Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Priority
Receipt is acknowledged of certified copies of papers required by 37 CFR 1.55.
Information Disclosure Statement
The information disclosure statement (IDS) submitted on 12/12/2025 is being considered by the examiner.
Claim Rejections - 35 USC § 103
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
Claim(s) 1-16 and 18 is/are rejected under 35 U.S.C. 103 as being unpatentable over Takahashi et al (US 20110183263 A1).
Regarding Claims 1, and 3-13, Takahashi teaches an actinic-ray sensitive composition comprising a resin P, containing a repeating unit A, that when exposed to radiation decomposes to generate an acid and at least two repeating units B1 and B2 are decomposed by acid so as to generate alkali-soluble functionalities – and where B1 and B2 are different subunits.
Takahashi does not specifically disclose an experimental embodiment meeting the limitations of the claim(s).
These limitations are met by the general disclosure of the reference.
The resin (P) is described from [00073]-[0449] , where the resin comprises a repeating unit (A) described by any of the formulas (I) and/or (II)
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Wherein R11-R13 may each be H, alkyl (See [0042]), an aliphatic hydrocarbon ring ([0044), a halogen, cyano, or alkoxycarbonyl group. These groups may be substituted with halogen, nitro, cyano, hydroxyl, or another group mentioned at [0046].
X11-X13 may each independently be a single bond, ether bond, thiol bond, carbonyl, -SO2-, -NR- (R is H or alkyl), a bivalent nitrogenous nonaromatic heterocyclic group (See [0050]), or a group composed of a combination of these.
L11 may be a single bond, alkylene, alkenylene, bivalent aromatic or aliphatic hydrocarbon ring, or combination thereof ([0054]-[0060]).
L12 may be a group as described by L11, provided that the group be at least partially fluoro or fluoroalkyl or nitro or cyano-substituted ([0061]-[0068]
Ar1 is a bivalent aromatic ring or group composed from a combination of aromatic ring and alkylene group, where a substituent may be introduced on the aromatic ring group.
Z1 is a moeity that when exposed to actinic rays or radiation is converted to a sulfonate group, imidate group, or methide group – preferably an onium salt such as those of formulas (Z-I) to (ZIII) in [0075], where A+ is a sulfonium cation or an iodonium cation. The cation is further described from [0083]-[0209].
Exemplary (but not limiting) embodiments of the monomer units corresponding to subunits conforming to formula (I) are depicted at [0210].
Monomers conforming to formula (II) are discussed from [0211]-[0250]
Wherein R21-R23 may each be H, alkyl, an aliphatic hydrocarbon ring, a halogen, cyano, or alkoxycarbonyl group. These groups may be substituted with halogen, nitro, cyano, hydroxyl, or another group mentioned at [0046].
X21-X23 may each independently be a single bond, ether bond, thiol bond, carbonyl, -SO2-, -NR- (R is H or alkyl), a bivalent nitrogenous nonaromatic heterocyclic group, or a group composed of a combination of these.
L21 may be a single bond, alkylene, alkenylene, bivalent aromatic or aliphatic hydrocarbon ring, or combination thereof
L22 may be a group as described by L21, provided that the group be at least partially fluoro or fluoroalkyl or nitro or cyano-substituted
Ar2 is a bivalent aromatic ring or group composed from a combination of aromatic ring and alkylene group, where a substituent may be introduced on the aromatic ring group.
Z2 is a moeity that when exposed to actinic rays or radiation is converted to a sulfonate group, imidate group, or methide group – preferably an onium salt such as those of formulas (Z-I) to (ZIII) in [0075], where A+ is a sulfonium cation or an iodonium cation.
Exemplary (but not limiting) embodiments of the monomer units corresponding to subunits conforming to formula (II) are depicted at [0249].
The subunits (I) and/or (II) meet the limitations of the claim, when in monomer form, where:
Formula (I):
Z1 is a sulfonic acid anion associated to a sulfonium/iodonium cation (claimed *-SO3- ZI+)
L12 is a C6 aryl group (phenyl) having 4x fluorines thereon (Claimed phenylene ring, where R1 is F, m1=4)
X13 is an -O-, -CO-O-, -O-CO-, -O-CO-O- linkage (ether group, single bond, -CO-, and/or groups composed thereof) (claimed X1)
Claim 3 for where claimed X1 is -CO-O-, or -O-CO-
L11 is a single bond, or an alkylene, alkenylene, bivalent aromatic or aliphatic hydrocarbon ring, or combination thereof between 1-28 carbons in size (Claimed L1)
Claim 4 for where L11 is a single bond or a linear alkylene group having 1-6 carbons ([0055] (Claimed L1 is a single bond or C1-C6 linear alkanediyl group)
X12 is a single bond attached to Ar1 (Claimed Ar), where Ar1 is an aromatic group preferably having 1-18 carbon atoms therein ([0070])
X11 is an -O-, -CO-O-, -O-CO-, -O-CO-O- linkage (ether group, single bond, -CO-, and/or groups composed thereof) (claimed L2 is a single bond, attached to claimed X0 which is -O-, -CO-O-, -O-CO-, or -O-CO-O-)
Claims 5 and 6, wherein when claimed L2 is a single bond and claimed L1 is as described regarding claim 4 above
Claim 7, where when claimed X0 is -CO-O or -O-CO-O, formulas X10-1 and X10-2 are met, respectively
Claim 8, where claimed X0 is -CO-O formula X10-1 is met
R13 is H, alkyl (See [0042]) having 1-20 carbons, an aliphatic hydrocarbon ring ([0044] – having 3-8 carbons ), a halogen, cyano, or alkoxycarbonyl group. These groups may be substituted with halogen, nitro, cyano, hydroxyl, or another group mentioned at [0046] when applicable. R11 and R12 are H. (claimed R5 is halogen, cyano, nitro, or a C1-C12 haloalkyl group or a C1-C18 alkyl group)
The subunit (I) (as well as subunit (II)) as described above generates an acid upon exposure to actinic radiation and as such functions as an acid generator, and is incorporated into the resin (P) (claims 9 and 10). The composition comprising the resin (P) is used in the production of a resist film ([0029] claim 11). The resin (P) also comprises structural units having acid labile groups – the units (B1) and (B2) as described from [0285]-[0358] and more specifically depicted by formulas (V) and (VI) (claim 12 and 13).
Takahashi ascribes excelling sensitivity and resolution, as well as improved line edge roughness in patterned resist films made, to the composition comprising the resin (P) and other components ([0031])
A person having ordinary skill in the art would have found it obvious to arrive at the claimed invention prior to the filing date in view of the disclosure of Takahashi using the known materials to arrive at a composition having improved sensitivity for use in forming patterned resist films exhibiting improved resolution and line edge roughness.
Regarding claim 2, Takahashi teaches an actinic-ray sensitive composition comprising a resin P, containing a repeating unit A, that when exposed to radiation decomposes to generate an acid and at least two repeating units B1 and B2 are decomposed by acid so as to generate alkali-soluble functionalities – and where B1 and B2 are different subunits, as discussed above regarding claims 1,11, and 13.
Takahashi does not specifically disclose an experimental embodiment meeting the limitations of the claim(s).
These limitations are met by the general disclosure of the reference.
Takahashi’s Ar1 (see above – Claimed Ar) is not explicitly substituted with halogen atoms, but may be a substituted C6-C18 aromatic ring such as a phenylene ring. Elsewhere in the reference, such as L12, the explicit mention of fluorinated phenylene rings is given as preferable. The reference at multiple points when discussing formula (I) discusses that substituents may be halogens such as fluorines when substituents are brought up regarding the functional groups of the monomer.
The inclusion of at least one fluorine into the phenylene group of the reference’s Ar1 would be a matter of simple substitution (substituting at least one fluorine), and as the art does not recite deleterious effects to the use of such substitutions when describing them, such substitution would be expected to behave similarly to the non-substituted variant of the phenylene group.
A person having ordinary skill in the art would have found it obvious to arrive at the claimed invention by substituting at least one hydrogen for a fluorine in the phenylene group of Ar1 in Takahashi with the expectation that the substituted group would behave similarly.
Regarding Claim 14, Takahashi teaches an actinic-ray sensitive composition comprising a resin P, containing a repeating unit A, that when exposed to radiation decomposes to generate an acid and at least two repeating units B1 and B2 are decomposed by acid so as to generate alkali-soluble functionalities – and where B1 and B2 are different subunits, as discussed above regarding claims 1,11, and 13.
Takahashi does not specifically disclose an experimental embodiment meeting the limitations of the claim(s).
These limitations are met by the general disclosure of the reference.
Takahashi teaches the subunit structure of the monomer corresponding to claimed formula (I) as discussed above regarding claim 1. Additionally disclosed is a polymerization method incorporating the monomer(s) of the resin ([0408]-[0435], wherein the polymer is made from a radical polymerization method that may or may not include a chain transfer agent.
Takahashi also teaches that a low-molecular weight (non-polymeric) acid generating salt may also be incorporated ([0451]-[0454], wherein the additional acid generator may be a single species or multiple species used in admixture. Incorporating unpolymerized acid-generating monomer into the composition functions as a nonpolymeric acid generator, wherein the monomeric form would be more readily compatible with the composition due to the chemical similarity of the monomer to the polymeric embodiment thereof as opposed to a more chemically disparate embodiment. This incorporation amounts to the simple substitution of one element for another (the monomer acid generator conforming to formula (I) for a generic small-molecule acid generator) with the expectation of similar and/or predictable results.
A person having ordinary skill in the art would have found it obvious to arrive at the claimed invention prior to the effective filing date from the disclosure of the reference by incorporating the monomer of Takahashi’s formula (I) into the photoresist composition with the expectation that it would behave predictably and produce acid to abet lithographic processing.
Regarding Claim 15, Takahashi teaches an actinic-ray sensitive composition comprising a resin P, containing a repeating unit A, that when exposed to radiation decomposes to generate an acid and at least two repeating units B1 and B2 are decomposed by acid so as to generate alkali-soluble functionalities – and where B1 and B2 are different subunits, as discussed above regarding claims 1,11, and 12.
Takahashi does not specifically disclose an experimental embodiment meeting the limitations of the claim(s).
These limitations are met by the general disclosure of the reference.
The resin (P), in addition to an acid generating unit, also comprises structural units having acid labile groups – the units (B1) and (B2) as described from [0285]-[0358] and more specifically depicted by formulas (V) and (VI):
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Wherein
Each of R51-R53 may be H, C1-C20 alkyl, a C3-C8 monovalent hydrocarbon ring, halogen, cyano, or an alkoxycarbonyl group
L5 is a single bond, or a bivalent linking group, or if/when R52 is part of a ring system, L5 is a trivalent linking group connected thereto.
Exemplary linking groups include phenylene rings, ester linkages, combinations thereof, or other linkages as described at [0315]
R54-R56 may each be a C1-C20 alkyl group, or R55 and R56 may each additionally be a hydrogen atom, aliphatic hydrocarbon group having 3-20 carbons, or C6-C20 monovalent aromatic rings. The groups R54-R56 may be bonded together in pairs or triply to form a ring system.
Exemplary subunits (V) are depicted at [0322]
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Wherein R61-R63 may each be H, C1-C20 alkyl, a C3-C8 monovalent hydrocarbon ring, halogen, cyano, or an alkoxycarbonyl group
Ar6 is an aromatic ring group ranging from 6-18 carbons (see [0333])
Y is a group cleaved by the action of an acid, such as group VI-A:
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L1 and L2 are H, C1-C8 alkyl, C6-C15 aryl, or a combination of the two
M is a single bond or a bivalent linkage such as an alkylene group such as methylene, octylene, or group having an intermediate number of carbons; or an ether, thiol, carbonyl, sulfonyl, or group arising from a combination of the preceding groups,
Q is an alkyl group such as those regarding L1 and L2.
The subunit (V) meets the limitations of the claim for where the acid-labile group bearing subunit a1) as claimed is represented by a formula (a1-0):
Claimed Ra01 is Reference R53, where R53 is a hydrogen atom, halogen, or C1-C6 alkyl
Claimed La01 is -O-, and the combination of La01 and the preceding carbonyl group are analogous to the ester functionality of the reference where reference L5 is a single bond
Claimed Ra02 through Ra04 are analogous to R54-R56, which may each be C1-C8 alkyl group, or R55 and R56 may each additionally be a hydrogen atom, aliphatic hydrocarbon group having 3-20 carbons, or C6-C18 monovalent aromatic rings.
The subunit (V) meets the limitations of the claim for where the acid-labile group bearing subunit a1) as claimed is represented by a formula (a1-1):
Claimed Ra01 is Reference R53, where R53 is a hydrogen atom, halogen, or C1-C6 alkyl
Claimed La1 is -O-, and the combination of La1 and the preceding carbonyl group are analogous to the ester functionality of the reference where reference L5 is a single bond
Claimed Ra6 is are analogous to R54, which may each be C1-C8 alkyl group, when R55 and R56 may each additionally be an aliphatic hydrocarbon group having 3-20 carbons and bonded together (See V-42, which bears an ethyl group attached to an adamantyl group). M1’ is 0
The subunit (V) meets the limitations of the claim for where the acid-labile group bearing subunit a1) as claimed is represented by a formula (a1-2):
Claimed Ra01 is Reference R53, where R53 is a hydrogen atom, halogen, or C1-C6 alkyl
Claimed La2 is -O-, and the combination of La2 and the preceding carbonyl group are analogous to the ester functionality of the reference where reference L5 is a single bond
Claimed Ra7 is are analogous to R54, which may each be C1-C8 alkyl group, when R55 and R56 may each additionally be an aliphatic hydrocarbon group having 3-20 carbons and bonded together (See V-25, which bears an ethyl group attached to a cyclopentyl group), and n1’ may be 0-3
The subunit (VI) meets the limitations of the claim for where the acid-labile group bearing subunit a1) as claimed is represented by a formula (a1-3):
Wherein R63 may be H, C1-C6 alkyl, or halogen, (claimed Ra32)
Claimed Aa30 is a single bond
Ar6 is a phenylene group (claimed phenyl ring)
Y is a group cleaved by the action of an acid, such as group VI-A :
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Claimed Ra34 and Ra35are H, C1-C8 alkyl, C6-C12 aryl,
M is a single bond
Claimed Ra36 is C1-C8 alkyl, C6-C15 aryl, or a combination of the two having no more than 20 carbon atoms.
Takahashi ascribes excellent sensitivity and resolution, as well as improved line edge roughness in patterned resist films made, to the composition comprising the resin (P) and other components ([0031])
A person having ordinary skill in the art would have found it obvious to arrive at the claimed invention prior to the filing date in view of the disclosure of Takahashi using the known materials to arrive at a composition having improved sensitivity for use in forming patterned resist films exhibiting improved resolution and line edge roughness.
Regarding Claim 16, Takahashi teaches an actinic-ray sensitive composition comprising a resin P, containing a repeating unit A, that when exposed to radiation decomposes to generate an acid and at least two repeating units B1 and B2 are decomposed by acid so as to generate alkali-soluble functionalities – and where B1 and B2 are different subunits, as discussed above regarding claims 1,11, and 12.
Takahashi does not specifically disclose an experimental embodiment meeting the limitations of the claim.
These limitations are met by the general disclosure of the reference.
Takahashi describes that the resin (P) may include a unit having an alkali soluble group having an aromatic ring, wherein the subunit conforms to formula (IV):
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Wherein:
R41-R43 are each independently a hydrogen, C1-C20 alkyl group, monovalent hydrocarbon ring group, halogen, cyano group, or alkoxycarbonyl group.
Ar4 is an aromatic ring such as phenylene or naphthalene, which may be substituted with alkyl groups or alkoxy groups as discussed at [0385].
Subscript a is an integer of 0-2
Exemplary subunits are depicted at [0388]-[0389], such as hydroxystyrene, ethylhydroxystyrene, dichlorohydroxystyrene and dihydroxystyrene
The subunit (IV) meets the limitations of the claim for the claimed formula (a2-A) where:
Claimed Ra50 is a hydrogen, halogen, or alkyl having 1-6 carbon atoms (Reference R43, where R41-42 are H)
Claimed Aa50 is a single bond
Reference subscript a is 1, and a single hydroxy group is present
Subscript mb is 0-2
Takahashi ascribes excellent sensitivity and resolution, as well as improved line edge roughness in patterned resist films made, to the composition comprising the resin (P) and other components ([0031])
A person having ordinary skill in the art would have found it obvious to arrive at the claimed invention prior to the filing date in view of the disclosure of Takahashi using the known materials to arrive at a composition having improved sensitivity for use in forming patterned resist films exhibiting improved resolution and line edge roughness.
Regarding Claim 18, Takahashi teaches an actinic-ray sensitive composition comprising a resin P, containing a repeating unit A, that when exposed to radiation decomposes to generate an acid and at least two repeating units B1 and B2 are decomposed by acid so as to generate alkali-soluble functionalities – and where B1 and B2 are different subunits, as discussed above regarding claims 1 and 11.
Takahashi does not specifically disclose an experimental embodiment meeting the limitations of the claim and therefore does not teach an experimental embodiment that is processed in a photolithographic method.
These limitations are met by the general disclosure of the reference.
The composition(s) of Takahashi is processed as per [00578]-[0592], wherein the composition is dissolved in solvent, filtered, and then applied onto a substrate, then dried to form a composition layer. The resultant layer is exposed to radiation, then post-exposure baked (heated). After post-exposure baking, the layer is developed using a developer composition such as an ammonium or alkali metal hydroxide solution.
A person having ordinary skill in the art would have found it obvious to arrive at the claimed invention prior to the filing date from the taught composition of Takahashi and the processing method described – such teachings amount to the use of a known composition/component to be processed in a known method of lithographic exposure, which an ordinarily skilled artisan would expect to result in a patterned resist layer.
Claim(s) 17 is rejected under 35 U.S.C. 103 as being unpatentable over Takahashi et al (US 20110183263 A1) as applied to claims 1 and 11 above, and further in view of Fukushima et al (US 20190079399 A1).
Regarding Claim 17, Takahashi teaches the limitations of the claims as discussed above regarding claims 1 and 11.
Takahashi however does not teach a salt generating an acid having an acidity lower than that of an acid generated from the primary acid generator.
This limitation is met by Fukushima.
Fukushima teaches a monomer, resin comprising the monomer, and photoresist composition comprising the resin, acid generators, and additives such as quenchers.
The base resin and monomer comprised therein are described from [0044 to [0109], wherein the base resin comprises monomer subunits that decompose upon action of an acid to form alkali-soluble functionalities ([0049], [0053], [0070]), as well as subunits that function as acid generating species ([0082]-[0102].
An additional acid generator that comprises a sulfonium or iodonium cation and fluorinated sulfonate/imidate/methide anion is also included in the composition, along with an organic solvent ([0111]-[0153].
Additional components included may be quenchers, where specific quenchers contemplated by the art include onium salts of non-fluorinated sulfonic acids or onium salts of carboxylic acids, where the onium cations may be sulfonium. The sulfonium carboxylate salts will generate carboxylic acids upon irradiation. In a system using a strong acid generating salt and a weak acid generating salt, the weak acid salt results in a diffusion modulation effect to control the diffusion of strong acid from reaching unwanted areas in the patterned resist and improving the contrast in an exposed area and improving depth of focus (DOF) ([0155]-[0168].
A person having ordinary skill in the art would have found it obvious to arrive at the claimed invention prior to he filing date by including the sulfonium carboxylate salt quencher of Fukushima into the composition of Takahashi in order to facilitate acid diffusion control during process and result in a patterned resist having improved contrast and depth of focus.
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to ANDREW PRESTON TRAYWICK whose telephone number is (571)272-2982. The examiner can normally be reached Monday - Friday 8-5.
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If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Sally Merkling can be reached at 571-272-6297. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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/A.P.T./Examiner, Art Unit 1737
/SALLY A MERKLING/SPE, Art Unit 1738
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