DETAILED ACTION
Table of Contents
I. Notice of Pre-AIA or AIA Status 3
II. Priority Date for Current Claims 3
III. Claim Objections 3
IV. Claim Rejections - 35 USC § 102 4
A. Claims 18, 20, 23, and 24 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by US 2016/0233309 (“Miyamoto”). 4
B. Claims 18-22, 25, 26, 32, 33, 35-38, 40, and 41 are rejected under 35 U.S.C. 102(a)(2) as being anticipated by US 2019/0067016 (“Zhu”). 5
V. Claim Rejections - 35 USC § 103 9
A. Claims 27-30 and 34 are rejected under 35 U.S.C. 103 as being unpatentable over Zhu. 9
B. Claims 35, 36, 38, and 39 are rejected under 35 U.S.C. 103 as being unpatentable over Miyamoto in view of Zhu. 11
VI. Allowable Subject Matter 13
Conclusion 13
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I. 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 .
II. Priority Date for Current Claims
The provisional application, 62/483,857, fails to provide written descriptive support for either of the new independent claims 18 and 35 for failing to disclose (1) the claimed multi-component molybdenum-containing film and the bulk molybdenum layer formed thereon (claim 18) or (2) the claimed molybdenum-containing film and the molybdenum film formed thereon (claim 35). Rather said provisional application provides support for depositing a molybdenum layer on a tungsten-based nucleation layer. As such, the effective filing date for instant claims 18 and 35 appears to be that of the application, 15/948,143, that matured to US patent 10,510,590, which has support for at least claims 18 and 35 and was filed on 04/09/2018. As such, the earliest date to which the claims 18-41 of the Instant Application are entitled priority is 04/09/2018.
III. Claim Objections
Claims 25, 26, and 30 are objected to because of the following informalities:
In each of claims 25 and 26, replace “H2” with “H2” for correct chemical nomenclature.
In claim 30, replace “200OC” with “200°C” for correct nomenclature.
Appropriate correction is required.
IV. 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 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.
(a)(2) the claimed invention was described in a patent issued under section 151, or in an application for patent published or deemed published under section 122(b), in which the patent or application, as the case may be, names another inventor and was effectively filed before the effective filing date of the claimed invention.
A. Claims 18, 20, 23, and 24 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by US 2016/0233309 (“Miyamoto”).
With regard to claims 18, 20, 23, and 24, Miyamoto discloses, generally in Fig. 12,
18. (New) A method comprising:
[1] forming a multi-component molybdenum-containing film 18a1, 18c1 [i.e. MoN (¶ 142)] on a substrate surface 11/14 [¶¶ 64, 67-68]; and
[2] forming a bulk molybdenum layer 18a2, 18c2 [i.e. Mo (¶ 142)] on the molybdenum-containing multi-component film 18a1, 18c1.
20. (New) The method of claim 18, wherein the substrate surface 11/14 comprises a dielectric material 14 [¶¶ 67-68].
23. (New) The method of claim 18, wherein the multi-component molybdenum-containing film 18a1, 18c1 is a binary film containing molybdenum (Mo) and one other element [i.e. MoN (¶ 142)].
24. (New) The method of claim 23, wherein the multi-component molybdenum-containing film 18a1, 18c1 contains molybdenum and nitrogen [i.e. MoN (¶ 142)].
B. Claims 18-22, 25, 26, 32, 33, 35-38, 40, and 41 are rejected under 35 U.S.C. 102(a)(2) as being anticipated by US 2019/0067016 (“Zhu”).
With regard to claim 18, Zhu discloses, generally in Figs. 1a-1b and 2,
18. (New) A method comprising:
[1] forming a multi-component [e.g. may contain O, H, Cl, other halide, or C (¶ 64)] molybdenum-containing film [i.e. the seed layer portion of 23 in Fig. 2 (¶ 34) formed by the process of Fig. 1a (¶ 38)] on a substrate surface [¶¶ 34, ; and
[2] forming a bulk molybdenum layer [i.e. the bulk layer portion of 23 in Fig. 2 (¶ 34) formed by the process of Fig. 1b (¶ 38)] on the molybdenum-containing multi-component film.
Zhu states,
[0034] FIG. 2 shows a cross-section of a gap structure on a substrate filled with a layer according to an embodiment of this disclosure.
[0038] A conformal metal layer 23 is deposited on the surface of the gap by depositing a seed layer by sequentially repeating a pretreatment ALD cycle with a first precursor and depositing a bulk layer by sequentially repeating a bulk ALD cycle with a second precursor. Details of the used method are shown in FIGS. 1a and 1b and the related description.
[0016] FIGS. 1a and 1b show a flowchart illustrating a method of depositing a layer according to an embodiment, wherein a seed layer may be deposited in the gap and a bulk layer may be deposited on the seed layer. A pretreatment ALD cycle 1 for the seed layer may be shown in FIG. 1a and a bulk ALD cycle 2 for the bulk layer may be shown in FIG. 1b.
[0023] The first and second precursor may comprise the same halogen atom. The halogen atom may be a chloride. By having the same halogen the qualification of the tool and the process in the fab may be simplified since only one halogen may need to be assessed. The first precursor [for Mo seed layer by process step 5 in Fig. 1a] may comprise molybdenum pentachloride (MoCl5).
[0025] The second precursor [for bulk Mo layer by process step 11 in Fig. 1b] may comprise an additional atom not being a metal or halogen atom. The additional atom may be a chalcogen. The chalcogen may be oxygen, sulfur, selenium or tellurium. The second precursor may comprise molybdenum (VI) dichloride dioxide (MoO2Cl2).
(Zhu: ¶¶ 34, 38, 16, 23, 25; emphasis added)
With regard to the “multi-component” nature of the Mo seed layer, Zhu states,
[0064] In additional embodiments, the seed or bulk layer may comprise less than about 40 at. %, less than about 30 at. %, less than about 20 at. %, less than about 10 at. %, less than about 5 at. %, or even less than about 2 at. % oxygen. In further embodiments, the seed or bulk layer may comprise less than about 30 at. %, less than about 20 at. %, less than about 10 at. %, or less than about 5 at. %, or less than about 2 at. %, or even less than about 1 at. % of hydrogen. In some embodiments, the seed or bulk layer may comprise halide or chloride less than about 10 at. %, or less than about 5 at. %, less than about 1 at. %, or even less than about 0.5 at. %. In yet further embodiments, the seed or bulk layer may comprise less than about 10 at. %, or less than about 5 at. %, or less than about 2 at. %, or less than about 1 at. %, or even less than about 0.5 at. % carbon. In the embodiments outlined herein, the atomic percentage (at. %) concentration of an element may be determined utilizing Rutherford backscattering (RBS).
(Zhu: ¶ 64; emphasis added)
This is all of the limitations of claim 18.
With regard to claims 19-22, Zhu further discloses,
19. (New) The method of claim 18, wherein the substrate surface comprises a diffusion barrier 21 [¶ 43, e.g. TiN].
20. (New) The method of claim 18, wherein the substrate surface comprises a dielectric material 19 [¶ 43, e.g. Al2O3].
21. (New) The method of claim 20, wherein the dielectric material 19 comprises silicon or aluminum [¶ 43, e.g. Al2O3].
22. (New) The method of claim 20, wherein the dielectric material 19 is an aluminum oxide [¶ 43, e.g. Al2O3].
Zhu states,
[0043] … Further the material of the surface whether it is Al2O3 19 or TiN 21 doesn't seem to influence the thickness of the layer 23 either.
(Zhu: ¶ 43; emphasis added)
With regard to claims 25 and 26, Zhu further discloses,
25. (New) The method of claim 18, wherein forming the bulk molybdenum layer comprises using H2 as reducing agent.
26. (New) The method of claim 18, wherein forming the multi-component molybdenum-containing film comprises using H2 as reducing agent.
Zhu states,
[0028] One or both of the first [for Mo seed layer deposition in step 9 of Fig. 1a] and second [for bulk Mo layer deposition in step 15 of Fig. 1b] reactants may have hydrogen atoms. At least one of the first and second reactant may comprise hydrogen (H2).
[0040] The first and second reactants were hydrogen (H2) which was supplied in the reaction chamber for a duration T2, T4 of 5 seconds with a flow of 495 sccm.
(Zhu: ¶¶ 28, 40; emphasis added)
With regard to claims 32-33, Zhu further discloses,
32. (New) The method of claim 18, wherein the multi-component molybdenum-containing film [seed portion of 23 in Fig. 2 (supra)] is formed on an underlying topography [as shown in Fig. 2] and has a step coverage of greater than 90% on the underlying topography [¶ 33: “In some embodiments, a deposited film comprising Mo may have a step coverage … greater than about 90%, greater than about 95%, greater than about 98%, greater than about 99%.”].
33. (New) The method of claim 18, wherein the bulk molybdenum layer is deposited in a wordline feature [¶¶ 12-13; Fig. 2].
With regard to claim 35, Zhu discloses,
35. (New) A method comprising:
[1] providing a substrate [¶ 34 (supra)] having a dielectric material [e.g. “Al2O3 19” (¶ 43, supra)] formed thereon;
[2] forming a molybdenum-containing layer [i.e. the seed layer portion of 23 in Fig. 2 (¶ 34) formed by the process of Fig. 1a (¶ 38)] on the dielectric material 19; and
[3] supplying a molybdenum-containing gas [e.g. MoO2Cl2 (¶ 25; supra)] and a reducing gas [e.g. H2 (¶¶ 28, 40; supra)] to the substrate having the molybdenum-containing layer [i.e. the Mo seed portion of 23] formed thereon, to form a molybdenum film on the molybdenum-containing layer [i.e. the bulk layer portion of 23 in Fig. 2 (¶ 34) formed by the process of Fig. 1b (¶ 38, supra)].
36. (New) The method of claim 35, wherein the dielectric material comprises silicon or aluminum [e.g. “Al2O3 19” (¶ 43, supra)].
37. (New) The method of claim 35, wherein the dielectric material is an aluminum oxide [e.g. “Al2O3 19” (¶ 43, supra)].
38. (New) The method of claim 35, wherein the molybdenum-containing layer comprises molybdenum (Mo) and at least one other element [¶ 64 (supra)].
40. (New) The method of claim 35, wherein the reducing gas comprises H2 [¶¶ 28, 40, supra]
41. (New) The method of claim 35, wherein one of the molybdenum-containing layer and the molybdenum film is formed using two different temperatures [¶¶ 24, 26].
Note that the two temperatures used for the deposition of each of the Mo seed layer portion of 23 and the bulk Mo portion of 23 include a heating temperature of the “vessel” holding the Mo precursor for the respective layer being formed and the reaction chamber temperature. The vessel temperatures are less than that of the reaction chamber.
V. Claim Rejections - 35 USC § 103
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102 of this title, 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.
A. Claims 27-30 and 34 are rejected under 35 U.S.C. 103 as being unpatentable over Zhu.
Claims 27-30 read,
27. (New) The method of claim 18, wherein the multi-component molybdenum-containing film and the bulk molybdenum layer are formed at different substrate temperatures.
28. (New) The method of claim 27, wherein the multi-component molybdenum-containing film is formed at a first deposition temperature and the bulk molybdenum layer is formed at a second deposition temperature, wherein the first deposition temperature is less than the second deposition temperature.
29. (New) The method of claim 28, wherein the second deposition temperature is 500°C or greater.
30. (New) The method of claim 28, wherein the first deposition temperature is 200°C or greater.
The prior art of Zhu, as explained above, teaches each of the features of claim 18.
With regard to claims 27-30, Zhu further discloses,
[0024] The process temperature in the reaction chamber may be selected between 300 and 800, preferably 400 and 700, and more preferably 450 and 550° C. during the pretreatment ALD cycle [i.e. Mo seed layer formation step in Fig. 1a]. …
[0026] The process temperature may be between 300 and 800, preferably 400 and 700, and more preferably 500 and 650° C. during the bulk ALD cycle [i.e. bulk Mo layer formation step in Fig. 1b]. …
(Zhu: ¶¶ 24, 26; emphasis added)
It would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to the more preferable temperature ranges for each of the Mo seed layer formation of 450 ℃ to 550 ℃ and bulk Mo layer formation of 500 ℃ to 650 ℃, as required by claims 29 and 30, because these are the more preferable than the broader ranges.
In addition, it would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to make the first (Mo seed) deposition temperature different, i.e. less than, that of the second (bulk Mo) deposition step, as required by claims 27 and 28, because the deposition range for the Mo seed layer formation is less than that for the bulk Mo layer deposition.
Claim 34 reads,
34. (New) The method of claim 18, wherein the bulk molybdenum layer has a resistivity of less than 100 micro-ohm-cm at 200 Angstroms.
Zhu states,
The molybdenum film may have an electrical resistivity of less than 3000 μΩ-cm, or less than 1000 μΩ-cm, or less than 500 μΩ-cm, or less than 200 μΩ-cm, or less than 100 μΩ-cm, or less than 50 μΩ-cm, or less than 25 μΩ-cm, or less than 15 μΩ-cm or even less than 10 μΩ-cm.
(Zhu: ¶ 20)
The bulk layer may have a thickness between 1 and 100, preferably 5 and 50, more preferably between 10 and 30 nm [i.e. 100 Å to 300 Å].
(Zhu: ¶ 21)
It would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to make the thickness of the bulk Mo film portion of Mo layer 23 to from 100 Å to 300 Å having a resistivity of “less than 100 μΩ-cm, or less than 50 μΩ-cm, or less than 25 μΩ-cm, or less than 15 μΩ-cm or even less than 10 μΩ-cm” because these ranges are the more preferred or suggested ranges in Zhu.
Moreover, in the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); MPEP 2144.05(I)). In such a situation, Applicant must show that the particular ranges are critical, generally by showing that the claimed range achieves unexpected results relative to the prior art range. See In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990). (See MPEP 2144.05(III)(A); emphasis added.)
B. Claims 35, 36, 38, and 39 are rejected under 35 U.S.C. 103 as being unpatentable over Miyamoto in view of Zhu.
Claim 35 reads,
35. (New) A method comprising:
[1] providing a substrate having a dielectric material formed thereon;
[2] forming a molybdenum-containing layer on the dielectric material; and
[3] supplying a molybdenum-containing gas and a reducing gas to the substrate having the molybdenum-containing layer formed thereon, to form a molybdenum film on the molybdenum-containing layer.
With regard to claim 35, Miyamoto discloses, generally in Fig. 12,
35. (New) A method comprising:
[1] providing a substrate 11 having a dielectric material 14 formed thereon [¶¶ 64, 67-68];
[2] forming a molybdenum-containing layer 18a1, 18c1 [i.e. MoN (¶ 142)] on the dielectric material 14; and
[3] … form a molybdenum film 18a2, 18c2 [i.e. Mo (¶ 142)] on the molybdenum-containing layer 18a1, 18c1.
With regard to feature [3] of claim 35, Miyamoto does not discuss how the Mo films, 18a2 and 18c2, are formed on the MoN films, 18a1 and 18c1, respectively.
As explained above, Zhu teaches a process of forming a bulk Mo portion of a Mo conformal film 23 by “supplying a molybdenum-containing gas [e.g. MoO2Cl2 (Zhu: ¶ 25; supra)] and a reducing gas [e.g. H2 (Zhu: ¶¶ 28, 40; supra)] to the substrate having the molybdenum-containing layer [i.e. the Mo seed portion of 23] formed thereon”.
It would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to use the process of Zhu to form the Mo films, 18a2 and 18c2, of Miyamoto because Miyamoto is merely silent as to the process such that one having ordinary skill in the art would use known processes for forming bulk Mo conformal films on an underly Mo-containing film, such as the known process of Zhu. (See MPEP 2143.)
This is all of the limitations of claim 35.
With regard to claims 36, 38, and 39, Miyamoto further discloses,
36. (New) The method of claim 35, wherein the dielectric material 14 comprises silicon or aluminum [¶¶ 67-68].
38. (New) The method of claim 35, wherein the molybdenum-containing layer 18a1, 18c1 comprises molybdenum (Mo) and at least one other element [i.e. MoN (¶ 142)].
39. (New) The method of claim 38, wherein the molybdenum-containing film contains molybdenum and nitrogen [i.e. MoN (¶ 142)].
VI. Allowable Subject Matter
Claim 31 is objected to as being dependent upon a rejected base claim, but would be allowable if rewritten in independent form including all of the limitations of the base claim and any intervening claims.
The following is a statement of reasons for the indication of allowable subject matter:
Claim 31 reads,
31. (New) The method of claim 18, wherein forming the bulk molybdenum layer comprises using multiple substrate temperatures.
The prior art does not reasonably teach or suggest—in the context of claim 31—the use of multiple temperatures to form the bulk molybdenum layer.
Conclusion
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Signed,
/ERIK KIELIN/
Primary Examiner, Art Unit 2814
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