Detailed Action
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 .
Response to Arguments
Applicant’s Arguments regarding the rejection of Claim(s) 2, 5-6, 8, 11, 14-15, and 17 under 35 U.S.C. 103 as being unpatentable over Cardolaccia et al (US 20220043342 A1) as applied to claims 1, 9, and 10 , and further in view of Goetz et al (US 2003/0100675 A1) and Luo et al (Polym. Chem, Tailor-made compositional gradient copolymer by a many-shot RAFT emulsion polymerization method, 2014, 5, 3363), and the rejections of Claims 7, 16, and 20 as rejected under 35 U.S.C. 103 as being unpatentable over Cardolaccia et al (US 20220043342 A1) as applied to claims 1, 9, and 10 , and further in view of Goetz et al (US 2003/0100675 A1) are considered persuasive and these rejections are withdrawn.
However – Applicant’s arguments over the rejection of claims 1, 3, 4, 9, 10, 12, 13, 18, and 19 as rejected under 35 U.S.C. 103 as being unpatentable over Cardolaccia et al (US 20220043342 A1) are not persuasive. These rejections are maintained.
The examiner is aware of the dictionary definition of a block copolymer. However, the Examiner, when considering the instant claim language of claim 1, considered the following factors:
What defines the block(s) in the claim?
The structural units define the blocks in the claim (at least two structurally different repeating units, wherein the units comprise those having an acid-labile group, a lactone group, a salt group, or a hydroxyaryl group)
Are there differences in the structural units present in each block?
The claim language explicitly states the same type of monomers are present in each block. There is no difference in the type of structural units in the claimed blocks (wherein the two or more structurally different repeating units of the first block are the same as the two or more structurally different repeating units of the second block).
Is the morphology (ordering of present structural units and/or relative abundance of each of the present structural units) of each block known and stated in claim 1?
The morphology of the claimed blocks is not stated until claim 2
What claimed boundary between blocks or other distinguishing structural feature allows the differentiation of one block from the other block, when both blocks have the same units present?
There is no differentiable feature between the blocks, as both blocks contain the same sets of units in unclaimed amounts/abundances and unclaimed morphologies
Claim 2 recites that the gradient direction of structural units from a first end to a second end is the same between each block and that the ratio of units to one another is substantially the same
As currently written, it appears that there is no significant morphological distinction between the first block and the second block of the independent claim, wherein both “blocks” comprise the same units in any order or arrangement and in any set of abundances. When the arrangement of subunits in a copolymer may be in any order, this may be a random copolymer. If there are two sections in a copolymer with an undefined set of morphologies comprising the same subunits, this copolymer may be a random copolymer. Applicant has not defined in claim 1 what makes one block different from another when both “blocks” comprise the same units in any undetermined order or abundance.
In the interest of compact and productive prosecution, the examiner suggests moving the subject matter of claim 2, which defines the relative abundances of subunits and the morphologies of each block so as to distinguish one from the other, into claim 1.
In the provided Arguments, Applicant points to a specific structural embodiment of the exemplary block copolymer alleged to refer to claim 1 and seemingly envisioned by applicant to be indicative of the claimed scope of claim 1. The examiner respectfully disagrees and considers that this structural embodiment does not correspond to the full scope of claim 1. Claim 1’s scope is broader than that of the example provided.
Further, the Examiner submits that it is improper to import limitations from the Specification into the claims when the claims are broader in scope, and that the plain meaning of a “block copolymer” would inherently lend to a differentiable structural distinction between the supposed blocks of the polymer. As claim 1’s copolymer does not make these structural distinctions apparent, the examiner considers that claim 1’s required structural features may be met by a random copolymer.
Applicant’s arguments that Cardolaccia does not cover polymerization methods for using monomers to arrive at the morphology required by the block copolymers of claim 1 are not persuasive as claim 1 as written does not cover polymerization methods.
After further consideration, the Examiner makes a new grounds of rejection as set forth in the body of the office action below. As such, this action is Non-final.
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.
Regarding Claim Interpretation - claim 1 presents a block copolymer comprising two blocks each having two or more structurally different units (e.g. a lactone-bearing unit and hydroxystyrene unit), wherein the two blocks have the same structurally different units. Classically, a block copolymer is interpreted to have a definable boundary from one block to the next, such as in an SBS copolymer, or a gradient copolymer such as in Frey et al (Macromolecules, 2018, 51, 10246-10258, provided by Applicant in IDS ) where the blocks comprise regions of (AB)n monomers in a defined volume fraction relative to each other and wherein the gradient of volume fraction defines the blocks.
As claim 1 does not delimit what renders block 1 distinct from block 2 or vice-versa so as to call block 1 or 2 “a block” (be it the % abundance of monomers, sequence of monomers, or a gradient block morphology of monomers), the embodiments encompassed by a broadest reasonable interpretation of claim 1’s polymer may be, for instance, a random copolymer having two arbitrarily defined sections called blocks.
Claim 2 delimits a gradient direction from a first end to a second end of each block – thus defining the blocks in a manner more definite than by the presence of the same monomers in each block. Claim 2 is dependent from claim 1 and as such these limitations cannot be considered a part of claim 1 by nature of dependency. This analysis also extends to claims 11 and 17, which recite substantially the same limitations as claim 2 but are dependent from claims 9 and 10 respectively.
Claims 1, 3, 4, 9, 10, 12, 13, 18, and 19 is/are rejected under 35 U.S.C. 103 as being unpatentable over Cardolaccia et al (US 20220043342 A1)
Regarding Claims 1, 3, 4, 9, 10, 12, 13, 18, and 19, Cardolaccia discloses a photoresist composition comprising a first polymer generated from free radical polymerization using polymerized units formed form a monomer comprising an ethylenically unsaturated bond and an acid labile group, a photoacid generator, and a quencher (Abstract).
However, Cardolaccia does not explicitly disclose an experimental embodiment meeting the limitations of the claims.
These limitations are met by the general disclosure of the reference.
The composition of Cardolaccia also comprises solvent, described at [0065], such as isopropanol, acetonitrile, ethyl lactate, or PGMEA (claim 9)
Patterning methods using the composition of Cardolaccia are described from [0071]-[0082], wherein the composition is disposed onto a substrate, patternwise exposed to radiation, and developing the exposed photoresist composition layer to provide a relief image (claim 10).
The first polymer is described from [0011]]-[0044], wherein the polymer is “prepared by free radical polymerization using techniques well known to those skilled in the art” and may comprise monomers in production that are mixed or added separately into a reactor. The polymer may be a random copolymer, a star block copolymer, a gradient copolymer, or a block copolymer, or the like, as described at [0015]. The monomers of the polymer include those having acid-labile groups (1a-1d) as described from [0116]-[0032] such as but not limited to acrylic acid esters (or methacrylic acid esters, or other units having substitutions on the acrylate backbone) whose side groups are acid-labile (claim 3, 12, and 18), lactones (2) as described from [0032]-[0035] (claim 4, 13, and 19), units having a base-soluble group (3) described from [0036]-[0037], and/or polar group-bearing monomers (4) described at [0038]-[0040] such as hydroxystyrene or vinyl hydroxynaphthalene. Various exemplary copolymers are presented at [0041]. The molecular weight of the polymer may be between 1000 and 50,000 Da.
Regarding block copolymer morphologies - claim 1 presents a block copolymer comprising two blocks each having two or more structurally different units (e.g. a lactone-bearing unit and hydroxystyrene unit), wherein the two blocks have the same structurally different units. Classically, a block copolymer is interpreted to have a definable boundary from one block to the next, such as in an SBS copolymer or a gradient block copolymer. As the claim recites that the two blocks are of substantially the same composition but does not distinguish their morphology beyond such as to delimit the boundaries of one block from another, a random copolymer comprising the required subunits appears to meet the limitations of the claims. Additionally and/or alternatively, as the only distinguishing features of the blocks is the subunit, the claim reads as if the presence of the requisite monomers would naturally arrive at the blocks during polymerization. The disclosure of Cardolaccia covers polymer morphologies including random and block copolymers and describes a selection of monomers that meet the limitations of the claims as well as polymerization methods for using these monomers.
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 general disclosure of the reference using the teachings thereof – using known monomers in a conventional radical polymerization process to arrive at a polymer composition for use in a photolithographic composition to be patterned.
Claim(s) 1, 3-10, 12-16, and 18-20 are is/are rejected under 35 U.S.C. 103 as being unpatentable over Cho et al (US 2015007291 A1)
Regarding Claim 1, Cho disclsoses a graft block copolymer comprising a first block polymer comprising a backbone polymer and a first graft polymer wherein the first graft polymer comprises a surface energy reducing moeity such as a halocarbon or silicon-containing moiety or a combination of the two, and a second block polymer that is attached to the first block, where the second block comprises the backbone polymer and a graft polymer where the second graft polymer comprises a functional group that is operative to undergo acid-catalyzed deprotection and causes a change of solubility in the graft block copolymer in a developer solvent (Abstract).
The backbone polymer used to form the polymer backbone of the graft copolymer is described at [0027] and may be one of a polyacrylic, a polycarbonate, a polyphenylene sulfide, a polyvinyl chloride, a polyquinoxaline, or another embodiment described in the cited section.
The first graft polymer block is grafted through the backbone, and may be a homopolymer such as one generated from the fluorinated monomers discussed at [0032].
In an exemplary example, the backbone is polynorbornene and the first grafted polymer block is a polymer derived from 5,5,5-trifluoro-4-hydroxy-2-methy 1-4-(trifluoromethyI)pentyI methacrylate (See [0035]).
In one embodiment, the second block copolymer is a graft comprising a polynorbornene backbone to which a copolymer block of 1-ethylcyclopentyl methacrylate and gamma-butryolactone-2-yl methacrylate has been polymerized (formula (3), [0040].
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In a further embodiment, at [0042], a grafted copolymer comprising a polynorbornene backbone to which a polymer comprising subunits of 1-ethylcyclopentyl methacrylate and triphenylsulfonium 1,1-difluoro2(methacryloxy)ethanesulfonate has been grafted (formula (4).
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In a further embodiment, the reference’s second polymer is a block comprising N-phenyl maleimide units and Boc-protected hydroxystyrene units (formula (5)):
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Where for the subscripts above: m is 10-40, x is 0.25 to 1, y is 0.25 to 1, and p is 3-75.
In yet further embodiments, the second polymer can comprise two diblock copolymers, wherein the first diblock copolymer comprises two blocks that are derived from the polymerization of any two of 1-ethylcyclopentyl methacrylate, y-butyrolactone-2-yl methacrylate, BOC-protected hydroxystyrene, N-phenyl maleimide and triphenylsulfonium 1,1-difluoro-2-(methacryloxy )ethanesulfonate and where the second diblock copolymer is different from the first diblock copolymer and is derived from the copolymerization of any two of 1-ethylcyclopentyl methacrylate, y-butyrolactone- 2-yl methacrylate, BOC-protected hydroxystyrene, N-phenyl maleimide and triphenylsulfonium 1,1-difluoro-2-(methacryloxy)ethanesulfonate. In one such further embodiment, the second block graft comprising the polynorbomene backbone to which is grafted the second polymer that comprises the first diblock derived from the copolymerization of triphenylsulfonium 1,l-difluoro-2-(methacryloxy)ethanesulfonate and 1-ethylcyclopentyl methacrylate and the second diblock derived from the copolymerization of 1-ethylcyclopentyl methacrylate and y-butyrolactone-2-yl methacrylate as shown below in the formula (7):
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Wherein q is 10-40, n7 is 2-10, n8 is 10-30, n9 is 5-20, and n10 is 5-20.
Further embodiments include the copolymer of formula (10):
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where p is 10 to 30, q is 2 to 8, n7 is 2 to 6, n8 is 10 to 20, n9 is 10 to 20, n10 is 7 to 15 and o is 12 to 25.
The copolymer of (10) can be made in a batch process or continuous process involving single or multiple of each of reactors, solvents, and catalysts/initiators ([0051]. This process, in one embodiment, is described from [0052] to [0070], wherein the norbornene monomers are used as a scaffold on which to graft one set of desired polymer embodiments and a separate set of other desired polymer embodiments, and all norbornene scaffolds are then polymerized with a modified Grubbs catalyst to form the graft block copolymer. The polymerization of the materials on the norbornene monomer scaffolds is performed using a dithioester chain transfer agent.
The graft block copolymer after purification may be used to manufacture a photoresist composition comprising the copolymer, a solvent, a quencher, and a photoacid generator ([0074]) (claim 9), wherein the polymer and other components are cast onto a substrate to form a film, then the film is dried to remove solvents ([0081]. After drying, the film is exposed to electron beam radiation through a mask to form a photoacid in exposed regions, and then optionally baked, to deprotected the functional moeities on the polymers. The deprotected portions of the film may then be removed using an aqueous alkaline developer to leave behind a patterned film with a positive tone (a relief image) (claim 10).
The examples of (7) and (10) comprise block copolymer arm having two blocks thereon, and are bonded to another part of the polymer (the norbornene backbone). Neither particular reference figure discloses that the second block (or, a second block) is the same as the first block, nor discloses a second/additional embodiment of one of the first two blocks connected thereto.
This limitation is met by the general disclosure of the reference.
At [0013]-[0014], the reference asserts that the blocks of the same monomer(s) aggregate to form periodic domains and the spacing and morphology of domains is dependent upon the interaction, size, and volume fraction among different blocks.
At [0020] the reference disclsoses that the graft block copolymer, when disposed onto a substrate, forms a film that comprises bottle-brush polymers that are deprotected by reacting the functional groups to alter their solubility.
At [0085], the reference asserts: “The structural and morphological features of the graft block copolymers can be tuned in the lateral and longitudinal directions thus enabling the preparation of high-sensitivity photoresists. Furthermore, the structural and morphological features of the graft block copolymers can be tuned in the lateral and longitudinal directions to
facilitate an enhanced anisotropic vertical diffusion of photoacid catalyst”
A person having ordinary skill in the art wishing to tune the structural and morphological features of the graft block copolymers - such as size of the domains - and thus influence the aggregation of the polymers would consider the size and distribution of polymerized embodiments present thereon. One such manner of doing this would be to duplicate blocks on an arm, such as in the modified examples produced by the examiner for illustrative purposes:
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The above embodiments meet the limitations of the claim 1 for where:
The block copolymer comprises two blocks – the instant claim makes no exclusion as to the presence of additional unrecited blocks and is not specific on their arrangement relative to other blocks.
An additional block(s) is present (claims 7, 16, and 20)
The block comprising 1-ethylcyclopentyl methacrylate and y-butyrolactone-2-yl methacrylate in A is additional to the other two blocks
The block comprising triphenylsulfonium 1,1-difluoro-2-(methacryloxy)ethanesulfonate and 1-ethylcyclopentyl methacrylate in B is additional to the other two blocks
The additional block makes the number of blocks in the grafted block copolymer 3 (claims 6 and 15)
The first block and second block each comprises two structurally different repeating units
In A, each block comprises triphenylsulfonium 1,1-difluoro-2-(methacryloxy)ethanesulfonate and 1-ethylcyclopentyl methacrylate (claims 3, 12, 18, where 1-ethylcyclopentyl methacrylate is a monomer with an acid-labile group) (claims 4, 13, and 19, where triphenylsulfonium 1,1-difluoro-2-(methacryloxy)ethanesulfonate is a salt group unit)
In B, each block comprises 1-ethylcyclopentyl methacrylate and y-butyrolactone-2-yl methacrylate (claims 4, 13, and 19, where y-butyrolactone-2-yl methacrylate is a lactone group unit)
As for the number of subunits in each block, the
reference provides ranges of monomers in blocks ranging from 2 to 20 (see above in reference to figures (7) and (10)), overlapping the claimed range of claims 5 and 14 at “greater than 5”)
The first and second block each comprise the same structurally different repeating units
The embodiment(s) above also comprise a polymer, comprising one of more polymers as per claim 1 bonded to another part of the polymer (the norbornene skeleton/backbone) (claim 8)
Modifying the arms of the polymer as above extends the arm outward and changes the domain size, which as guided by the reference, would result in the tuning of the morphological configurations of the resultant polymers when disposed on a substrate so as to attenuate the performance of the photoresist composition. These modifications use the taught monomers of the reference and would/could be performed with the methods taught by and materials taught by the reference - a person having ordinary skill in the art would be able to make use of the materials and methods provided to arrive at the modified embodiment(s). Such a person having ordinary skill in the art would likely consider the modifications still suitable for arriving at a polymer to be used in a photoresist because of the resultant polymer’s present acid-generating moeities - the modifications amount to the combination of prior art elements (monomers and polymers) according to known methods (the polymerizations taught by the reference) to arrive at a predictable result (an acid-generating polymeric embodiment).
Claim(s) 2, 11, and 17 are rejected under 35 U.S.C. 103 as being unpatentable over Cho et al (US 2015007291 A1) as applied to claims 1, 9, and 10 above, and further in view of Thackeray et al (US 20170031244 A1)
Regarding Claims 2, 11, and 17 , Cho teaches the limitations of the claims as discussed above regarding claims 1, 9, and 10.
Cho however does not make explicit that the polymer blocks discussed are/may be gradient blocks comprising similar ratios of repeating units and an identical structural unit gradient from one end to a second end of the block. Cho does disclose that RAFT agents may be used in the synthetic procedures ([0054]).
This limitation is met by Thackeray
Thackeray discloses a composite comprising a blend of nanoparticles functionalized with a ligand, and a polymer, wherein the polymer is the polymerization of a photoacid generator comprising a polymerizable group and at least one unsaturated monomer, as well as a thioester chain transfer agent (Abstract).
The polymers of Thackeray include polymer-bound photoacid generators, such as sulfonium or iodonium salts as described at [0106]- [0114] and [0154]-[0157]. The other monomers of Thackray include unsaturated monomers such as lactone-containing monomers as discussed at [0125]-[0133], acid-deprotectable monomers as discussed at [0115]-[0119], and base-soluble monomers such as hydroxyaryl-containing units as discussed at [0123].
The copolymer of Thackeray may be prepared by radically-initiated polymerization of the monomers in the presence of a RAFT chain transfer agent. Polymerization may be carried out by a batch addition of monomers and/or initiator into a solution containing the chain transfer agent, by metered addition of separate feeds of one or more monomers/initiator(s)/chain transfer agent, and/or other suitable methods for combining the reactants. Block copolymers may be produced by sequential addition of monomers and gradient polymer compositions may be formed by gradually changing the monomer proportions/composition in the feed over time ([0150]-[0152]).
Thackeray discloses a polymeric embodiment having substantially similar subunits as those of Cho (photoacid-generating monomers, acid-labile subunits, and lactone-bearing subunits) and uses a RAFT chain transfer agent in the synthetic procedure. Further, Thackeray disclsoses that gradient copolymer synthesis is performed by varying the component monomer feed compositions. Referring back to Cho, the sequential or stepwise formation of blocks by gradient monomer feeds of the same set of monomers in each block results in two blocks having substantially the same monomer ratios and gradient compositions across the morphology of the block.
Modifying the arms of the polymer of Cho as extends the arm outward and changes the domain size, which as guided by Cho, would result in the tuning of the morphological configurations of the resultant polymers when disposed on a substrate so as to attenuate the performance of the photoresist composition. These modifications use the taught monomers of the reference and would/could be performed with the methods taught by and materials taught by the reference - a person having ordinary skill in the art would be able to make use of the materials and methods provided to arrive at the modified embodiment(s). Such a person having ordinary skill in the art would likely consider the modifications still suitable for arriving at a polymer to be used in a photoresist because of the resultant polymer’s present acid-generating moeities - the modifications amount to the combination of prior art elements (monomers and polymers as per Cho and Thackeray) according to known methods (the gradient block polymerizations taught by Thackeray) to arrive at a predictable result (an acid-generating polymeric embodiment).
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
