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 .
Continued Examination Under 37 CFR 1.114
A request for continued examination under 37 CFR 1.114, including the fee set forth in 37 CFR 1.17(e), was filed in this application after final rejection. Since this application is eligible for continued examination under 37 CFR 1.114, and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114. Applicant's submission filed on 3/26/2026 has been entered.
Response to Arguments
Applicant's arguments directed to the newly amended claims filed 3/18/2026 have been fully considered but they are not persuasive.
The applicant argues that the removal of formula 3 and the specific requirement for molybdenum carbonyl overcomes the prior art. This argument is unpersuasive.
While formula 3 was removed and the remaining structures renumbered as Formulas 4-20, the remaining formulas still encompass the molybdenum-based precursors taught by the prior art. Kim explicitly identifies molybdenum(O)-based hydrocarbon compounds, including those containing carbonyl groups (See Kim [0005] and [0041]). The structural characteristics of the remaining Formulas 4-20, specifically those featuring molybdenum bonded to carbonyl and hydrocarbon ligands, continue to be taught of suggested by the preferred embodiments in Kim.
Furthermore, the modification of these, specific molybdenum precursors with the growth regulator and NH3 process of Yeon remains obvious. Molybdenum and Titanium are both transition metals; therefore, a person of ordinary skill in the art would expect the growth regulation and nitridation mechanisms taught in Yeon to function predictably with the molybdenum precursors of Kim. The omission of formula 3 and renumbering of the formulas dos not change the fact that the amendment represents a simple substitution of known elements to yield predictable results.
Prior Art of Record
The applicant's attention is directed to additional pertinent prior art cited in the accompanying PTO-892 Notice of References Cited, which, however, may not be currently applied as a basis for the following rejections. While these references were considered during the examination of this application and are deemed relevant to the claimed subject matter, they are not presently being applied as a basis for rejection in this Office action. The pertinence of these documents, however, may be revisited, and they may be applied in subsequent Office actions, particularly in light of any amendments or further clarification of the claimed invention.
Claim Rejections - 35 USC § 103
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 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.
Claim(s) 1-16 is/are rejected under 35 U.S.C. 103 as being unpatentable over Kim et al. (US 20220018017 A1) in view of Yeon et al. (AIP Advances 11, 015218 (2021); doi: 10.1063/5.0031127Submitted: 9 November 2020 •Accepted: 14 December 2020 •Published Online: 7 January 2021).
CLAIM 1. Claim 1 recites: a metal thin film precursor composition, comprising
a thin film precursor compound; and
a growth regulator,
wherein the thin film precursor compound comprises a compound represented by Chemical Formula 4-39 below, and the growth regulator is a straight-chain, branched, cyclic, or aromatic compound represented by Chemical Formula 2 below.
[Chemical Formula 4 -20]
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696
888
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[Chemical Formula 21-31]
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320
514
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[Chemical Formula 32-39]
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246
492
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[Chemical Formula 2]
AnBmXoYiZj,
wherein A is carbon, silicon, nitrogen, phosphorus, or sulfur; B is hydrogen, an alkyl having 1 to 10 carbon atoms, a cycloalkyl having 3 to 10 carbon atoms, or an alkoxy having 1 to 10 carbon atoms; X comprises one or more of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I); Y and Z independently comprise one or more selected from the group consisting of oxygen, nitrogen, sulfur, and fluorine and are different from each other; n is an integer from 1 to 15; o is an integer greater than or equal to 1; m is 0 to 2n+1; and i and j are integers from 0 to 3.
Claim 1 requires a metal thin film precursor composition comprising a thin film precursor compound represented by Chemical Formulas 3-39 and a growth regulator represented by Chemical Formula 2, AnBmXoYiZj, where X comprises one or more of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).
Kim et al. teaches a method for manufacturing a molybdenum-containing thin film using a molybdenum(0)-based hydrocarbon compound, specifically identifying molybdenum carbonyl Mo(CO)6 (Abstract & ¶¶[0004-5 & 41])1, which is structurally identical to the precursor represented by the applicant's Chemical Formula 3.
Regarding the growth regulator, Kim et al. explicitly teaches the use of a reaction gas that is ""alkyl iodide"2 (¶[0018]) to describe its reaction gas, an alkyl iodide is a chemical species characterized by an iodine atom bonded to an alkyl group, satisfying the "X" component requirement of Formula 2.
This teaching is further supported by Yeon, which explicitly teaches the use of a growth regulator to control thin film deposition in paragraph, specifically identifying tert-butyl iodide (C4H9I) as a material suitable for both growth inhibition and growth activation (Yeon Abstract: “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.”). Yeon identifies the iodide species a particularly effective because the C-Ibond (200KJ/mol) is weaker thatn the C-Br (244 kJ/mol) of C-Cl(296 kJ/mol) bonds (Yeon Table 1), making it more active for ligand exchange.
In accordance with the guidance set forth in MPEP § 2143(I)(A) and the principles of KSR, the modification of the process in Kim et al. involves simply swapping the metal precursor of one reference with the growth regulator teachings of Yeon. Specifically, a person of ordinary skill in the art would have found it obvious to apply the growth regulation methodology and specific organic halide species taught by Yeon to the molybdenum precursor system taught by Kim et al.
The predictability of this combination is reinforced by the fact that molybdenum (Mo) and titanium (Ti) are both transition metals. Given their shared classification and similar electronic configurations, a person of ordinary skill in the art would expect these metals to exhibit analogous reactivity and behavior during thin-film deposition.
This technical expectation is further supported by the fact that Kim et al. generically teaches the use of "alkyl iodide," providing a direct motivation to utilize the specific tertiary alkyl halides (such as tert-butyl iodide) taught by Yeon, which are identified as the most effective species in that class for improving film quality and reducing resistivity. Specifically, Yeon demonstrates that these materials can function as growth inhibitors, defined as materials that decrease the growth rate by more than 5%, to improve conformality, or growth activators, defined as materials that increase the growth rate by more than 5%, to reduce resistivity, depending on the feed sequence. Substituting or combining the "alkyl iodine" of Kim et al. with the specific "tert-butyl iodide" of Yeon represents a simple substitution of known elements according to known methods to yield predictable results
CLAIM 2. Kim et al. in view of Yeon teaches et al. in view of Yeon metal thin film precursor composition according to claim 1, wherein, in Chemical Formula 1, n is an integer from 1 to 6 (Kim ¶[0005, 21-22] – Mo(CO)6 – Kim teaches C1-C7 alkyl precursor compositions meeting the scope.; – Yeon – TiCl4 precursor: n= (four chloride ligands), which is withing the claimed range, see Abstract.).
CLAIM 3. Kim et al. in view of Yeon teaches metal thin film precursor composition according to claim 1, wherein, in Chemical Formula 1, N is F, Cl, or Br or a ligand consisting of a combination of two or more selected from the group consisting of F, Cl, and Br (Kim et al. ¶[0005] – Cl; Yeon - TiCl4 is a embodiment of the Chemical Formula 1 [below] where M=Ti, N=Cl, x=1, n=4 and m=0, see Abstract.).
CLAIM 4. Kim et al. in view of Yeon teaches metal thin film precursor composition according to claim 1, wherein the growth regulator is Cl, Br, or I or has a halide terminal group consisting of a combination of two or more selected from the group consisting of Cl, Br, and I (Kim et al. – akyl iodide; Yeon - Tert-butyl iodide growth regulator disclose by Yeon contains I (iodine) which is explicitly included in the claimed list, see Abstract.).
CLAIM 5. Kim et al. in view of Yeon teaches metal thin film precursor composition according to claim 1, comprising one or more selected from compounds represented by Chemical Formulas 40 to 60 below.
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1575
825
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wherein, in Chemical Formulas 40 to 60, a line is a bond; carbon is located at a point where bonds meet without indicating a separate element; and the number of hydrogen atoms satisfying a valence of the carbon is omitted (Kim et al. – akyl iodides share terminal halide characteristics with the claimed branched structures; Yeon et al. - tert-butyl iodide is the first skeletal structure on the top left of the image, and also taught by Yeon. Note: For the tert-butyl iodide structure shown, the three methyl groups (the "ends" of the lines) each have three implied hydrogen atoms (CH3) to reach four bonds. The central, tertiary carbon atom is already bonded to three other carbons and one iodine atom, satisfying all four of its bonds, so it has zero implied hydrogen atoms.).
CLAIM 6. Kim et al. in view of Yeon teaches metal thin film precursor composition according to claim 1, wherein the metal thin film precursor composition is used in an atomic layer deposition (ALD) process, a plasma atomic layer deposition (PEALD) process, a chemical vapor deposition (CVD) process, or a plasma chemical vapor deposition (PECVD) process (Kim et al. - ¶[0004-5] – CVD, PVD, ALD, etc.. ; Yeon discloses using the composition TiCl4 and tert-butyl iodide in an ALD process , see Abstract.).
CLAIM 7. Kim et al. in view of Yeon teaches method of forming a thin film, comprising injecting the metal thin film precursor composition according to claim 1 into a chamber and adsorbing the metal thin film precursor composition on a surface of a loaded substrate (Kim et al. - ¶[0004-5] – CVD, PVD, ALD, etc..; Yeon discloses using the composition TiCl4 and tert-butyl iodide in an ALD process. The recited language is fundamental to ALD.).
CLAIM 8. Kim et al. in view of Yeon teaches method according to claim 7, comprising:
i) vaporizing a growth regulator and adsorbing the growth regulator on a surface of a substrate loaded in a chamber (Inhibitor-type ALD, of Yeon, requires the vaporization of liquid tert-butyl iodide and its adsorption, which is the self-limiting mechanism of ALD.);
ii) performing first purging of an inside of the chamber using a purge gas (Yeon discloses purging between various cycle steps. Purging is a conventional requirement of all sequential ALD processes. It is understood in the art necessary to prevent uncontrolled gas-phase mixing (CVD) between the growth regulator and precursor, thus purging as claimed would be an obvious expected step in the cycle by a POSITA.);
iii) vaporizing a thin film precursor compound in the chamber and adsorbing the thin film precursor compound on a surface area different from the surface area of the substrate on which the growth regulator is adsorbed or bonding the thin film precursor compound to a terminal of the growth regulator adsorbed on the substrate (Taught by the "Inhibitor-type ALD" sequence of Yeon. The inhibitor, forces the TiCl4 (precursor) to adsorb onto the unblocked/different surface areas.);
iv) performing second purging of the inside of the chamber using a purge gas (A second purge is a standard ALD practice, required to remove excess precursor (TiCl4) before the Reaction Gas is introduced, ensuring film quality and self-limited growth. Standard Purging would be a obvious expectation by a POSITA.);
v) supplying a reaction gas into the chamber (Yeon discloses ammonia (NH3) as the reaction gas to form the TiN fil. Forming MoN as per the modification of Kim et al. in view of Yeon would be formed in the same manner.); and
vi) performing third purging of the inside of the chamber using a purge gas (A final purge is standard ALD practice, thus would be an obvious expectation by a POSITA, as it is considered necessary to clear the chamber of the reaction gas and gaseous byproducts before the next cycle starts).
Note: In accordance with the rationale set forth in MPEP § 2143(I)(A) and the principles of KSR, the modification of the process in Kim involves simply substituting the metal precursor of one reference with the growth regulator and coreactant teachings of Yeon. Specifically, a person of ordinary skill in the art would have found it obvious to apply the growth regulation methodology and ammonia (NH3) reaction steps taught by Yeon to the specific molybdenum precursor system taught by Kim.
The predictability of this combination is reinforced by the chemical similarity between molybdenum (Mo) and titanium (Ti). As both are transition metals, they exhibit analogous reactivity profiles in Atomic Layer Deposition (ALD) environments. Therefore, the process of forming molybdenum nitride (MoN) using an NH3 coreactant is technically equivalent to the process of forming titanium nitride (TiN) described in Yeon, with the only significant variation being the specific metal precursor used
CLAIM 9. Kim et al. in view of Yeon teaches method according to claim 7, comprising:
i-1) vaporizing a growth regulator and a thin film precursor of a thin film precursor compound, adsorbing the growth regulator on a surface area of the substrate loaded in the chamber, and adsorbing the thin film precursor compound on a surface area of the substrate that is different from the surface area of the substrate on which the growth regulator is adsorbed, or bonding the thin film precursor compound to a terminal of the growth regulator adsorbed on the substrate ("Activator-type ALD" sequence. The cycle begins with the TiCl4 (precursor) feed, which is vaporized and adsorbs on the surface. Reactive gases are vaporized also.);
ii) performing first purging of an inside of the chamber using a purge gas (The recited step is understood as routine purging, necessary to remove excess TiCl4 to ensure a self-limiting reaction, even when the intermediate GR step is omitted from the claim. Purging between introducing gasses is a obvious expectation by a POSITA.);
v) supplying a reaction gas into the chamber (Yeon discloses the use of ammonia (NH3) as the reaction gas); and
vi-1) performing additional purging of the inside of the chamber using a purge gas (As provided above, a purging step is routine a routine step in ALD, and is a obvious expectation by a POSITA. The term "additional" is a matter of degree and is considered an obvious parameter optimization for a POSITA. A POSITA would be expected to perform additional purging as needed or desired.).
CLAIM 10. Kim et al. in view of Yeon teaches method according to claim 7, comprising:
i-2) vaporizing a thin film precursor compound and adsorbing the thin film precursor compound on a surface of a substrate loaded in a chamber ("Activator-type ALD" sequence. The cycle starts with the TiCl4 (precursor) feed, which is vaporized and adsorbs on the surface.);
ii) performing first purging of an inside of the chamber using a purge gas (Routine purging is a obvious expectation to a POSITA, necessary to remove excess TiCl4 before the Growth Regulator is introduced.);
iii) vaporizing a growth regulator in the chamber and adsorbing the growth regulator on a surface area different from the surface area of the substrate on which the thin film precursor compound is adsorbed or bonding the growth regulator to a terminal of the thin film precursor compound adsorbed on the substrate ("Activator-type ALD" sequence. As taught in Yeon, tert-butyl iodide bonds to the precursor layer via in situ ligand exchange (the activation mechanism);
iv) performing second purging of the inside of the chamber using a purge gas (Routine purging is understood in the art as a obvious step by a POSITA. Purging is necessary to remove excess tert-butyl iodide before the Reaction Gas is introduced.);
v) supplying a reaction gas into the chamber (Yeon teaches a ammonia (NH3) as the reaction gas.); and
vi) performing third purging of the inside of the chamber using a purge gas (Routine purging is a obvious expectation by a POSITA, as it is necessary to clear the chamber of the reaction gas and byproducts.).
CLAIM 11. Kim et al. in view of Yeon teaches method according to claim 7, wherein the metal thin film precursor composition is transferred into an ALD chamber (Yeon, Abstract), a CVD chamber, a PEALD chamber, or a PECVD chamber by a VFC method, a DLI method, or an LDS method (Yeon teaches ALD, which requires precursor delivery. Using standard delivery methods like VFC (Vapor Flow Control), DLI (Direct Liquid Injection), or LDS (Liquid Delivery System) is routine and obvious if not implicit in ALD and thus at least obvious to a POSITA. The specific delivery method does not provide a non-obvious difference over the teaching in Yeon.).
CLAIM 12. Kim et al. in view of Yeon teaches method according to claim 7, wherein the reaction gas is a reducing agent, a nitrifying agent, or an oxidizing agent (Yeon discloses the use ammonia NH3, which serves as a nitrifying agent TiN and a mild reducing agent in the ALD process).
CLAIM 13. Kim et al. in view of Yeon teaches method according to claim 7, wherein deposition temperature is 50 to 700° C (NPL discloses that TiN films were deposited at a specific temperature (e.g., 300C that falls within the broad claimed range of 50-700C. MoN would be formed in analogous manner.).
CLAIM 14. Kim et al. in view of Yeon teaches method according to claim 7, wherein the thin film is an oxide film, a nitride film, or a metal film (This limitation is not understood to provide any further distinction over the prior art method of Kim et al. in view of Yeon, as Kim et al. in view of Yeon teaches discloses, for example, TiN is formed by the process.).
CLAIM 15. Kim et al. in view of Yeon teaches method according to claim 7, wherein the thin film comprises a multilayer structure consisting of two or three layers (Multilayer film deposition using an existing ALD process, such as disclosed by Yeon, is a routine and obvious design choice in semiconductor manufacturing. It is well-known to stack materials. The ALD process in itself stacks atomic layers of the formed material to form a layer having a total thickness.).
CLAIM 16. A semiconductor substrate fabricated using the method according to claim 7 (This claim is not understood to provide any clear patentable distinction. Kim et al. in view of Yeon teaches forming a layer. By definition a layer is a substrate. A substrate refers to an underlying substance, base, or foundation material upon which another layer or process is applied or conducted. The formed layer is capable of such, thus may be considered a substrate meeting the scope of the claim.).
Conclusion
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JARRETT J. STARK
Primary Examiner
Art Unit 2822
4/6/2026
/JARRETT J STARK/Primary Examiner, Art Unit 2898
1 Kim et al. – Abstract: Abstract
The present invention provides a method for manufacturing a molybdenum-containing thin film and a molybdenum-containing thin film manufactured thereby. By using a molybdenum (0)-based hydrocarbon compound and a predetermined reaction gas, the method for manufacturing a molybdenum-containing thin film according to the present invention enables easy manufacturing of a highly pure thin film in a simple process.
Description:
[0004] Meanwhile, as a thin film deposition method in a semiconductor element, methods using molecular beam epitaxy (MBE), chemical vapor deposition (CVD), physical vapor deposition (PVD), or the like have been studied. Recently, as a design rule is decreased in accordance with a miniaturization of a semiconductor elements, as a deposition method satisfying a low temperature process, precise thickness control, uniformity and coatability of the thin film, a thin film formation using atomic layer deposition (ALD) according to self-limiting surface reaction mechanism has been widely studied.
[0005] Molybdenum carbonyl [Mo(CO).sub.6], molybdenum acetylacetonate, molybdenum chloride (MoCl.sub.3 or MoCl.sub.5), molybdenum fluoride (MoF.sub.6), organic molybdenum compounds such as MoO.sub.2(2,2,6,6-tetramethylheptane-3,5-dione).sub.2, biscyclopentadienyl molybdenum dihydride, bismethylcyclopentadienyl molybdenum dihydride, bisethylcyclopentadienyl molybdenum dihydride, bisisopropylcyclopentadienyl molybdenum dihydride, biscyclopentadienylimide molybdenum, and molybdenum oxychloride (MoO.sub.2Cl.sub.2 or MoOCl.sub.4) have been reported as raw materials for chemical vapor epitaxy for manufacturing a molybdenum oxide-containing thin film. In addition, a molybdenum amideimide compound has been reported as raw materials for forming a
[0041] A carbonyl-containing compound described herein may be used as a ligand of a molybdenum(0)-based hydrocarbon compound, and may be any compound having a carbonyl group, however, as a preferred example, the carbonyl-containing compound may be CO or acetylacetonate, but is not limited thereto.
2 Kim et al. – [0018] c) injecting a reaction gas which is iodine, (C1-C3)alkyl iodide, iodo silane, or a mixture thereof to manufacture the molybdenum-containing thin film on the substrate.
Prosecution Insights