relatively high daily output of methanol relative to the current maximum single train production plant, such as those facilities producing in the neighborhood of 5,000 tons per day in 2005, where maximum efficiency is required and integration of the syn-gas compressor and recycle compressor can be achieved in order to make the use of a recycle compressor economically viable.
As an alternative to a recycle loop reactor, it has been conceived that the facility could utilize a multiple reactor set or cascade process (FIG. 2) whereby the syn-gas is initially fed to a first reactor for reaction with the catalyst contained therein to produce methanol. The product gas then enters a first separator or knock-out pot wherein the methanol produced in the first reactor is cooled into liquid form and separated from the excess syn-gas. The first separator can operate to separate the methanol for the syn-gas in any desired manner, such as by gravity or by applying centrifugal focus to the products. The remaining excess syn-gas is then fed to a second reactor, which undergoes the same reaction, thereby producing additional methanol. The additional methanol is removed from the second reactor and directed to a second separator in the same manner. The number of reactors and separators can be selected to create a multiple reactor set that achieves the desired conversion percentage of the syn-gas to methanol. For example, when using an optimal syn-gas composition that has a conversion to methanol of 50 percent in each reactor, the reactor set can be selected to include four reactors and four separators, which theoretically results in the achievement of a 95 percent overall conversion of the syn-gas to methanol after the fourth separator.
However, in more realistic situations, when the syn-gas composition is less optimal, such as when the stoichiometry of the syn-gas is away from the stoichiometry of the reaction desired, e.g., the ratio ([moles hydrogen]-[moles carbon dioxide])/([moles carbon monoxide]+[moles carbon dioxide]) is between 2.5 and 3.0, then more than four reactor sets and perhaps as many as 10 reactor sets are required for high conversion (>95%). Additionally, when there are stoichiometric quantities of reactant in the syn-gas, but high levels of inerts also present, then a high number of reactor sets will be required, such as where autothermal reforming with air is performed for the production of syn-gas resulting in dilution of the syn-gas with high levels of nitrogen.
There are several areas in a methanol production process where the ability to employ a cascade of reactors would be considered beneficial. Principally the benefit from using the cascade comes from not requiring a recycle compressor. Furthermore, it should be borne in mind that in a grass roots methanol production plant the recycle compressor is often part of the compressor associated with syn-gas compression. Thus, eliminating the syn-gas compressor along with the recycle compressor in a grass roots installation gives the maximum benefit.
While the use of a simple cascade of reactors for this particular purpose is disclosed in certain prior art references, the references that discuss the use of such a cascade of reactors focus exclusively on methods by which the reformer operating pressure can be matched to the methanol synthesis pressure. For example, U.S. Pat. Nos. 5,177,114; 5,245,110; 5,472,986; and 7,019,039 are each patents that disclose inventions in the field of autothermal reforming using air rather than oxygen. However, while these patents very generally disclose the use of cascade reactors in the methanol production process, they do not address the issues of how the cascade of reactors can be made cost effectively. Furthermore, each of U.S. Pat. Nos. 5,177,114; 5,245,110; and 5,472,986 disclose a methanol production process where the recycle compressor can be eliminated as a result of operating a reformer autothermally, and then converting the syn-gas to a methoxy compound using three to five reactor sets with product condensation between each stage. Recognizing conventional wisdom that a cascade process cannot achieve a high syn-gas to methanol conversion, carbon efficiencies for the methanol synthesis section of less than 80% are quoted, whereas in conventional plant efficiencies in excess of 95% are achievable.
Additionally, U.S. Pat. No. 6,255,357 discloses a methanol production process that uses pressurization of the oxidant gas for fired heating of the steam reformer as a means of achieving an mechanically feasible high pressure steam reformer with an operating pressure sufficient to ensure a sufficient operating pressure throughout the process. The process also includes a cascade of reactors downstream from the reformer in which the reformed syn-gas is converted to methanol. The pressurization of the incoming natural gas into the reformer avoids the requirement of a syn-gas compressor upstream of the cascade of reactors, as well as avoiding the need for a recycle compressor. However, as with the previous references, the cascade of reactors is only very generally disclosed without any discussion as to how the cascade can be made economically.
Other situations regarding a methanol production process where it would be considered advantageous to avoid use of a recycle compressor include those where the compressor would be added to an existing methanol production facility in a retro-fit capacity, or as part of an addition to a planned methanol production facility construction for the purpose of removing any remaining methanol from the purge gas discharged from the facility. One system of this type that addresses the loss of the potential and actual methanol present in the purge gas stream is disclosed in U.S. Pat. No. 6,258,860, which is incorporated by reference herein in its entirety. The process disclosed directs the purge gas stream produced by a methanol synthesis zone to another methanol synthesis or production zone in order to both collect the methanol present in the purge gas stream as well as to further react the unreacted components of the purge gas stream to produce additional methanol.
However, the process disclosed in the '860 patent has certain drawbacks in that it utilizes a compressor to compress the combined purge gas and recycled syn-gas stream prior to further reacting the combined stream. Because, as discussed previously, the recycle compressor is the highest cost item in a methanol production system, the use of additional recycle compressors to recover methanol from a purge gas is highly undesirable, especially for systems producing a relatively low daily output of methanol relative to the current maximum single train production plant, such as those facilities producing in the neighborhood of 5,000 tons per day in 2005.
Another example where additional compressor capacity may be avoided through the use of a set of cascade reactors could occur as part of a re-vamp or de-bottle-necking of a methanol plant. If the re-vamp or de-bottlenecking entails increased syn-gas production, then the capacity of the methanol converter would be required to be increased. It may be possible to increase the effectiveness of the reactor through better packing of catalyst or dividing the catalyst into multiple beds in a single reactor. However, where the reactor already makes effective use of the catalyst, it may not be possible to economically increase the performance of the reactor. Further, another limitation on the operation of the reactor in this situation is the pressure drop of the process gas across the reactor. Increasing the re-circulation rate, increasing the catalyst volume, increasing the feed flow or reducing the purge rate will all increase the pressure drop of the process gas through the reactor. There will of course be a consequent limitation on the capacity of the re-circulation compressor as well to recompress the gas for reintroduction into the reactor.
One alternative to mitigate these issues would be to operate the methanol converter at reduced conversion conditions, but with a higher gas feed rate, thereby allowing pressure drop limitations to be avoided and then utilizing a separate cascade reactor system to convert the un-reacted gases to methanol without the requirement of an additional compressor or replacing the original reactor. This also has the advantage of being a lower risk method of increased throughput, as the original reactor performance is well known. There will of course be many other circumstances under which a cascade system can be utilized, but all of these circumstances will be reliant on a cost-effective design of cascade system.
One significant drawback with the multiple or cascade reactor set types utilized in methanol production as described in the prior art results from the end use construction of each reactor, heat exchanger(s) and separator forming the individual reactor set. Specifically, because a portion of the syn-gas is lost in each reactor set based on its conversion to methanol, often each subsequent reactor set and separator is constructed to be smaller than the immediately preceding ones to accommodate the reduction in the flow rate of incoming syn-gas. This might initially be anticipated to be highly beneficial based upon the reduction in the amount of material necessary to construct each successive reactor set. However, each reactor set requires the same functionality, connections, cooling and access for catalyst replacement, which become more difficult and/or expensive to manufacture on a progressively smaller scale. In addition, the cooling, gas-liquid separation and re-heating of the methanol-bearing stream as it passes between the various reactor sets must be effected in an energy efficient and cost effective manner. Further, all of the reactor sets and separators must be constructed to be operable at the elevated pressures (40-100 bars) that the reactions occurring for the conversion of the syn-gas to methanol require.
One example of a system that attempts to address this shortcoming is disclosed in U.S. Pat. No. 6,723,886 in a methanol production process using reactive distillation. However, while there is removal of methanol between reactor beds by condensation within the reactor, the condensation takes necessarily takes place at reaction temperature, and condensation at elevated temperature limits the conversion of methanol to approximately 60%. However, even with the significant restriction this places on methanol production, this is in accord with the current industry view that condensation at reduced temperature is not viable.
Therefore, it is desirable to develop a multiple or cascade reactor set and a process for the production of products of equilibrium limited reactions, e.g., methanol, using the multiple reactor set to obtain a high percentage conversion of feed syn-gas to methanol by condensing the methanol in the reactor effluent in an interstage feed/effluent heat exchanger. It is also desirable that the multiple reactor set be operable without the need for a gas recycle compressor and preferably without the need for the construction of multiple individual reactors, heat exchangers, and separators. In other terms, the heat exchanger design should be suitable for efficient operation and integration into the reactor sets, while also minimizing the number of necessary equipment items.
With regard to the goal of minimizing the necessary number of equipment items in a reactor set, it is easier to understand the conventional approach to solving this problem of eliminating equipment items and reducing the cost of equipment items by reference to the specific problems of a conventional methanol synthesis loop. Apart from the recycle compressor, a methanol synthesis loop contains six principle operations: 1) pre-heat of the gas; 2) reaction of the gas to form methanol; 3) removal of the heat of reaction as high grade heat; 4) cooling of the gas to methanol condensation temperatures; 5) condensation of the methanol using cooling water; and 6) vapor/liquid separation. In a typical plant there may be two integrations of these functions for the purposes of minimizing the necessary equipment items which are removal of the heat of reaction is performed by steam raising in a shell and tube reactor, and pre-heat of the gas by feed-effluent exchange. Thus, a typical synthesis loop will consist of at least six equipment items: 1) a start up heater; 2) a feed/effluent heat exchanger; 3) a reactor; 4) a high grade heat recovery unit; 5) a water cooler; and 6) a gas-liquid separator.
Steam raising directly in the reactor does eliminate the requirement for a separate high-grade heat recovery unit. However, it also requires a steam drum with the reactor and so does not reduce the number of equipment items.
With regard to the use of the feed/effluent heat exchanger, the highest energy efficiency is achieved with a high effectiveness heat exchanger that is able to maximize the cooling of the effluent stream. Increasing the amount of high grade heat recovered reduces the temperature difference in the feed/effluent exchanger. Therefore, for maximum high grade heat recovery a high effectiveness heat exchanger is required. However, shell and tube heat exchangers as used in prior art multiple reactor sets can only achieve high effectiveness through the coupling of multiple heat exchanger units, again increasing the number of equipment items required. The usefulness of high grade heat recovery is, in part dependent, on the temperature at which it is recovered. In particular, for a methanol process the high grade heat recovery from the methanol synthesis section is utilized for steam raising for the reformer. This requires that the stream from which heat is being recovered is above a minimum temperature, typically 200-250 deg C. However methanol condensation temperatures are in the region of 60-100 deg C. For efficient operation, therefore, heat exchangers are required that can operate with a hot gas temperature span of approximately 150 deg C. The heat of reaction is recovered by cooling the reactant stream by the equivalent of typically 50-100 deg C. of sensible heating. If the feed gas is introduced to the methanol reactor at a temperature below high grade heat recovery temperature this represents a loss of energy efficiency in the system and increases the low grade cooling requirement. Consequently the temperature difference in the feed-effluent exchanger will be kept to less than 50 deg C. and typically 20-30 deg C. Where high single pass conversions can be achieved in the reactor, such as with a balanced stoichiometry, high operating pressure, efficient heat removal or a low overall conversion the temperature constraints may be more relaxed. However, this often brings greater reactor complexity or lower overall efficiency.
The performance measure of a heat exchanger can be described in terms of temperature span and log mean temperature difference between stream. The value (span divided my lmtd) is referred to as NTU count and as can be seen above it would be desired for an energy efficient methanol process that the fee/effluent exchangers would operate with an NTU count above 5, and more preferably above 7.
The problem concerning the number of equipment items is also not alleviated when a recycle loop is replaced with a cascade system. With no recycle there is no requirement for a recycle compressor. However, for each contact with the catalyst there will be up to six additional equipment items, as discussed previously. One option to reduce the number of equipment items is to eliminate some of the heat exchangers. For example, instead of recovering high grade heat from the reactor gases, the gases can be used to directly heat the incoming feed gases. The feed/effluent exchanger is then smaller as a result of an increased driving temperature, but the reaction heat is then lost to the cooling water and a less efficient process is produced.
Therefore, to improve the economics and efficiency of the prior art methanol cascade systems, it is necessary to solve the following issues: 1) to minimize the number of equipment items; 2) to increase the effectiveness of the feed/effluent exchangers; and 3) to integrate multiple functions into single equipment items.

Multiple reactor chemical production system


A power conversion apparatus capable of cheaply securing safety and achieving watertightness. The power conversion apparatus (100) has: a charging device (14) for charging from an external power source (20) to a cell (30); an inverter (13) for converting the current of the cell (30) from direct current to alternating current and supplying the current to a motor (40); and a junction box (15) for relaying an electrical connection. The inverter (13), the charging device (14), and the junction box (15) are contained in a single housing. Also, the charging device (14) and the junction box (15) are electrically connected, and the junction box (15) and the inverter (13) are electrically connected. Also, the junction box (15) and the inverter (13) are connected by a bus bar (16).

In recent years, electric vehicles (EVs) or plug-in hybrid electric vehicles (PHEVs) have become popular. These vehicles each include: a battery; a charging apparatus configured to charge the battery using an external power supply (commercial power supply); an inverter configured to convert a direct current from the battery to an alternating-current; and a motor configured to drive a wheel of the vehicle using the alternating-current from the inverter (e.g., see Patent Literature (hereinafter, referred to as "PTL") 1. These devices are electrically connected to each other.

This patent is subject to a terminal disclaimer.

Power conversion apparatus and junction box

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