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 .
Information Disclosure Statement
The information disclosure statement (IDS) submitted on 02/05/2024 is being considered by the examiner.
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claim 12 is rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
The claim language of claim 12 reads “the method of claim 1 wherein the additive comprises a composition represented by the formula:”, but does not present a formula or any further limitations. As such, the limitations of the claim cannot be determined beyond those carried down from claim 1 by nature of dependency. The Examiner has checked to see if the formula was missing/hidden by way of improper image formatting/technical issues, but it appears to not be present in the claims. Looking at the Instant Specification, under “Further Inventive Concepts” there is also a blank space at “concept A30” which appears to be formatted, relative to A31, similarly to claim 12.
For the purposes of examination over prior art, as there are no identifiable limitations beyond those present from claim 1 by nature of dependency, claim 12 will be considered to comprise the limitations of claim 1 as there are no further examinable limitations. Appropriate correction is required for this claim to be further examined under prior art.
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 1-6, 8-9, 11, and 16-34 is/are rejected under 35 U.S.C. 103 as being unpatentable over Zi et al (US 20190384173 A1) and Meyers et al (US 20170102612 A1).
Regarding Claim 1-6, 8-9, 11, 16-22, 24, and 26-34, Zi teaches an EUV metallic resist composition and additives to be added thereto (abstract), wherein the composition’s additives may comprise a solvent having a boiling point greater than 150 degrees Celsius, a photobase generator, a photoacid generator, a quencher, a photo decomposed base, a thermal acid generator, or a photosensitive crosslinker.
Zi discloses an assembly/apparatus for processing the composition from [0016]-[0037], including such components as masks and radiation sources.
The assembly of Zi comprises a substrate 140, a material layer 150 disposed thereatop which may also be a patternable layer, and a photoresist layer 160 which has a structure 200. The structure 200 may be a particle cluster including a core group 204 surrounded by ligands 212, wherein the core group includes at least one metallic atom in the form of an ion, compound, alloy, or combination thereof – metals suggested for use include tin, titanium, hafnium, or another metal as discussed at [0045] and [0046]. Ligands associated with the metal(s) include straight or cyclic alkyl, carboxylic acid, alkoxyl, alkene, or other functional groups having 1-12 carbon atoms therein. Multiple ligands may be present.
Additives may be added to the photoresist composition so as to improve aging and/or critical dimensional control problems, as discussed from [0047]-[0062]. One or multiple additives may be added.
A high-boiling point solvent such as cyclohexyl acetate or PGMEA may be added, or other solvents discussed from [0050]-[0051].
A photoacid generator may be added, where the amount of photoacid generator may be present in an amount ranging from 0.01-10% of the photoresist layer composition. Exemplary acid generators include those depicted at [0052]-[0054 and at Fig 6A and 6B, such as the salts of an aromatic sulfonium cation triphenylsulfonium (claims 2, 3, 5, 6, 8, 11, 32 ) and corresponding counterions such as nonafluorobutane sulfonate (claim 4).
A photobase generator may be used, wherein exemplary photobase generators include those in [0055].
A quencher may be used, wherein the quencher is present in an amount ranging from 0.01 to 10% of the photoresist composition. Embodiments of the quenchers include ammonium or amine compounds such as those in Fig 8 and at [0056] and [0062] (claim 33 and 34). Additives may be used singly or in admixture.
The resist material as described by the reference is substantially the metallic component mentioned above, wherein the metallic component may be, for instance, a tin compound having a number of organic ligands such as alkyl, alkoxy, among others. The amount of additives may individually vary from 0.01 to 10% of the photoresist composition – meaning, the amount of metallic component may vary from 99.99 to 90% of the composition.
The photoresist layer 160 is exposed to radiation as in [0044] and [0063]. After exposure, a developing process is used to remove exposed/irradiated regions.
Zi does not explicitly disclose a composition comprising an organotin oxide hydroxide composition as set forth in the claim. Zi does disclose organometallic compositions that may include tin and tin oxides functionalized with organic ligands such as alkyl.
This limitation is met by Meyers.
Meyers discloses organometallic precursors for forming high resolution patterning coatings based around metal oxide hydroxide chemistry (abstract).
The compositions of Meyers are alkyltin oxide hydroxides, bounded by the formula RzSnO(2-(z/2)-(x/2))(OH)x where Z is between 0 and 2, including 2, and (z+x) is between 0 and 4, including 4, overlapping with the claimed formula for where z is 0.5 to 2 and x is between 0 and 1.5 (relative to claimed variables n and x, respectively). The R group(s) of Meyers may be hydrocarbyl groups such as straight, branched (claim 21), or cyclic hydrocarbyl groups with 1-31 carbon atoms ([0051]), such as methyl, t-butyl, i-propyl, and/or tert-amyl (claim 20). The R group(s) may be substituted, such as with cyano, thiol, ether, silyl, ester, or halogenated groups thereof (claim 22 – “halogen” as a genus has only 4 members for practicable chemistry – a person having ordinary skill in the art immediately envisions all 4 possible members of the genus).
Upon deposition of the composition precursors, ligands having acids and water react to create oxide-hydroxide networks ([0055], [0059]-[0068]), wherein the precursor material is coated onto a substrate such as a wafer through a method such as vapor deposition or spin coating, after which the composition is heated to drive off solvent and promote densification of the material by forming a metal oxo-hydroxo network ([0074]) (claim 24 – the unexposed material comprises a metal oxo-hydroxo material, as such non-irradiated material comprises the metal oxo-hydroxo network).
The compositions of Meyers are used in photoresists for EUV patterning ([0085])(claim 29), at a dose of between 1mJ/sqcm to 150 mJ/sqcm (claim 30), after which the exposed resist is post-exposure baked at a temperature from 45 to 250 degrees Celsius (claim 27 and 28, wherein the exposed material defines a latent image by nature of patternwise exposure).
A developer composition is used to remove the irradiated (or unirradiated, for negative development) material as described from [0090]-[0103], wherein positive development is performed using a tetramethylammonium hydroxide developer comprising 0.5 to 30 wt% TMAH (claims 16-18). Similar quaternary ammonium hydroxide compositions may be used. Contact times for positive development are not explicitly recited, but negative development times are recited as being between 5 seconds and 15 minutes – a person having ordinary skill in the art would naturally look to the disclosure for development times in general, and as there is no admonition or teaching away of these times by the references in the context of positive development, such a person having ordinary skill would consider them likely options capable of successfully developing the resist (claim 19).
After development, a rinse and a post-development bake may be performed as discussed at [0097]-[0098]. The resultant structures from patterning can have low line-width roughness, and very well resolved two-dimensional patterns – the reference ascribes adjacent linear segments (line/space pattern) having an average pitch of no more than 60nm, or a half-pitch of no more than 30 nm – this is interpreted as “a half-pitch of 30nm or less”, overlapping the claimed limitation of “less than about 25nm” which is interpreted as “about 25nm or less” (see [0100]). The substrate of the assembly is discussed at [0069] where silicon wafers are substrates of particular interest – the experimental examples also use silicon wafers as discussed at [0115] (claim 31).
Regarding the inclusion of additives relative to the amount of metal component, Zi is silent on the overall amount of photoresist composition included as there are no experimental examples – however, additives are present in 0.01-10% by weight of the photoresist composition (or 1 to 20% when the additive(s) is/includes a high boiling point solvent) and it can be inferred that the metallic component comprises the remaining weight of the composition as at [0043]-[0045] does not recite a binder material or other non-metallic structure components. Zi also provides structural examples of additives such as PAGs, such as triphenylsulfonium nonafluorobutylsulfonate [0053]-[0054]. Meyer presents an experimental example at [0118]-[0121] wherein 6.5g or 24 mmol of tin material precursor is used in the preparation of a film for coating and exposure, and is converted into the tin oxide-hydroxide material. A person having ordinary skill in the art would naturally look to experimental examples from disclosures to direct their own experimentation. A combined composition of Zi and Meyers would, as directed by the experimental examples of Meyers and the disclosure of Zi, comprise 90-99.99% of Tin material and 0.01-10% PAG additive by weight, . A composition comprising 10% by weight PAG (triphenylsulfonium nonafluorosulfonate) and 90% tin material based on this example would weigh 7.22 grams – 0.72 grams or 1.28 mmols of which is the PAG – giving a molar ratio of additive to tin A:Sn of 0.053. In the instance where 99.99% of the composition is tin by weight, 0.00065gs or 0.00116mmols of PAG is present, giving a molar ratio of 4.82x10^-5 A:Sn. This range is calculated for one example for the purpose of brevity – examples of tin components and additives are present in both disclosures - however it is clear that the range molar ratio of additives to tin overlaps with the claimed range of 0.002 to “about” 2 for at least 0.002 to 0.053 (and also claim 26 for 0.005 to 0.053)
Meyers ascribes improved patterning capabilities and high resolution as well as improved line-width roughness to the compositions and patterned products therefrom described therein at [0099]-[0100]. Zi asserts improved aging stability is imparted by the additives disclosed therein as discussed at [0047]-[0062]. A person having ordinary skill in the art would have found it obvious to arrive at the claimed invention prior to the filing date by adding the tin composition(s) of Meyers to the composition of Zi to arrive at a composition having high patterning capability and stability that can be used in a method to arrive at high resolution, low line-width patterned resist.
Regarding Claim 9, neither Zi nor Meyers mention the decrease in absorption of EUV radiation by their respective compositions when additives are present. As such, it is assumed that the additives of Zi would not have a deleterious effect on EUV absorption.
A person having ordinary skill in the art would have found it obvious to arrive at the claimed invention prior to the filing date by adding the tin composition(s) of Meyers to the composition of Zi to arrive at a composition having high patterning capability and stability that can be used in a method to arrive at high resolution, low line-width patterned resist.
Regarding Claims 23 and 25, Zi and Meyers meet the limitations of the claim as discussed above regarding claim 1.
However, neither reference provides explicit experimental examples provided by Zi or Meyers that meet the limitations of the claims.
These limitations are met by the general disclosures of the references.
The compositions of Meyers are alkyltin oxide hydroxides, bounded by the formula RzSnO(2-(z/2)-(x/2))(OH)x where Z is between 0 and 2, including 2, and (z+x) is between 0 and 4, including 4, overlapping with the claimed formula for where z is 0.75 to 2 and x is between 0 and 1.5 (relative to claimed variables n and x, respectively). The R group(s) of Meyers may be hydrocarbyl groups such as straight, branched, or cyclic hydrocarbyl groups with 1-31 carbon atoms ([0050-[0051]]), such as methyl, t-butyl, i-propyl, and/or tert-amyl . The R group(s) may be substituted, such as with cyano, thiol, ether, silyl, ester, or halogenated groups thereof. As per [0050], multiple instances of R-Sn moieties may be present, each independently having a hydrocarbyl ligand that has 1-31 carbon atoms therein.
Meyers ascribes improved patterning capabilities and high resolution as well as improved line-width roughness to the compositions and patterned products therefrom described therein at [0099]-[0100]. Zi asserts improved aging stability is imparted by the additives disclosed therein as discussed at [0047]-[0062]. A person having ordinary skill in the art would have found it obvious to arrive at the claimed invention prior to the filing date by adding the tin composition(s) of Meyers to the composition of Zi to arrive at a composition having high patterning capability and stability that can be used in a method to arrive at high resolution, low line-width patterned resist.
Claim(s) 7 is rejected under 35 U.S.C. 103 as being unpatentable over Zi et al (US 20190384173 A1) and Meyers et al (US 20170102612 A1). as applied to claim 1 above, and further in view of Ogawa et al (US 20200183280 A1)
Regarding Claim 7, Zi and Meyers meet the limitations of the claim as discussed above regarding claim 1.
However, neither reference teaches or suggests a sulfonium or iodonium hydroxide compound as an additive. Zi does disclose PAGs, bases, and quenchers, of which some are onium salts.
This limitation is met by Ogawa.
Ogawa discloses a radiation-sensitive resin composition comprising a photoacid generator and a resin capable of increasing polarity by the action of an acid (abstract).
At [0261]-[0290], a basic compound is presented as part of the composition, where onium hydroxides, pyrazoles, piperidines, and onium carboxylates are discussed. Exemplary basic onium salts having hydroxides include those at [0267], such as triphenylsulfonium hydroxide and bis(t-butylphenyl) iodonium hydroxide. The resin and acid generator are generally disclosed from [0044]-[0255].
Ogawa discloses these basic compounds as acid control agents acting as quenchers that can suppress unwanted reactions in unexposed areas from acids generated during exposure.
A person having ordinary skill in the art would have found it obvious to arrive at the claimed invention prior to the filing date by adding the triphenylsulfonium hydroxide and/or bis(t-butylphenyl) iodonium hydroxide salts of Ogawa to the composition of Zi and Meyers to suppress unwanted reactions in unexposed areas from acids generated during exposure.
Claim(s) 10 is rejected under 35 U.S.C. 103 as being unpatentable over Zi et al (US 20190384173 A1) and Meyers et al (US 20170102612 A1) as applied to claim 1 above, and as evidenced by a technical disclosure from HeyNova Chemicals.
Regarding Claim 10, Zi and Meyers meet the limitations of the claim as discussed above regarding claim 1.
However, the hydrophobicity of the triphenylsulfonium nonaflate is not mentioned by Zi or Meyers.
This limitation is met inherently by the compound, and to avoid taking official notice, a Certificate of Analysis from HeyNova Chemicals is provided (see attachment to Office Action), which asserts that triphenylsulfonium is insoluble in water and soluble in organic solvents.
Claim(s) 13 is rejected under 35 U.S.C. 103 as being unpatentable over Zi et al (US 20190384173 A1) and Meyers et al (US 20170102612 A1). as applied to claim 1 above, and further in view of Robinson et al (US 20200272050 A1).
Regarding Claim 13, Zi and Meyers meet the limitations of the claim as discussed above regarding claim 1.
However, neither Meyers nor Zi disclose a triphenylsulfonium triflate (also known as trifluorosulfonate) salt as part of their compositions. Meyers discloses structurally similar acids salts such as triphenylsulfonium nonaflate, however, in Fig 6A and 6B.
This limitation is met by Robinson.
Robinson discloses a photoresist composition comprising a polymer and an acid-activated crosslinker, as well as photoacid generators such as triphenylsulfonium trifluorosulfonate and triphenyl sulfonium nonafluorobutanesulfonate ([0054], among other acid generators. Metal components such as tin and/or tin complexes may also be present as discussed in [0072].
Robinson, Zi, and Meyers are each directed to photoresist compositions comprising metal (tin) compounds and Robinson and Zi each teach sulfonium nonafluorobutane sulfonate salts – Robinson presents the nonafluorobutanesulfonate salt in tandem with the trifluorosulfonate salt and as such considers these two salts to be alternatives to one another.
A person having ordinary skill in the art would have found it obvious to arrive at the claimed invention prior to the filing date by adding and/or substituting the triphenylsulfonium trifluorosulfonate salt of Robinson into the composition of Zi and Meyers with recognition that it would behave similarly to the PAG additive triphenylsulfonium nonafluorobutane sulfonate.
Claim(s) 14 is rejected under 35 U.S.C. 103 as being unpatentable over Zi et al (US 20190384173 A1) and Meyers et al (US 20170102612 A1). as applied to claim 1 above, and further in view of Yamaguchi et al (JP2022032981A, published 02/25/2022).
Regarding Claim 14, Zi and Meyers meet the limitations of the claim as discussed above regarding claim 1.
However, neither Meyers nor Zi disclose the claimed as part of their compositions. Meyers discloses structurally similar acids salts such as triphenylsulfonium nonaflate, however, in Fig 6A and 6B.
This limitation is met by Yamaguchi.
Yamaguchi discloses a photoresist composition comprising a photoacid generating acid salt that is weaker than a main acid-generating salt, a resin having an acid labile group, and a metal carboxylate salt as described from [0005]-[0212], wherein quenchers (D) are presented at [0212]:
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While there is no associated water with the salt herein, the compositions of Meyers as described above regarding claim 1 may comprise additional water as described at [0075]. Such water would likely associate to a charged carboxylic acid functionality, thus arriving at the claimed structure.
The iodonium carboxylate salt of Yamaguchi functions by generating a weak acid – this functionality is a quenching functionality. The composition of Zi already establishes that quenchers have utility as additives in metal-containing resist compositions and help improve pattern parameters and composition aging. A person having ordinary skill in the art would have found it obvious to arrive at the claimed invention prior to the filing date by incorporating the quencher of Yamaguchi into the composition of Meyers and Zi so as to improve patterning and composition stability.
Claim(s) 15 is rejected under 35 U.S.C. 103 as being unpatentable over Zi et al (US 20190384173 A1) and Meyers et al (US 20170102612 A1). as applied to claim 1 above, and further in view of Hatakeyama et al (US 20220107559 A1)
Regarding claim 15, Zi and Meyers meet the limitations of the claim as discussed above regarding claim 1.
However, neither Meyers nor Zi disclose the claimed salt as part of their compositions. Meyers discloses structurally similar salts such as triphenylsulfonium salts, however, in Fig 6A and 6B.
This limitation is met by Hatakeyama.
Hatakeyama discloses a photoresist composition comprising an acid generator that is a sulfonium salt having a fluorinated cation and a fluorinated sulfonate anion, a quencher that is a fluorinated sulfonium cation or has a fluorinated cation and anion, and a base polymer having acid labile groups therein (Abstract).
The acid generator (A) of the reference is discussed from [0045]-[0076].
The quencher (B) is discussed from [0077]-[0093].
The base polymer is discussed from [0094]-[01146]. Additional components include solvents, other quenchers, other acid generators, surfactants, among other components.
Exemplary quenchers include the embodiment at [0192], Q-18:
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The quenchers of Hatakeyama functions by producing acids that do not deprotect polymers – inhibiting the spread of strong acid into unwanted regions so as to improve patterning. The composition of Zi already establishes that quenchers have utility as additives in metal-containing resist compositions and help improve pattern parameters and composition aging. A person having ordinary skill in the art would have found it obvious to arrive at the claimed invention prior to the filing date by incorporating the quencher of Hatakeyama into the composition of Meyers and Zi so as to improve patterning and composition stability.
Conclusion
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/A.P.T./Examiner, Art Unit 1737
/JONATHAN JOHNSON/Supervisory Patent Examiner, Art Unit 1734
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