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 .
Claims 1-8 and claims 15-20 are pending
Claims 9-14 are withdrawn due to restriction
Election/Restrictions
Applicant’s election without traverse of Invention I corresponding to claims 1-8 and 15-20 in the reply filed on 06/29/2026 is acknowledged.
Specification
Applicant is reminded of the proper content of an abstract of the disclosure.
A patent abstract is a concise statement of the technical disclosure of the patent and should include that which is new in the art to which the invention pertains. The abstract should not refer to purported merits or speculative applications of the invention and should not compare the invention with the prior art.
If the patent is of a basic nature, the entire technical disclosure may be new in the art, and the abstract should be directed to the entire disclosure. If the patent is in the nature of an improvement in an old apparatus, process, product, or composition, the abstract should include the technical disclosure of the improvement. The abstract should also mention by way of example any preferred modifications or alternatives.
Where applicable, the abstract should include the following: (1) if a machine or apparatus, its organization and operation; (2) if an article, its method of making; (3) if a chemical compound, its identity and use; (4) if a mixture, its ingredients; (5) if a process, the steps.
Extensive mechanical and design details of an apparatus should not be included in the abstract. The abstract should be in narrative form and generally limited to a single paragraph within the range of 50 to 150 words in length.
See MPEP § 608.01(b) for guidelines for the preparation of patent abstracts.
The abstract is objected to because it exceeds 150 words. Correction is required.
Double Patenting
The nonstatutory double patenting rejection is based on a judicially created doctrine grounded in public policy (a policy reflected in the statute) so as to prevent the unjustified or improper timewise extension of the “right to exclude” granted by a patent and to prevent possible harassment by multiple assignees. A nonstatutory double patenting rejection is appropriate where the conflicting claims are not identical, but at least one examined application claim is not patentably distinct from the reference claim(s) because the examined application claim is either anticipated by, or would have been obvious over, the reference claim(s). See, e.g., In re Berg, 140 F.3d 1428, 46 USPQ2d 1226 (Fed. Cir. 1998); In re Goodman, 11 F.3d 1046, 29 USPQ2d 2010 (Fed. Cir. 1993); In re Longi, 759 F.2d 887, 225 USPQ 645 (Fed. Cir. 1985); In re Van Ornum, 686 F.2d 937, 214 USPQ 761 (CCPA 1982); In re Vogel, 422 F.2d 438, 164 USPQ 619 (CCPA 1970); In re Thorington, 418 F.2d 528, 163 USPQ 644 (CCPA 1969).
A timely filed terminal disclaimer in compliance with 37 CFR 1.321(c) or 1.321(d) may be used to overcome an actual or provisional rejection based on nonstatutory double patenting provided the reference application or patent either is shown to be commonly owned with the examined application, or claims an invention made as a result of activities undertaken within the scope of a joint research agreement. See MPEP § 717.02 for applications subject to examination under the first inventor to file provisions of the AIA as explained in MPEP § 2159. See MPEP § 2146 et seq. for applications not subject to examination under the first inventor to file provisions of the AIA . A terminal disclaimer must be signed in compliance with 37 CFR 1.321(b).
The filing of a terminal disclaimer by itself is not a complete reply to a nonstatutory double patenting (NSDP) rejection. A complete reply requires that the terminal disclaimer be accompanied by a reply requesting reconsideration of the prior Office action. Even where the NSDP rejection is provisional the reply must be complete. See MPEP § 804, subsection I.B.1. For a reply to a non-final Office action, see 37 CFR 1.111(a). For a reply to final Office action, see 37 CFR 1.113(c). A request for reconsideration while not provided for in 37 CFR 1.113(c) may be filed after final for consideration. See MPEP §§ 706.07(e) and 714.13.
The USPTO Internet website contains terminal disclaimer forms which may be used. Please visit www.uspto.gov/patent/patents-forms. The actual filing date of the application in which the form is filed determines what form (e.g., PTO/SB/25, PTO/SB/26, PTO/AIA /25, or PTO/AIA /26) should be used. A web-based eTerminal Disclaimer may be filled out completely online using web-screens. An eTerminal Disclaimer that meets all requirements is auto-processed and approved immediately upon submission. For more information about eTerminal Disclaimers, refer to www.uspto.gov/patents/apply/applying-online/eterminal-disclaimer
Claims 1, 2, 7, and 8 are provisionally rejected on the ground of nonstatutory double patenting as being unpatentable over claims 14, 15, 17, and 18 of copending Application No. 18/542,776.
Although the claims at issue are not identical, they are not patentably distinct.
Regarding claim 1, claim 14 of copending Application No. 18/542,776 is directed to a substrate treatment method for etching a substrate at an atomic layer level including a surface treatment process in which the surface of the substrate is modified using plasma and a thermal treatment process that generates a desorption reaction on the surface of the substrate. Claim 17 of copending Application No. 18/542,776 further recites cooling the substrate such that the temperature of the substrate is maintained within a set temperature range and performing the cooling process after or simultaneously with the heating process. Claim 18 of copending Application No. 18/542,776 further recites performing the heating process using an upper heat source. Claim 1 of the instant application differs by reciting that the surface treatment process is performed in a processing unit, the desorption process and the temperature adjustment process are performed in a thermal treatment unit, and the substrate is cooled by a cooling plate in the thermal treatment unit. The difference is an obvious variation of the cyclic atomic layer etching process recited in claims 14, 17, and 18 of copending Application No. 18/542,776 because both claim sets recite the same sequence of plasma surface modification, thermal desorption by heating, substrate cooling to maintain a set temperature range, with the instant claim differing primarily in the organization of the processing equipment used to perform those processing steps.
Regarding claim 2, claim 14 of copending Application No. 18/542,776 recites that the surface treatment process and the thermal treatment process constitute one cycle and are repeated one or more times. The thermal treatment process of claim 14 includes both the heating process that produces desorption and the cooling process. Claim 2 of the instant application differs by separately identifying the desorption process and the temperature adjustment process as portions of the repeated cycle. The difference is an obvious variation of the repeated cyclic atomic layer etching process recited in claim 14 of copending Application No. 18/542,776 because the claimed thermal treatment process already includes both desorption by heating and subsequent or simultaneous substrate cooling.
Regarding claim 7, claim 17 of copending Application No. 18/542,776 recites performing the cooling process after the heating process or simultaneously with the heating process while maintaining the substrate within a set temperature range. Claim 7 of the instant application differs by reciting that the temperature adjustment process starts immediately after the desorption process or starts simultaneously with the desorption process. The difference is an obvious variation of the timing of the cooling operation in the cyclic thermal treatment process recited in claim 17 of copending Application No. 18/542,776 because the heating process is the process that generates the desorption reaction, and beginning cooling upon completion of that heating/desorption process or during that process would have predictably controlled the substrate temperature for the same thermal-treatment purpose.
Regarding claim 8, claim 15 of copending Application No. 18/542,776 recites that the heating process is performed in a state in which the substrate is moved upward from an upper surface of a support member on which the substrate is seated. Claim 8 of the instant application recites that the desorption process is performed either in a state in which the substrate is seated on the cooling plate or in a state in which the substrate is moved upward from the cooling plate. Because claim 8 is recited in the alternative, the claim encompasses the same raised-substrate configuration recited in claim 15 of copending Application No. 18/542,776. Accordingly, the additional limitation of claim 8 does not render the claim patentably distinct.
This is a provisional nonstatutory double patenting rejection because the patentably indistinct claims have not in fact been patented.
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.
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.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claims 1, 2, 7, and 8 are rejected under 35 U.S.C. 103 as being unpatentable over Paeng et al. (US 2022/0005740 A1) in view of Tsunekawa et al. (US 2012/0193071 A1).
Regarding claim 1, Paeng teaches a substrate treatment method etching a substrate at an atomic layer level (a thermal atomic layer etching process removes a predetermined amount of one or more layers during each cycle, including approximately 1 nm per cycle; paragraphs [0093]–[0096]).
Paeng teaches using a processing unit (processing chamber 108 includes substrate support 110, gas delivery system 160, RF generator 120-1, and controller 180 for performing substrate treatment operations; paragraphs [0071]–[0077]).
Paeng teaches a surface treatment process in which a surface of the substrate is modified in the processing unit (hydrogen, ammonia, or another gas is supplied with plasma during a first surface modification operation, followed by adsorption of oxygen, a halogen gas, nitrogen trifluoride, or another reactant during a second surface modification operation; paragraphs [0093]–[0094]).
Paeng teaches a desorption process in which the substrate that is surface-treated is heated, thereby generating a desorption reaction on the surface of the substrate that is surface-treated (rapid thermal processing is performed after surface modification and atomistic adsorption to thermally remove the modified material, including removal of a volatile titanium oxychloride layer; paragraphs [0093]–[0096] and [0125]–[0126]).
Paeng teaches heating the substrate by an upper heat source (heat source 126 includes flash lamps 128 disposed above processing chamber 108 and configured to direct thermal energy through window assembly 130 toward substrate 112; paragraph [0073]).
Paeng teaches a temperature adjustment process in which the substrate is cooled (the substrate cools during the surface-refresh operation, and active cooling may be provided to shorten the cooling time and permit additional cycles; paragraphs [0097] and [0103]).
Paeng teaches maintaining a temperature of the substrate at a set temperature range (temperature-control system 150 controls fluid supplied through fluid channels 114 and operation of heaters 116 to control the temperatures of substrate support 110 and substrate 112, and the rapid-thermal-pulse number, duration, intensity, and frequency are controlled to provide a selected substrate temperature profile; paragraphs [0074] and [0092]).
Paeng does not expressly teach performing the surface treatment process in a processing unit separate from a thermal treatment unit in which the desorption process and temperature adjustment process are performed.
Tsunekawa teaches a thermal treatment unit separate from other substrate-processing units (vacuum heating/cooling apparatus 29 is connected through vacuum transfer chamber 22 to separate film-forming chambers, etching chamber 27, and an optional oxidation-treatment chamber, permitting transfer between chambers without breaking vacuum; paragraphs [0077]–[0081]).
Tsunekawa teaches heating the substrate in the thermal treatment unit by an upper heat source (halogen lamp 2 is positioned above vacuum chamber 1 and irradiates substrate 5 through quartz window 3 while the substrate is positioned at heating position P3; paragraphs [0061], [0068], and [0081]).
Tsunekawa teaches cooling the substrate by a cooling plate in the thermal treatment unit (substrate-supporting base 9 is cooled by water-cooling jacket 10 and cooling-water path 12, and the substrate is cooled while placed on or positioned close to substrate-supporting base 9; paragraphs [0062]–[0064], [0067], and [0083]).
Tsunekawa teaches maintaining the temperature of the substrate at a set temperature range (the input power of halogen lamp 2 is controlled to maintain the substrate temperature at a certain value, followed by cooling the substrate on the cooled substrate-supporting base to approximately room temperature; paragraphs [0081]–[0084]).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to perform Paeng’s surface treatment process in a processing unit and to perform Paeng’s thermal removal and cooling operations in a separate thermal treatment unit configured as taught by Tsunekawa, because use of the separate thermal treatment unit would have predictably permitted the thermal removal and cooling conditions to be controlled independently from the surface treatment conditions while maintaining the substrate under vacuum and enabling rapid heating and cooling. The modification would have amounted to using Tsunekawa’s known separate vacuum heating/cooling arrangement to perform the corresponding thermal removal and cooling functions of Paeng, yielding the predictable result of Paeng’s thermal ALE process performed using separately controlled processing and thermal treatment units. See MPEP § 2143(I)(C).
Regarding claim 2, modified Paeng teaches the substrate treatment method of claim 1 as set forth above.
Paeng further teaches that the surface treatment process, the desorption process, and the temperature adjustment process constitute one cycle (a thermal ALE cycle includes pretreatment, atomistic adsorption, rapid thermal processing for thermal removal, and a surface-refresh operation during which the substrate cools; paragraphs [0093]–[0097]).
Paeng teaches that the cycle is repeated one or more times (the thermal ALE process is iteratively performed for a predetermined number of cycles to remove a predetermined amount of material, including an embodiment in which 100 cycles are performed; paragraphs [0093], [0095], and [0125]–[0126]).
Regarding claim 7, modified Paeng teaches the substrate treatment method of claim 2 as set forth above.
Tsunekawa further teaches that the temperature adjustment process starts immediately after the desorption process (substrate-supporting base 9 is cooled before the heating treatment is completed, power to halogen lamp 2 is stopped upon completion of the heating treatment, and the heated substrate is then lowered to cooling position P1 on the already-cooled substrate-supporting base 9; paragraphs [0082]–[0084] and [0090]).
Regarding claim 8, modified Paeng teaches the substrate treatment method of claim 7 as set forth above.
Tsunekawa further teaches that the desorption process is performed in a state in which the substrate is moved upward from the cooling plate (substrate 5 is raised by lift pins 13 from cooled substrate-supporting base 9 to heating position P3 closer to upper halogen lamp 2, and the heating treatment is performed while the substrate is held at the raised heating position; paragraphs [0065]–[0068] and [0081]).
Claim 3 is rejected under 35 U.S.C. 103 as being unpatentable over Paeng et al. in view of Tsunekawa et al., as applied to claim 2 above, and further in view of Kuznetsov et al. (US 2023/0416912 A1).
Regarding claim 3, modified Paeng teaches the substrate treatment method of claim 2 as set forth above.
Modified Paeng does not expressly teach that the cycle comprises a first substrate transfer process performed between the surface treatment process and the desorption process and a second substrate transfer process performed after the temperature adjustment process, wherein the substrate is transferred from the thermal treatment unit to the processing unit when a subsequent cycle exists.
Kuznetsov teaches a first substrate transfer process performed between a first process step and a second process step (substrate 24 is processed in subsequent and alternating first and second process steps in respective first and second single-substrate process chambers 12 and 14 and is transferred between the chambers between the subsequent process steps; paragraphs [0049] and [0051]–[0052]).
Kuznetsov teaches that the first substrate transfer process is performed such that the substrate is transferred to the second process chamber from the first process chamber (sealing ring 42 and pins 54 transport substrate 24 from first process chamber 12 to second process chamber 14; paragraphs [0038]–[0040]).
Kuznetsov teaches a second substrate transfer process performed after the second process step such that the substrate is transferred to the first process chamber from the second process chamber when a subsequent cycle exists (sealing ring 42 and pins 54 transport substrate 24 between first and second process chambers 12 and 14 in either direction, and the substrate is processed in subsequent and alternating process steps requiring transfer between the chambers; paragraphs [0038]–[0040] and [0049]).
Kuznetsov teaches repeatedly performing the alternating first and second process steps (a first precursor is supplied in first process chamber 12, second and third precursors are supplied in second process chamber 14, and the process cycle is repeatedly performed; paragraphs [0054], [0057]–[0058]).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to configure the modified Paeng process to transfer the substrate between the processing unit and thermal treatment unit for each successive surface-treatment and thermal-treatment step, as taught by Kuznetsov, because the alternating transfer arrangement would have predictably permitted each step to be performed under independently controlled chamber conditions and would have returned the substrate to the processing unit when another ALE cycle was required. The modification would have amounted to applying Kuznetsov’s known bidirectional chamber-transfer arrangement to the successive processing and thermal-treatment operations of modified Paeng, yielding the predictable result of repeated ALE cycles performed in the respective units. See MPEP § 2143(I)(C).
Claims 4, 5, and 6 are rejected under 35 U.S.C. 103 as being unpatentable over Paeng et al. in view of Tsunekawa et al. and Kuznetsov et al., as applied to claim 3 above, and further in view of Zhang et al. (WO 2020/150043 A1) and Abel (US 20230117790 A1).
Regarding claim 4, modified Paeng further modified by Kuznetsov teaches the substrate treatment method of claim 3 as set forth above.
Modified Paeng does not expressly teach that the surface treatment process comprises an oxidation process in which a process gas including oxygen is supplied to a processing space of the processing unit and then converted into plasma, thereby oxidizing the surface of the substrate, and a modification process in which a ligand of the surface oxidized by the oxidation process is exchanged by supplying a precursor to the processing space.
Zhang teaches that the surface treatment process comprises an oxidation process in which a process gas including oxygen is supplied to a processing space of the processing unit (molecular oxygen plasma is supplied to processing chamber 108 during a first surface-modification operation; paragraphs [0055], [0070]–[0071], and [0090]).
Zhang teaches that the process gas is converted into plasma, thereby oxidizing the surface of the substrate (O₂ plasma is supplied to convert a metal-containing surface, including TiN, to an oxidized surface such as TiO₂; paragraphs [0071], [0081]–[0085], and [0090]).
Zhang teaches supplying a precursor to the processing space during a subsequent modification process (the oxidized metal-containing surface is exposed to Hhfac, Hacac, chlorine, or another ligand or organic species to form a metal-ligand complex for subsequent thermal removal; paragraphs [0070]–[0072] and [0081]–[0085]).
Zhang does not expressly teach that a ligand of the surface that is oxidized by the oxidation process is exchanged by supplying the precursor to the processing space.
Abel teaches a modification process in which a ligand of an oxidized surface is exchanged by supplying a precursor containing a replacement ligand (a molybdenum surface is oxidized to form a molybdenum oxide passivation layer complexed with oxalic acid, and a dissolution solution containing ascorbic acid is supplied such that a ligand-exchange mechanism exchanges the oxalic acid in the oxymolybdenum oxalate complex with ascorbic acid to form an oxymolybdenum ascorbate complex; paragraphs [0080]–[0082] and [0086]).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to perform Zhang’s modification of the oxidized surface using the ligand-exchange mechanism taught by Abel because Abel teaches that supplying a replacement ligand to a ligand-metal complex on an oxidized surface exchanges the existing ligand and forms a different removable ligand-metal species. Applying Abel’s known ligand-exchange mechanism to Zhang’s oxidized surface would have predictably facilitated formation of a removable modified surface layer for the subsequent atomic-layer etching removal operation. See MPEP § 2143(I)(C).
Regarding claim 5, modified Paeng further modified by Kuznetsov, Zhang, and Abel teaches the substrate treatment method of claim 4 as set forth above.
Modified Paeng does not expressly teach that the surface treatment process further comprises a purge process purging the processing space of the processing unit, wherein the purge process is performed between the oxidation process and the modification process and after the modification process.
Zhang teaches that the surface treatment process further comprises a purge process purging the processing space of the processing unit (the gas-delivery system selectively supplies purge-gas mixtures during surface modification, atomistic adsorption, and purging operations; paragraph [0055]).
Zhang teaches that the purge process is performed between the oxidation process and the modification process (ALE includes a first operation A followed by pumping or purging residual material from the processing chamber before performing a second operation B; paragraph [0128]).
Zhang teaches that the purge process is performed after the modification process (the processing chamber is purged after atomistic adsorption and before thermal annealing, and remaining gases or products are pumped or purged after the second operation; paragraphs [0093], [0128], [0149], and [0167]).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to purge the processing space between Zhang’s oxygen-plasma oxidation operation and the subsequent ligand-modification operation and again after the ligand-modification operation, because the intervening purges would have predictably removed residual reactants and prevented the respective reactants from undesirably mixing outside their intended sequential surface reactions. The modification would have constituted use of a known purge sequence between successive ALE reaction steps to obtain predictable reaction isolation and process control. See MPEP § 2143(I)(C).
Regarding claim 6, modified Paeng further modified by Kuznetsov, Zhang, and Abel teaches the substrate treatment method of claim 4 as set forth above.
Modified Paeng does not expressly teach that the substrate comprises a ruthenium thin film and that the set temperature range is a temperature range in which RuO₄ is not generated on the ruthenium thin film during the oxidation process.
Kuznetsov teaches that the substrate comprises a ruthenium thin film (a ruthenium monolayer is formed and processed through successive Ru precursor and oxygen exposures; paragraph [0062]).
Kuznetsov teaches that the set temperature range is a temperature range in which RuO₄ is not generated on the ruthenium thin film during the oxidation process (the first process chamber is maintained within a selected temperature range during oxygen exposure, and the first process temperature is tuned to achieve the desired reaction while avoiding etching of ruthenium through formation of volatile RuO₄; paragraph [0062]).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention, when applying the oxidation and ligand-modification process to a ruthenium thin film, to control the substrate within the temperature range taught by Kuznetsov to avoid formation of volatile RuO₄, because Kuznetsov teaches that temperature selection during oxygen exposure permits the desired ruthenium oxidation reaction while avoiding undesirable etching through formation of volatile RuO₄. The modification would have predictably preserved the ruthenium surface for controlled atomic-layer processing while avoiding uncontrolled volatile-oxide formation. See MPEP § 2143 (I)(C).
Claim 15 is rejected under 35 U.S.C. 103 as being unpatentable over Paeng et al. (US 2022/0005740 A1) in view of Tsunekawa et al. (US 2012/0193071 A1) and further in view of Kuznetsov et al. (US 2023/0416912 A1).
Regarding claim 15, Paeng teaches a substrate treatment method etching a substrate at an atomic layer level (a thermal atomic layer etching process removes a predetermined amount of one or more layers during each cycle, including approximately 1 nm per cycle; paragraphs [0093]–[0096]).
Paeng teaches using a processing unit (processing chamber 108 includes substrate support 110, gas delivery system 160, RF generator 120-1, and controller 180 for performing substrate-treatment operations; paragraphs [0071]–[0077]).
Paeng teaches a surface treatment process in which a surface of the substrate is modified in the processing unit (hydrogen, ammonia, or another gas is supplied with plasma during a first surface-modification operation, followed by adsorption of oxygen, a halogen gas, nitrogen trifluoride, or another reactant during a second surface-modification operation; paragraphs [0093]–[0094]).
Paeng teaches a desorption process in which the substrate that is surface-treated is heated, thereby generating a desorption reaction on the surface of the substrate that is surface-treated (rapid thermal processing is performed after surface modification and atomistic adsorption to thermally remove the modified surface material, including removal of a volatile titanium oxychloride layer; paragraphs [0093]–[0096] and [0125]–[0126]).
Paeng teaches that the substrate is heated by an upper heat source during the desorption process (heat source 126 includes flash lamps 128 positioned above processing chamber 108 and configured to direct thermal energy through window assembly 130 toward substrate 112; paragraph [0073]).
Paeng teaches a temperature adjustment process in which the substrate is cooled (the substrate cools during the surface-refresh operation, and active cooling may be provided to shorten the cooling time and permit additional cycles; paragraphs [0097] and [0103]).
Paeng teaches maintaining a temperature of the substrate at a set temperature range (temperature-control system 150 controls fluid supplied through fluid channels 114 and operation of heaters 116 to control the temperatures of substrate support 110 and substrate 112, and the number, duration, intensity, and frequency of the rapid thermal pulses are controlled to provide a selected substrate-temperature profile; paragraphs [0074] and [0092]).
Paeng teaches that the surface treatment process, the desorption process, and the temperature adjustment process constitute one cycle (the thermal ALE cycle includes pretreatment, atomistic adsorption, rapid thermal processing for thermal removal, and a surface-refresh operation during which the substrate cools; paragraphs [0093]–[0097]).
Paeng teaches that the cycle is repeated one or more times (the thermal ALE process is iteratively performed for a predetermined number of cycles to remove a predetermined amount of material, including an embodiment in which 100 cycles are performed; paragraphs [0093], [0095], and [0125]–[0126]).
Paeng does not expressly teach using a processing unit and a separate thermal treatment unit such that the surface treatment process is performed in the processing unit and the desorption process and temperature adjustment process are performed in the thermal treatment unit.
Tsunekawa teaches a thermal treatment unit separate from other substrate-processing units (vacuum heating/cooling apparatus 29 is connected through vacuum transfer chamber 22 to separate film-forming chambers, etching chamber 27, and an optional oxidation-treatment chamber, permitting transfer between the chambers without breaking vacuum; paragraphs [0077]–[0081]).
Tsunekawa teaches performing the desorption process in the thermal treatment unit by heating the substrate with an upper heat source (halogen lamp 2 is positioned above vacuum chamber 1 and irradiates substrate 5 through quartz window 3 while the substrate is positioned at heating position P3; paragraphs [0061], [0068], and [0081]).
Tsunekawa teaches performing the temperature adjustment process in the thermal treatment unit by cooling the substrate with a cooling plate (substrate-supporting base 9 is cooled by water-cooling jacket 10 and cooling-water path 12, and substrate 5 is cooled while placed on or positioned close to substrate-supporting base 9; paragraphs [0062]–[0064], [0067], and [0083]).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to perform Paeng’s surface treatment process in a processing unit and to perform Paeng’s thermal desorption and cooling operations in a separate thermal treatment unit configured as taught by Tsunekawa because the separate thermal treatment unit would have predictably permitted the thermal-desorption and cooling conditions to be controlled independently from the surface-treatment conditions while maintaining the substrate under vacuum and enabling rapid heating and cooling. See MPEP § 2143(I)(C).
Modified Paeng does not expressly teach that the substrate comprises a ruthenium thin film.
Kuznetsov teaches a substrate comprising a ruthenium thin film (a ruthenium layer is formed and subjected to successive Ru-precursor, oxygen, and hydrogen exposures; paragraph [0062]).
Modified Paeng does not expressly teach a first substrate transfer process in which the substrate that is surface-treated in the surface treatment process is transferred to the thermal treatment unit from the processing unit.
Kuznetsov teaches a first substrate transfer process in which a substrate is transferred from a first process chamber to a second process chamber between subsequent and alternating process steps (substrate 24 is transferred from first single-substrate process chamber 12 to second single-substrate process chamber 14 using sealing ring 42 and pins 54; paragraphs [0038]–[0040] and [0049]).
Modified Paeng does not expressly teach a second substrate transfer process of transferring the substrate in which the temperature adjustment process is completed to the processing unit from the thermal treatment unit when a subsequent cycle exists.
Kuznetsov teaches a second substrate transfer process of transferring the substrate from the second process chamber to the first process chamber when a subsequent alternating process step exists (sealing ring 42 and pins 54 transfer substrate 24 between first and second process chambers 12 and 14 in either direction, and the substrate is processed in subsequent and alternating process steps requiring repeated transfer between the respective chambers; paragraphs [0038]–[0040], [0049], and [0054]).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to apply the modified Paeng process to a substrate comprising a ruthenium thin film and to transfer the substrate between the processing unit and the thermal treatment unit for each successive surface-treatment and thermal-treatment step, as taught by Kuznetsov. Ruthenium was a known material for cyclic atomic-layer processing, and Kuznetsov’s bidirectional transfer arrangement would have predictably permitted each process step to be performed under independently controlled chamber conditions while returning the substrate to the processing unit when a subsequent cycle existed. See MPEP § 2143(I)(C).
Claims 16–20 are rejected under 35 U.S.C. 103 as being unpatentable over Paeng et al. in view of Tsunekawa et al. and Kuznetsov et al., as applied to claim 15 above and further in view of Zhang et al. (WO 2020/150043 A1) and Abel (US 2023/0117790 A1).
Regarding claim 16, modified Paeng teaches the substrate treatment method of claim 15 as set forth above.
Modified Paeng does not expressly teach...
Zhang teaches that the surface treatment process comprises an oxidation process in which a process gas comprising oxygen is supplied to a processing space of the processing unit (molecular oxygen plasma is supplied to processing chamber 108 during a first surface-modification operation; paragraphs [0055], [0070]–[0071], and [0090]).
Zhang teaches that the process gas is converted into plasma, thereby oxidizing the surface of the Ru thin film (O₂ plasma oxidizes a metal-containing surface, including conversion of a metal or metal nitride to a metal oxide, and the established combination applies that oxidation process to the Ru thin film taught by Kuznetsov; Zhang paragraphs [0071], [0081]–[0085], and [0090]; Kuznetsov paragraph [0062]).
Zhang teaches supplying a precursor to the processing space during a subsequent modification process (the oxidized metal-containing surface is exposed to Hhfac, Hacac, chlorine, or another ligand or organic species to form a metal-ligand complex for subsequent thermal removal; paragraphs [0070]–[0072] and [0081]–[0085]).
Zhang does not expressly teach that a ligand of the surface of the Ru thin film that is oxidized by the oxidation process is exchanged by supplying the precursor to the processing space.
Abel teaches a modification process in which a ligand of an oxidized metal surface is exchanged by supplying a precursor containing a replacement ligand (a molybdenum surface is oxidized to form a molybdenum oxide passivation layer complexed with oxalic acid, and a dissolution solution containing ascorbic acid is supplied such that a ligand-exchange mechanism exchanges the oxalic acid in the oxymolybdenum oxalate complex with ascorbic acid to form an oxymolybdenum ascorbate complex; paragraphs [0080]–[0082] and [0086]).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to perform Zhang’s modification of the oxidized surface using the ligand-exchange mechanism taught by Abel because Abel teaches that supplying a replacement ligand to a ligand-metal complex on an oxidized surface exchanges the existing ligand and forms a different removable ligand-metal species. Applying Abel’s known ligand-exchange mechanism to the oxidized Ru surface of modified Paeng would have predictably facilitated formation of a removable modified surface layer for the subsequent atomic-layer etching removal operation. See MPEP § 2143(I)(C).
Regarding claim 17, modified Paeng further modified by Kuznetsov, Zhang, and Abel teaches the substrate treatment method of claim 16 as set forth above.
Paeng teaches a temperature adjustment process performed during repetition of the cycle (the substrate cools during each surface-refresh operation, active cooling shortens the recovery time, and repeated heating and cooling cycles are performed without substantially increasing the temperature of the bulk substrate; paragraphs [0069], [0093]–[0097], and [0103]).
Paeng does not expressly teach that the temperature adjustment process prevents a generation of RuO4 in the oxidation process due to repetition of the cycle from occurring.
Kuznetsov teaches preventing generation of RuO₄ in an oxidation process by controlling the temperature of the ruthenium substrate during oxygen exposure (the first process temperature is tuned to permit the desired Ru/O₂ reaction while avoiding etching of ruthenium through formation of volatile RuO₄; paragraph [0062]).
Accordingly, modified Paeng teaches that the temperature adjustment process prevents a generation of RuO₄ in the oxidation process due to repetition of the cycle from occurring (Paeng cools the substrate during repeated cycles to prevent cumulative heating, while Kuznetsov controls the temperature during oxygen exposure of ruthenium to avoid formation of volatile RuO₄; Paeng paragraphs [0069], [0093]–[0097], and [0103]; Kuznetsov paragraph [0062]).
Regarding claim 18, modified Paeng further modified by Kuznetsov, Zhang, and Abel teaches the substrate treatment method of claim 16 as set forth above.
Modified Paeng does not expressly teach wherein the surface treatment process further comprises a purge process purging the processing space of the processing unit, and the purge process is performed between the oxidation process and the modification process and is performed after the modification process.
Zhang teaches that the surface treatment process further comprises a purge process purging the processing space of the processing unit (delivery system 160 selectively supplies purge-gas mixtures during surface modification, atomistic adsorption, and purging operations; paragraph [0055]).
Zhang teaches that the purge process is performed between the oxidation process and the modification process (ALE includes a first operation followed by pumping or purging residual material before a second operation is performed; paragraph [0128]).
Zhang teaches that the purge process is performed after the modification process (the processing chamber is purged after atomistic adsorption and before thermal annealing, and remaining gases or products are pumped or purged after the second operation; paragraphs [0093], [0128], [0149], and [0167]).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to purge the processing space between the oxygen-plasma oxidation operation and the subsequent ligand-modification operation and again after the ligand-modification operation, because the intervening purges would have predictably removed residual reactants, prevented unintended gas-phase mixing, and isolated the respective sequential surface reactions. See MPEP § 2143(I)(C).
Regarding claim 19, modified Paeng teaches the substrate treatment method of claim 16 as set forth above.
modified Paeng further teaches that the temperature adjustment process starts immediately after the desorption process (Tsunekawa further teaches substrate-supporting base 9 is cooled before the heating treatment finishes, power to upper halogen lamp 2 is then stopped, and the heated substrate is lowered to cooling position P1 on the already-cooled substrate-supporting base; paragraphs [0082]–[0084] and [0090]).
Regarding claim 20, modified Paeng further modified by Kuznetsov, Zhang, and Abel teaches the substrate treatment method of claim 19 as set forth above.
modified Paeng further teaches that the desorption process is performed in a state in which the substrate is moved upward from the cooling plate (Tsunekawa further teaches substrate 5 is moved upward by lift pins 13 from cooled substrate-supporting base 9 to heating position P3, which is positioned closer to upper halogen lamp 2, and the heating treatment is performed while the substrate is held at the raised heating position; paragraphs [0065]–[0068] and [0081]).
Conclusion
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/JONATHAN L CARTER/Examiner, Art Unit 1713
/ERIN F BERGNER/Primary Examiner, Art Unit 1713
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