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 .
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and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114.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 6/1/2026 has been entered.
Response to Amendment
The amendment filed 6/1/2026 is entered and fully considered.
The amendment incorporates limitations from claims 2 and 3 and further limits the pre-treatment of the substate to be UV radiation instead of UV or plasma. In view of the amendment, a new rejection with additional prior art is used to teach the pretreatment of a substrate using UV radiation.
Claim Rejections - 35 USC § 103
The text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
Claim(s) 1, 4, 5, 8-10, 12-15, and 21-23 is/are rejected under 35 U.S.C. 103 as being unpatentable over RABKIN et al. (US 9,721,963) in view of BROGAN et al. (US 2023/0260834) and HAN et al. (US 2020/0361969) and NELSON et al. (US 2014/0061649).
Regarding claims 1, 5, and 21,
RABKIN teaches a method of making a metal dichalcogenide layer 60L on a memory film 50 which includes dielectric material hafnium oxide, aluminum oxide column 13 lines 42-51 and dichalcogenides of transition metals column 13 lines 52+. Referring to Fig. 3F, the dichalcogenide layer 60L is formed on an epitaxial pedestal 11 which is a semiconductor material column 9 lines 49-54. The metal dichalcogenide layer is formed by first depositing a metal oxide by ALD process and converting the metal oxide to a metal dichalcogenide column 15 lines 1-12. The metal that is provided for the ALD process is considered a metal precursor for the metal oxide film.
The RABKIN reference teaches using oxygen as the reactant to form the metal oxide (molybdenum or tungsten oxide) film but does not teach using deionized or deoxygenated water. However, when performing an ALD process for a diffusion barrier on semiconductor, BROGAN teaches tungsten precursors [0102] and [0112] can be used with water or oxygen (equivalents) [0113]. At the time of filing the invention it would have been prima facie obvious to one of ordinary skill in the art to use alcohol instead of oxygen as a simple substitution of equivalent oxidants when making metal oxides.
The BROGAN reference does not specify that the water is deionized or deoxygenated. However, HAN teaches ALD deposition of metal oxides and notes that the water used as the oxidant can be deionized or distilled water [0159]. Distilled water is interpreted to be deoxygenated water. At the time of filing the invention it would have been prima facie obvious to use deionized or distilled water as the water in BROGAN because one of ordinary skill is naturally inclined to use pure reactants.
RABKIN teaches ALD but does not teach pretreatment of the substrate surface with ultraviolet radiation. However, NELSON teaches prior to depositing a layer by ALD a pretreating step can be performed including dry cleaning by UV-ozone treatment [0062]. At the time of filing the invention it would have been prima facie obvious to one of ordinary skill in the art to use the pretreatment process of NELSON to provide a clean surface for subsequent ALD.
Regarding claims 4 and 10,
RABKIN teaches an annealing step at 200°C for the metal oxide before sulfurization (transition to dichalcogenide) column 15 lines 14-19. The annealing process is a removing organic contaminants (purging precursor and alcohol oxidant). The subsequent conversion to metal dichalcogenide is done by ramping up the temperature of up to 900°C column 15 lines 20-22. The examiner notes that when ramping up the temperature, at least some of the conversion of oxide to dichalcogenide occurs within the required temperature range and satisfies the claim language.
Regarding claims 8 and 9,
RABKIN teaches depositing a metal oxide (tungsten and molybdenum) by ALD but does not expressly teach the metal precursors used. However, BROGAN teaches that when depositing metal oxide by ALD [0102] tungsten precursors include bis(tert-butylimido)bis(dimethylamido) tungsten [0112]. At the time of filing the invention it would have been prima facie obvious to one of ordinary skill in the art to use the metal precursor of BROGAN as a substitution of art recognized equivalent precursors for metal oxides deposited by ALD.
Regarding claims 12-13,
The conversion of oxide to chalcogenide is argon and H2S (chalcogenide precursor) column 15 line 22. The flows are oxygen-free.
Regarding claim 14,
The deposition of material into the memory hole (at least one feature) is considered to be formation of the oxide and transition to dichalcogenide “on” the at least one feature.
Regarding claim 15,
RABKIN does not refer to any transfer of the substrate during fabrication. Accordingly, the method is interpreted to be performed in a single chamber.
Regarding claims 22-23,
The claims limit the UV process but do not positively require the UV treatment to be used. The UV treatment is required in the alternative with the plasma treatment. Accordingly, when BROGAN teaches the use of CO2 plasma [0005] and [0101] the claim limitations are met.
Claim(s) 3, 22 and 23 is/are rejected under 35 U.S.C. 103 as being unpatentable over RABKIN et al. (US 9,721,963) in view of BROGAN et al. (US 2023/0260834) and HAN et al. (US 2020/0361969) and NELSON et al. (US 2014/0061649) further in view of GANESAN et al (US 5,275,667).
Regarding claims 3, 22, and 23,
NELSON teaches performing a UV-ozone treatment but does not teach the duration of the cleaning process. However, GANESAN generally teaches that when performing a UV/ozone clean, the duration of the process is determined by a desired level of cleanliness columns 1-2. The contamination and time are linearly related (see the unlabeled figure) exact time can be found experimentally columns 3-4. At the time of filing the invention it would have been prima facie obvious to one of ordinary skill in the art to find an optimal time for cleaning by achieving a desired level of cleanliness without wasting time and energy beyond the target cleanliness.
Claim(s) 4 is/are rejected under 35 U.S.C. 103 as being unpatentable over RABKIN et al. (US 9,721,963) in view of BROGAN et al. (US 2023/0260834) and HAN et al. (US 2020/0361969) further in view of CLOTHIER et al. (US 2012/0164324).
Regarding claim 4,
RABKIN teaches an annealing step at 200°C for the metal oxide before sulfurization (transition to dichalcogenide) column 15 lines 14-19. The annealing process is a removing organic contaminants (purging precursor and alcohol oxidant). The subsequent conversion to metal dichalcogenide is done by ramping up the temperature of up to 900°C column 15 lines 20-22. The reference does not expressly teach using a lower temperature for conversion of oxide to dichalcogenide. However, COTHIER teaches that when converting metal oxide to metal sulfide the temperature can be maintained at 100-300°C [0029]. Generally changes in temperature are not patentable without showing unexpected results. In this instance the prior art shows that the reaction of metal oxide to metal sulfide (chalcogenide) can be performed at lower temperatures if needed. At the time of filing the invention it would have been prima facie obvious to one of ordinary skill in the art to change the temperature of the conversion reaction as routine optimization MPEP 2144.05.II.
Claim(s) 6 is/are rejected under 35 U.S.C. 103 as being unpatentable over RABKIN et al. (US 9,721,963) in view of BROGAN et al. (US 2023/0260834) and HAN et al. (US 2020/0361969) further in view of ZHOU et al. (US 2024/0379424).
Regarding claim 6,
RABKIN teaches making a memory opening 49 with a depth of up to 1-50nm column 9 lines 10-11. The reference is silent to the width of the opening or the resulting aspect ratio, but one of ordinary skill would look to the art to determine a suitable memory structure. However, ZHOU teaches a method of etching memory holes in a similar alternating stack and teaches the memory openings have can have an aspect ratio of 3-20 [0095]. At the time of filing the invention it would have been prima facie to use a known memory hole aspect ratio because the RABKIN reference does not specifically teach the width or aspect ratio of the etched memory holes.
Claim(s) 11, 16, 19, and 20 is/are rejected under 35 U.S.C. 103 as being unpatentable over RABKIN et al. (US 9,721,963) in view of BROGAN et al. (US 2023/0260834) and HAN et al. (US 2020/0361969) further in view of JAHANGIR et al. (US 2018/0226248) and CLOTHIER et al. (US 2012/0164324).
Regarding claim 11
RABKIN teaches a flow rate of argon and precursor during conversion of oxide to chalcogenide but does not expressly teach the pressure. However, generally changes in temperature and pressure are not considered patentable without showing unexpected results, MPEP 2144.05.II. In addition, JAHANGIR teaches that when converting a metal oxide to chalcogenide the partial pressure of the chalcogenide is 0.1 to 20 Torr [0052]. At the time of filing the invention it would have been prima facie obvious to one of ordinary skill in the art to use relatively low pressure as a change in pressure that is shown as operable in JAHANGIR, MPEP 2144.05.II.
Regarding claims 16 and 19,
RABKIN teaches a method of making a metal dichalcogenide layer 60L on a memory film 50 which includes dielectric material hafnium oxide, aluminum oxide column 13 lines 42-51 and dichalcogenides of transition metals column 13 lines 52+.. Referring to Fig. 3F, the dichalcogenide layer 60L is formed on an epitaxial pedestal 11 which is a semiconductor material column 9 lines 49-54. The metal dichalcogenide is a transition metal dichalcogenide column 12 lines 24-27. The metal dichalcogenide layer is formed by first depositing a metal oxide by ALD process and converting the metal oxide to a metal dichalcogenide column 15 lines 1-12. The metal that is provided for the ALD process is considered a metal precursor for the metal oxide film.
The reference teaches using oxygen as the reactant to form the metal oxide (molybdenum or tungsten oxide) film but does not teach using deionized or deoxygenated water. However, when performing an ALD process for a diffusion barrier on semiconductor, BROGAN teaches tungsten precursors [0102] and tungsten precursors include bis(tert-butylimido)bis(dimethylamido) tungsten [0112] can be used with water or oxygen (indicating equivalent reactants) [0113]. At the time of filing the invention it would have been prima facie obvious to one of ordinary skill in the art to use the metal precursor of BROGAN as a substitution of art recognized equivalent precursors for metal oxides deposited by ALD.
The BROGAN reference does not specify that the water is deionized or deoxygenated. However, HAN teaches ALD deposition of metal oxides and notes that the water used as the oxidant can be deionized or distilled water [0159]. Distilled water is interpreted to be deoxygenated water. At the time of filing the invention it would have been prima facie obvious to use deionized or distilled water as the water in BROGAN because one of ordinary skill is naturally inclined to use pure reactants. The HAN reference shows the different purified forms of water used to make metal oxides by ALD.
RABKIN teaches a flow rate of argon and precursor during conversion of oxide to chalcogenide but does not expressly teach the pressure. However, generally changes in temperature and pressure are not considered patentable without showing unexpected results, MPEP 2144.05.II. In addition, JAHANGIR teaches that when converting a metal oxide to chalcogenide the partial pressure of the chalcogenide is 0.1 to 20 Torr [0052]. At the time of filing the invention it would have been prima facie obvious to one of ordinary skill in the art to use relatively low pressure as a change in pressure that is shown as operable in JAHANGIR, MPEP 2144.05.II.
RABKIN teaches an annealing step at 200°C for the metal oxide before sulfurization (transition to dichalcogenide) column 15 lines 14-19. The annealing process is a removing organic contaminants (purging precursor and alcohol oxidant). The subsequent conversion to metal dichalcogenide is done by ramping up the temperature of up to 900°C column 15 lines 20-22. The reference does not expressly teach using a lower temperature for conversion of oxide to dichalcogenide. However, COTHIER teaches that when converting metal oxide to metal sulfide the temperature can be maintained at 100-300°C [0029]. Generally changes in temperature are not patentable without showing unexpected results. In this instance the prior art shows that the reaction of metal oxide to metal sulfide (chalcogenide) can be performed at lower temperatures if needed. At the time of filing the invention it would have been prima facie obvious to one of ordinary skill in the art to change the temperature of the conversion reaction as routine optimization MPEP 2144.05.II.
Regarding claim 20,
RABKIN does not refer to any transfer of the substrate during fabrication. Accordingly, the method is interpreted to be performed in a single chamber.
Claim(s) 18 is/are rejected under 35 U.S.C. 103 as being unpatentable over RABKIN et al. (US 9,721,963) in view of BROGAN et al. (US 2023/0260834) and HAN et al. (US 2020/0361969) further in view of JAHANGIR et al. (US 2018/0226248) and CLOTHIER et al. (US 2012/0164324) further in view of GANESAN et al (US 5,275,667).
Regarding claim 18,
NELSON teaches performing a UV-ozone treatment but does not teach the duration of the cleaning process. However, GANESAN generally teaches that when performing a UV/ozone clean, the duration of the process is determined by a desired level of cleanliness columns 1-2. The contamination and time are linearly related (see the unlabeled figure) exact time can be found experimentally columns 3-4. At the time of filing the invention it would have been prima facie obvious to one of ordinary skill in the art to find an optimal time for cleaning by achieving a desired level of cleanliness without wasting time and energy beyond the target cleanliness.
Conclusion
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/AUSTIN MURATA/Primary Examiner, Art Unit 1712
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