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.
Response to Amendment
Applicant’s Amendments filed 07/23/2026 are considered and entered. Claims 1, 12, 16-19, and 28 are amended. New claims 35-37 are added. No new matter appears to have been added with these claims – the compound of claim 12 draws support from Figure 10F in particular.
The Specification has been amended – no new matter has been added with this amendment to incorporate the compound of Figure 10F into the table added and was not retained in the original table during submission of the application.
Response to Arguments
Regarding the Amendments and arguments stemming therefrom, the rejection over 35 USC 112(b) for claim 12 is withdrawn as moot.
Regarding the amendments and argument stemming therefrom over claim 1 and the claims dependent therefrom, the Examiner respectfully disagrees with the characterization that Zi and Meyers are not suitable in combination and do not meet the limitations of the amended claim.
As currently written – the amended claim comprises a method for patterning a radiation sensitive material on a substrate, where the method comprises the developing of an exposed patternable material. The material prior to irradiation comprises an organotin composition represented by the formula present in the claim, where the R group of the formula is a C1-C31 hydrocarbyl ligand, and an Additive (A) in a molar ratio of 0.002 to about 2, and wherein the additive comprises a photoacid generator or a quencher or a mixture of quencher and photoacid generator. The additive further comprises an onium ion or zwitterion. Development comprises the selective removal of the irradiated regions.
The amended claim now recites “wherein the method expands the positive tone development processes window associated with the radiation dose as compared to an equivalent method performed without the additive.
As written, this expansion of the positive tone appears to be a result of the inclusion of the additive into the composition. When the composition comprising the additive as claimed and the tin material as claimed is present, exposing and developing (performing the claimed method) the material should naturally expand the positive tone development processes window associated with radiation dose as compared to an equivalent method performed on a material that lacks the additive.
As written, claim 1 recites a generic onium ion or zwitterion as the additive that may comprise an acid generator and/or quencher.
There are no further recited genera of chemical compounds, nor any particular species presented in the claim, regarding each/either of the photoacid generator and/or quencher. As such the structure of the claim may be met by any photoacid generator and/or quencher. Applicant’s claim language, not the Specification or Figures, is what controls the metes and bounds of patentability. Under a Broadest Reasonable Interpretation of the claims, any onium ion or zwitterionic species meets the limitations of the claimed additive, including but not limited to Ammonium, Phosphonium, Arsonium, Sulfonium, Selenonium, and Telluronium. As written, any and all species of these genera of ions meet the limitations of the claim when present in an additive in the required molar ratio of additive:Sn.
Further - applicant uses the transitional phrase “comprising” in describing the method and the material acted upon – this material is recited as “comprising an organotin composition represented by…”. The presence of additional unrecited components is not excluded from the claim.
The limitation added to this claim by the amendment is considered by the Examiner to be a natural result of performing the method using a material comprising a tin composition meeting the limitations of the formula recited and a generic additive comprising an onium salt, wherein the additive is included in a molar ratio of A:Sn ranging from about 0.003 to about 2.
As set forth in the prior office action, Zi discloses an additive in an organometallic photoresist material, and teaches additives that meet the limitations of the claims. Further, Zi purports in no uncertain language that there are improvements to critical dimension control when using these additives. Likewise, Meyers teaches the limitations of the tin material component as set forth in the prior office action, and ascribes the materials therein as amenable to high resolution pattern. The combination of the rejection is not required to be motivated by the same motivation as Applicant, and the reference Zi discloses a clear teaching of an advantage when using the additives therein (See MPEP 2144.II and MPEP 2144.IV).
It is the Examiner’s opinion that the best way for Applicant to overcome the obviousness-type rejection over Zi and Meyers is to provide data that is commensurate with the scope of the independent claim and claims dependent therefrom to abet an assertion of superior unexpected results in support of Applicant’s sought claim coverage.
In reference to claim 9, the Examiner reiterates that Applicant’s additive A is chemically generic and may be any onium ionic/zwitterionic additive as per claim 1 and discussed above. Claim 9 carries the limitations of claim 1 by nature of dependency. Zi’s additive(s) meet the limitations of claim 1 and, further, Zi does not ascribe any decrease in the absorption of EUV radiation to the presence of these additives and as such the additives are interpreted to not “significantly” decrease the EUV absorption.
The 35 USC 103 rejections over Zi and Meyers as set forth in the prior office action are maintained. The rejection over claim 1 has been edited to reflect the addition of the new limitation, but the thrust of the argument remains the same.
After further search and consideration, the Examiner makes a new grounds of rejection over Claim 12 to reflect that it is now examinable over prior art. Applicant’s amendment necessitated this new grounds of rejection.
After further search and consideration, the Examiner makes a new grounds of rejection over newly added claims 35-37. Applicant’s amendment necessitated this new grounds of rejection.
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 16-35 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 (a first) 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).
Regarding the limitation “wherein the method expands the positive tone development processes window associated with the radiation dose as compared to an equivalent method performed without the additive - as written, this expansion of the positive tone appears to be a result of the inclusion of the additive into the composition. When the composition comprising the additive as claimed and the tin material as claimed is present, exposing and developing (performing the claimed method) the material should naturally expand the positive tone development processes window associated with radiation dose as compared to an equivalent method performed on a material that lacks the additive.
As written, claim 1 recites a generic onium ion or zwitterion as the additive that may comprise an acid generator and/or quencher.
There are no further recited genera of chemical compounds, nor any particular species presented in the claim, regarding each/either of the photoacid generator and/or quencher. As such the structure of the claim may be met by any photoacid generator and/or quencher. Applicant’s claim language, not the Specification or Figures, is what controls the metes and bounds of patentability. Under a Broadest Reasonable Interpretation of the claims, any onium ion or zwitterionic species meets the limitations of the claimed additive, including but not limited to Ammonium, Phosphonium, Arsonium, Sulfonium, Selenonium, and Telluronium. As written, any and all species of these genera of ions meet the limitations of the claim. Meyers and Zi disclose the limitations of the claim 1 as described above and as such this improvement in process window is considered a natural result of the addition of the additive to the composition to be exposed and developed
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.
Regarding Claim 35, 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. At [0057], Meyers states that the energy absorbed by Tin during exposure is modulated by metal-organic interactions and can result in the rupturing of the metal-ligand bond. At [0048], the metallic compound are described to have a hydrocarbyl ligand to provide radiation sensitivity. While the reference never explicitly states it is the Sn-C bond that is radiation sensitive, it can be implied from the disclosure that if the metal-ligand bond in a radiation sensitive ligand can rupture upon absorption of radiation then the Sn-C bond is radiation sensitive. Further - the organotin compounds of Meyers meet the limitations of the claimed compounds of claim 1 as described regarding claim 1. The radiation sensitivity is a property of the bond in the claimed compounds and is therefore present regardless of explicit recitation (See MPEP 2112.01.II and MPEP 2144.09).
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) 12 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 Iwato et al (US 20130078433 A1).
Regarding Claim 12, Zi and Meyers meet the limitations of the claim as discussed above regarding claim 1.
However, neither Meyers nor Zi disclose the clamed triphenylsulfonium adamantane-difluoro-ethyl sulfonate salt as part of their compositions. Zi discloses structurally similar acids salts such as triphenylsulfonium nonaflate, however, in Fig 6A and 6B.
This limitation is met by Iwato.
Iwato disclsoses an actinic ray sensitive composition or radiation-sensitive composition comprising a base resin and an acid generator.
Photoacid generators are broadly described at [0356] and [0394], including sulfonium nonaflate embodiments such as those taught by Zi (see Iwato (z2) at [0394]). In the experimental examples, Iwato disclsoses the following compound as PAG-3 and further disclsoses it at [0356], Page 57:
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Iwato, Zi, and Meyers are each directed to photoresist compositions comprising acid generators and resins intended to react with the acids generated therefrom and Iwato and Zi each teach sulfonium nonafluorobutane sulfonate salts – Iwato presents the nonafluorobutanesulfonate salt in tandem with the trifluorosulfonate salt and as such considers these two salts to be alternatives to one another. Further, the combination of components of a two compositions each known to be useful for a particular purpose so as to form a third composition to also be used for that particular purpose is considered prima facie obvious ( See MPEP 2144.06, in re Kerkhoven).
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 Iwato into the composition of Zi and Meyers with recognition that it would behave similarly to the PAG additive triphenylsulfonium nonafluorobutane sulfonate (See MPEP 2144.09).
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 trifluoromethylsulfonate) salt as part of their compositions. Zi 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 iodonium salt as part of their compositions. Zi 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. Zi 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.
Claim(s) 36 and 37 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). as applied to claim 1 and 28 above, and further in view of Kocsis et al (US 2020124970 A1).
Regarding Claim 36 and 37, Zi and Meyers meet the limitations of the claim as discussed above regarding claim 1 and 28.
As described above, the compositions of Meyers are post-exposure baked at a temperature from 45 to 250 degrees Celsius ([0088]).
Meyers does teach that a developer composition is used to remove the irradiated (or unirradiated, for negative development) material as described from [0090]-[0103], wherein (a first) positive development is performed using a tetramethylammonium hydroxide developer comprising 0.5 to 30 wt% TMAH. 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.
After development, a rinse and a post-development bake may be performed as discussed at [0097]-[0098]. A second bake may take place at a temperature range from 100 to 600 degrees Celsius - a temperature range with a start point higher than that of the post-exposure bake and an end point also higher than that of the post exposure bake. A person having ordinary skill in the art would easily arrive at a baking temperature at least 5 degrees higher than the post-baking temperature as the overall range of 100 to 600 comprises temperature embodiments significantly higher than 45 and/or 250. Baking times may be from 1 to 25 minutes, overlapping the claimed range of 0.1 minutes (6 seconds) or greater.
However, neither reference describes a second development step.
This limitation is met by Kocsis.
Kocsis disclsoses a rinse process for processing an initially patterned structure formed with an organometallic radiation-sensitive material, wherein the resin process can remove portions of the composition remaining after pattern development to improve uniformity of the structures formed.
At [0018]-[0019], Kocsis describes the exposure and development of an organometallic radiation sensitive composition, such as an organotin oxide hydroxide composition, where the second development step generally may be performed using a different developer than the first. Kocsis does not explicitly state an embodiment wherein second development on a positive resist first developed with an alkaline developer. Kocsis does state that “generally” the first developer is organic and the second is alkaline at [0018] – however, prior to this Kocsis does broadly call for a second development step to remove material not removed by the first development in the same section [0018].
Kocsis therefore implicitly provides two options for the second development step: using a developer of a different ‘type’ than the first developer (using a first organic solvent in a first developer step and a second alkaline developer in a second developer step - or vice-versa where the first developer is organic and the second is alkaline) as appears preferred by the reference, or using a second developer that is the same type.
The post-development bake of Meyers is used to further condense the material disclosed, and further dehydrate or densify it while driving off developer ([0098]). A rinse or second development using an alkali step after a first alkali development would remove any residual alkali-soluble portions left behind after the first development or crashed-out of solution by the removal of residual alkaline developer during the post-development bake. As Meyers disclsoses a TMAH developer, a person having ordinary skill in the art would readily use the same embodiment again to perform what is essentially a repeat development step (claim 37), as the reference establishes that the TMAH developer is suitable as an alkaline developer in the first development step.
A person having ordinary skill in the art would have found it obvious to arrive at the claimed invention in view of the disclosures of Zi, Meyers, and Kocsis by incorporating the second development step of Kocsis into the method of Zi and Meyers so as to further improve the uniformity of resist structures, wherein the second development is a repetition of the first development step intended to remove any residues deposited during a post-development bake or undeveloped portions missed during the first development step.
Conclusion
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
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/A.P.T./Examiner, Art Unit 1737
/SALLY A MERKLING/SPE, Art Unit 1738
