DETAILED ACTION
STATUS OF THE APPLICATION
Receipt is acknowledged of Applicant’s Amendments and Remarks, filed 25 October 2023, in the matter of Application No. 18/288,228. Said documents have been entered on the record. The Examiner further acknowledges the following:
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Claims 5-23 have been withdrawn.
Claims 14-19 and 21 have been amended.
No claims have been cancelled.
Applicant’s election of Group I (claims 1-4), without traverse, is acknowledged.
Election/Restrictions
Applicant’s election without traverse of Group I (claims 1-4) in the reply filed on 21 April 2026 is acknowledged.
Claims 5-23 are withdrawn from further consideration pursuant to 37 CFR 1.142(b) as being drawn to a nonelected invention, there being no allowable generic or linking claim. Election was made without traverse in the reply filed on 21 April 2026.
Applicant’s election without traverse of a species in the reply filed on 21 April 2026 is acknowledged. The Examiner notes the following election of species (A) specific forming material: CpHf, a compound represented by Chemical Formula 3-1:
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and the following election of species (B) specific inorganic material: tert-butyl iodide (TBI), a compound represented by Chemical Formula 3-2:
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Applicant submits that the claims encompassing the elected species are claims 1-4.
These designations of species (A) and (B) appear to have been made in error. Therefore, species (A) will be interpreted as the specific inorganic material, and species (B) will be interpreted as the specific film-forming material. As such, the CpHf species (CpHf(NMe2)3) elected by Applicant will be interpreted as reading on the “inorganic precursor” limitation of instant claim 3, and the species tert-butyl iodide (TBI) elected by Applicant will be interpreted as reading on the genus of Chemical Formula 1 of instant claim 4 when A is carbon, n is 1, B is methyl, m is 3 (i.e., 2n+1), X is I, o is 1, and i and j are 0.
Thus, claims 1-4 are presented and represent all claims currently under consideration.
Priority
Domestic Priority data as claimed by Applicant:
This application is a 371 of PCT/KR2022/007539 (05/27/2022)
Foreign Applications:
REPUBLIC OF KOREA 10-2022-0063835 (05/25/2022)
REPUBLIC OF KOREA 10-2021-0069947 (05/31/2021)
Receipt is acknowledged of certified copies of papers required by 37 CFR 1.55.
Drawings
The drawings are objected to because Figures 4-6 are blurry and difficult to read.
Corrected drawing sheets in compliance with 37 CFR 1.121(d) are required in reply to the Office action to avoid abandonment of the application. Any amended replacement drawing sheet should include all of the figures appearing on the immediate prior version of the sheet, even if only one figure is being amended. The figure or figure number of an amended drawing should not be labeled as “amended.” If a drawing figure is to be canceled, the appropriate figure must be removed from the replacement sheet, and where necessary, the remaining figures must be renumbered and appropriate changes made to the brief description of the several views of the drawings for consistency. Additional replacement sheets may be necessary to show the renumbering of the remaining figures. Each drawing sheet submitted after the filing date of an application must be labeled in the top margin as either “Replacement Sheet” or “New Sheet” pursuant to 37 CFR 1.121(d). If the changes are not accepted by the examiner, the applicant will be notified and informed of any required corrective action in the next Office action. The objection to the drawings will not be held in abeyance.
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.
Claims 1-4 are 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.
Regarding claims 1-3, claim 1 recites “A film-forming material, comprising a blocking agent and a ligand exchange reaction agent.” Yet, claim 2 recites “…wherein the blocking agent is…formed from the film-forming material in a film formation process.” and claim 3 recites “…wherein the ligand exchange reaction agent is…formed from the film-forming material in a film formation process…” Therefore, it is unclear how the recited “film-forming material” of claim 1 can comprise a blocking agent and a ligand exchange reaction agent when both the blocking agent and the ligand exchange reaction agent are the product of a reaction of the recited “film-forming material”, and it is likewise unclear how the blocking agent or ligand exchange reaction agent of claims 2-3 can be a part of the film-forming material of claim 1 on which they depend when they are the products of a “film formation process” of the recited “film-forming material”. In the specification as filed, the “film-forming material” is described as both either providing or including a blocking agent and a ligand exchange reaction agent (Specification; pages 4-5, paragraphs 8 and 11), however it is not clear which is meant in the claims.
Further regarding claims 1-3, Examples 1-14 of the present application states that tert-butyl iodide (TBI) was used as the film-forming material (Specification; page 45, paragraph 193; page 56, paragraph 266, Table 1, Examples 1-14). Furthermore, the present application describes Fig. 4 as a flowchart for schematically explaining a first process in which a blocking agent generated when a film is formed using a film-forming material according to Example 1, wherein the blocking agent is 2-methylpropene and the ligand exchange reaction agent is hydrogen iodide (Fig. 4b and Specification; pages 19-20, paragraph 91). Thus, the present application recites TBI as the film-forming material, and this compound does not comprise a blocking agent and a ligand exchange reaction agent. Instead, the film-forming material (TBI) must be further transformed into the blocking agent (2-methylpropene) and the ligand exchange reaction agent (hydrogen iodide). This lack of clarity renders instant claims 1-3 indefinite.
For the purposes of compact prosecution, a “film-forming material” will be reasonably interpreted as either (1) TBI; or (2) a mixture of 2-methylpropene and HI (as shown in Figs. 4-5), until the 112 issues detailed herein are resolved.
Regarding claims 2-4, these dependent claims do not resolve the indefiniteness of claim 1 described above.
Claim 3 recites the limitation "the film formation process" in line 3. There is insufficient antecedent basis for this limitation in the claim.
The following is a quotation of 35 U.S.C. 112(d):
(d) REFERENCE IN DEPENDENT FORMS.—Subject to subsection (e), a claim in dependent form shall contain a reference to a claim previously set forth and then specify a further limitation of the subject matter claimed. A claim in dependent form shall be construed to incorporate by reference all the limitations of the claim to which it refers.
The following is a quotation of pre-AIA 35 U.S.C. 112, fourth paragraph:
Subject to the following paragraph [i.e., the fifth paragraph of pre-AIA 35 U.S.C. 112], a claim in dependent form shall contain a reference to a claim previously set forth and then specify a further limitation of the subject matter claimed. A claim in dependent form shall be construed to incorporate by reference all the limitations of the claim to which it refers.
Claim 4 is rejected under 35 U.S.C. 112(d) or pre-AIA 35 U.S.C. 112, 4th paragraph, as being of improper dependent form for failing to further limit the subject matter of the claim upon which it depends, or for failing to include all the limitations of the claim upon which it depends.
Claim 4 recites “…wherein the film-forming material is a branched, cyclic, or aromatic compound represented by Chemical Formula 1…” in lines 1-2. However, the instant claim recites that the film-forming material is the genus of Chemical Formula 1, and therefore does not further comprise a blocking agent and a ligand exchange reaction agent as recited in claim 1 on which the instant claim depends.
Applicant may cancel the claim(s), amend the claim(s) to place the claim(s) in proper dependent form, rewrite the claim(s) in independent form, or present a sufficient showing that the dependent claim(s) complies with the statutory requirements.
Claim Rejections - 35 USC § 102
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless –
(a)(1) the claimed invention was patented, described in a printed publication, or in public use, on sale, or otherwise available to the public before the effective filing date of the claimed invention.
Claims 1-4 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by R. Heasley et al. (“Vapor Deposition of Halide Perovskites and Hole- Transport Materials for Use in Thin-Film Photovoltaics” PhD Dissertation; published 08-2017; hereinafter “Heasley”).
Regarding claims 1-4, Heasley discloses the growth of methylammonium tin halide perovskite materials by atomic layer deposition and chemical vapor deposition using the reaction between precursors N,N’-di-tert-butyl-2,3-diamidobutanetin(II) and HI or HBr (page 9, paragraph 1). Thin films of nominal SnI2 were deposited by ALD and CVD using the reaction between precursors N,N’-di-tert-butyl-2,3-diamidobutanetin(II) (Sn(cyc)) and anhydrous hydrogen iodide (HI). This process involves ligand exchange between the in situ generated HI and the ligands of the Sn(cyc):
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HI is not commercially available and it was therefore necessary to generate HI in situ during each deposition of an iodine-containing film through the thermal decomposition of tert-butyl iodide. Heasley further discloses that pulsed-CVD, in which Sn(cyc) and HI are present simultaneously, deposited films containing tin and iodine. In addition to the desired HI, this reaction also produces isobutene (page 9, paragraph 1; page 13, paragraph 2; page 14, Fig. 2.1; page 16, paragraph 2; page 22, Fig. 2.6):
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Thus, Heasley discloses the production of SnI2 thin films via pulsed-CVD, wherein tert-butyl iodide is thermally decomposed in a process that produces HI and 2-methylpropene in situ, and the HI generated forms SnI2 via a ligand exchange reaction.
tert-Butyl iodide (TBI) is the same film-forming material recited in the present application that reacts to form HI and 2-methylpropene (Specification; page 56, paragraph 266, Table 1, Examples 1-14; Fig. 4), in a manner consistent with instant claim 1. In addition, TBI resides within the genus of Chemical Formula 1 of instant claim 4 when A is carbon, n is 1, B is methyl, m is 3 (i.e., 2n+1), X is I, o is 1, and i and j are 0.
Heasley discloses that the in situ generated HI reacts with Sn(cyc) to for SnI2 via an exchange reaction with the ligands of the inorganic precursor, in a manner consistent with the limitation of instant claim 3.
2-Methylpropene is the same blocking agent formed from TBI as described in the written description (Fig. 4), in a manner consistent with instant claim 1, and 2-methylpropene is an unsaturated hydrocarbon have 4 carbon atoms and is formed in the film formation process, as recited in instant claim 2. Although Heasley does not explicitly teach that 2-methylpropene is a blocking agent, Heasley inherently teaches this limitation. MPEP § 2112(II) states that “There is no requirement that a person of ordinary skill in the art would have recognized the inherent disclosure at the relevant time, but only that the subject matter is in fact inherent in the prior art reference.”
Therefore, regardless of whether the Applicant elected TBI or a mixture of 2-methylpropene and HI, Heasley anticipates either interpretation.
Claims 1-4 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Yeon et al. (“Tertiary alkyl halides as growth activator and inhibitor for novel atomic layer deposition of low resistive titanium nitride” AIP Advances, 2021, 11, 015218, pages 1-9; published 01-07-2021; IDS of 11-14-2024; hereinafter “Yeon”).
Regarding claims 1-4, Yeon discloses a novel atomic layer deposition (ALD) that utilizes tertiary alkyl (tert-alkyl) halides as both growth activator and inhibitor for the deposition of a low resistive TiN film using TiCl4 and NH3 (Abstract).
Yeon further discloses that among the alkyl halides, tert-butyl iodide is identified as a suitable material for both growth inhibition and growth activation without any incorporation of C impurity in the film (Abstract). For inhibitor-type ALD, tert-butyl iodide is fed prior to TiCl4 source feed, and the base-induced elimination reaction occurs when tert-butyl iodide approaches the OH-terminated substrate, resulting in the formation of 2-methylpropene and hydrogen iodide (page 4, Col. 1, paragraph 1). Both 2-methylpropene and the adsorbed iodine are expected to reduce the sticking probability of the subsequent TiCl4 precursor on the substrate, decreasing the growth per cycle (GPC), and it is predicted that the Ti-I bond can be formed by direct ligand exchange between tert-butyl iodide and -TiCl3 or -TiCl2 group adsorbed on the substrate (page 4, Col. 1, paragraph 3 and Col. 2, paragraph 1).
Thus, Yeon discloses the production of TiN thin films via ALD with TiCl4 and tert-butyl iodide, wherein the tert-butyl iodide is decomposed in the process and produces HI and 2-methylpropene in situ. The 2-methylpropene acts as a blocking agent (i.e., reduces the sticking probability of the subsequent TiCl4 precursor), and the HI generated forms Ti-I bonds by direct ligand exchange, as detailed above.
tert-Butyl iodide (TBI) is the same film-forming material recited in the present application that reacts to form HI and 2-methylpropene (Specification; page 56, paragraph 266, Table 1, Examples 1-14; Fig. 4), in a manner consistent with instant claim 1. In addition, TBI resides within the genus of Chemical Formula 1 of instant claim 4 when A is carbon, n is 1, B is methyl, m is 3 (i.e., 2n+1), X is I, o is 1, and i and j are 0.
Yeon discloses that the in situ generated HI reacts with -TiCl3 or -TiCl2 group adsorbed on the substrate via direct ligand exchange, in a manner consistent with the limitation of instant claim 3.
2-Methylpropene is the same blocking agent formed from TBI as described in the written description (Fig. 4), in a manner consistent with instant claim 1, and 2-methylpropene is an unsaturated hydrocarbon have 4 carbon atoms and is formed in the film formation process, as recited in instant claim 2. Furthermore, Yeon discloses that reduces the sticking probability of the subsequent TiCl4 precursor, as detailed above, and therefore acts as a blocking agent.
Therefore, regardless of whether the Applicant elected TBI or a mixture of 2-methylpropene and HI, Yeon anticipates either interpretation.
Applicant cannot rely upon the certified copy of the foreign priority application to overcome this rejection because a translation of said application filed 31 May 2021 has not been made of record in accordance with 37 CFR 1.55. When an English language translation of a non-English language foreign application is required, the translation must be that of the certified copy (of the foreign application as filed) submitted together with a statement that the translation of the certified copy is accurate. See MPEP §§ 215 and 216.
Claims 1-4 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Tan et al. (“Utilizing tertiary butyl iodide as an effective film quality enhancing agent for atomic layer deposition of HfO2 dielectric thin films” AIP Advances, 2021, 11, 075008, pages 1-6; published 07-02-2021; hereinafter “Tan”).
Regarding claims 1-4, Tan discloses the effects of the initial pulse of tert-butyl iodide as a surfactant in atomic layer deposition of HfO2 using cyclopentadienyl tris(dimethylamino) hafnium, CpHf(NMe2)3, and ozone (O3), wherein the formation of 2-methylpropene and hydrogen iodide from tert-butyl iodide via elimination reactions is the key idea of the effective approach for improving film conformality, film quality, and leakage current simultaneously (Abstract).
The predicted growth mechanisms and experimental results of Tan suggest that different blocking probabilities by 2-methylpropene and hydrogen iodide on the top and bottom of the trench feature lead to 10% improvement in film conformality. In addition, ligand exchanges between the Hf precursor and hydrogen iodide lead to effective removal of large portions of carbon-containing ligands, resulting in a significant reduction in carbon residues (Abstract; page 4, Figs. 5-6).
Thus, Tan discloses the production of HfO2 thin films with CpHf(NMe2)3 and tert-butyl iodide, wherein the tert-butyl iodide is decomposed in the process and produces HI and 2-methylpropene in situ. The 2-methylpropene acts as a blocking agent, and the HI generated effectively removes large portions of carbon-containing ligands via ligand exchanges, as detailed above.
tert-Butyl iodide (TBI) is the same film-forming material recited in the present application that reacts to form HI and 2-methylpropene (Specification; page 56, paragraph 266, Table 1, Examples 1-14; Fig. 4), in a manner consistent with instant claim 1. In addition, TBI resides within the genus of Chemical Formula 1 of instant claim 4 when A is carbon, n is 1, B is methyl, m is 3 (i.e., 2n+1), X is I, o is 1, and i and j are 0.
Tan discloses that the in situ generated HI effectively removes large portions of carbon-containing ligands via ligand exchanges, in a manner consistent with the limitation of instant claim 3.
2-Methylpropene is the same blocking agent formed from TBI as described in the written description (Fig. 4), in a manner consistent with instant claim 1, and 2-methylpropene is an unsaturated hydrocarbon have 4 carbon atoms and is formed in the film formation process, as recited in instant claim 2. Furthermore, Tan discloses that 2-methylpropene acts as a blocking agent, as detailed above.
Therefore, regardless of whether the Applicant elected TBI or a mixture of 2-methylpropene and HI, Tan anticipates either interpretation.
Applicant cannot rely upon the certified copy of the foreign priority application to overcome this rejection because a translation of said application filed 31 May 2021 has not been made of record in accordance with 37 CFR 1.55. When an English language translation of a non-English language foreign application is required, the translation must be that of the certified copy (of the foreign application as filed) submitted together with a statement that the translation of the certified copy is accurate. See MPEP §§ 215 and 216.
Conclusion
Any inquiry concerning this communication or earlier communications from the Examiner should be directed to Derek Rhoades whose telephone number is (703)-756-5321. The Examiner can normally be reached Monday–Thursday, 7:30 am–5:00 pm EST; Friday, 7:30 am–4:00 pm EST.
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/D.R./Examiner, Art Unit 1692
/AMY C BONAPARTE/Primary Examiner, Art Unit 1692
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