DETAILED ACTION
Table of Contents
I. Notice of Pre-AIA or AIA Status 3
II. Claim Rejections - 35 USC § 112 3
A. Claim 8 is rejected under 35 U.S.C. 112(d) as being of improper dependent form … 3
III. Claim Rejections - 35 USC § 103 4
A. Claims 1-3 and 9 are rejected under 35 U.S.C. 103 as being unpatentable over US 2005/0215052 (“Liang”). 4
B. Claims 4 and 5 are rejected under 35 U.S.C. 103 as being unpatentable over Liang in view of US 2016/0013051 (“Zeng”). 7
C. Claims 6-8 are rejected under 35 U.S.C. 103 as being unpatentable over Liang in view of Zeng, as applied to claims 4 and 5 above, and further in view of US 5,922,411 (“Shimizu”). 9
D. Claims 1-3 and 9 are rejected under 35 U.S.C. 103 as being unpatentable over US 2019/0244803 (“Suzuki”). 11
Conclusion 15
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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. Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(d):
(d) REFERENCE IN DEPENDENT FORMS.—Subject to subsection (e), a claim in dependent form shall contain a reference to a claim previously set forth and then specify a further limitation of the subject matter claimed. A claim in dependent form shall be construed to incorporate by reference all the limitations of the claim to which it refers.
A. Claim 8 is rejected under 35 U.S.C. 112(d) as being of improper dependent form …
… for failing to further limit the subject matter of the claim upon which it depends, or for failing to include all the limitations of the claim upon which it depends.
Claims 6-8 read,
6. (Original) The manufacturing method of the insulation film according to claim 5, wherein the heating process is performed in an atmosphere of N2 or an inert gas.
7. (Original) The manufacturing method of the insulation film according to claim 6, wherein the SOG further includes a silazane.
8. (Original) The manufacturing method of the insulation film according to claim 7, wherein the heating process is performed in an atmosphere of one among H2O, O2, or H2O2.
Because of the claim dependency, claim 8 omits the “atmosphere of N2 or an inert gas” required by claim 6, from which claim 8 indirectly depends. Thus, claim 8 fails to require all of the limitations of the claim upon which is depends.
Applicant may cancel the claim(s), amend the claim(s) to place the claim(s) in proper dependent form, rewrite the claim(s) in independent form, or present a sufficient showing that the dependent claim(s) complies with the statutory requirements.
III. 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 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 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 1-3 and 9 are rejected under 35 U.S.C. 103 as being unpatentable over US 2005/0215052 (“Liang”).
With regard to claim 1, Liang discloses, generally in Figs. 3 and 7,
1. (Original) A manufacturing method 30 of an insulating film, the method including a deposition process 32, a heating process 34, and an exposure process 36,
[1] wherein the deposition process 32 includes depositing a film deposition material [i.e. low-k dielectric (¶ 9)] on a substrate 72 to form a deposition material layer 74 [i.e. “inter-level dielectric layers 74” made from the low-k dielectric made according to the invention] [¶¶ 20, 26],
[2] wherein the heating process 34 includes heating the deposition material layer 74 on the substrate 72 at a temperature equal to or higher than 85°C to equal to or lower than 450°C [i.e. 200°C to 450°C (¶ 20)],
[3] wherein the exposure process 36 includes irradiating a surface of the deposition material layer 74 on the substrate 72 with a plasma containing hydrogen radicals to make hydrogen diffuse into a structure of the deposition material layer and bind the hydrogen to a component of the deposition material layer [¶ 20; see discussion below], and
[4] wherein a product of an irradiation time and a density of radicals formed by the plasma is equal to or higher than 25×1014 min-pcs/cm3 [see discussion below].
With regard to features [3] and [4] of claim 1, Liang uses an exposure process significantly overlapping the conditions used in the Instant Application. In this regard, Liang uses the following conditions:
Second treatment process 36 of integrated method 30 comprises subjecting the low dielectric material to microwave hydrogen plasma. The time duration for the exposure may range about 30 to about 600 seconds [i.e. 0.5 minutes to 10 minutes], and the wafer temperature may range about 200 to about 450 degrees Celsius. The chamber pressure may range about 10 mTorr to about 100 mTorr [1.3 Pa to 13 Pa], with the microwave power in the range of about 300 Watts to about 3000 Watts. The second processing step of microwave hydrogen plasma hardens the material in addition to lower the film shrinkage and stress problems. The result is a more robust and stable low dielectric material that has a lower dielectric constant.
(Liang: ¶ 20; 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 use a pressure of 100 mTorr (13 Pa) for the hydrogen plasma pressure, a microwave power of e.g. 1000 W or 2000 W or 3000 W, and an exposure time of e.g. 10 minutes because Liang explains that these are suitable microwave hydrogen plasma treatment conditions for treating the low-k dielectric layer.
The Instant Application uses a microwave hydrogen plasma at a pressure of 5 Pa to 50 Pa, e.g. 20 Pa, a microwave power ranging from 500 W to 1500 W, with 1000 W achieving the H radical density of 3×1015 pcs/cm3, exposure times of 1, 2, 3, 4, 5, 10, and 15 minutes at 1500 W (Instant Specification: ¶¶ 39-45 at pp. 8-12 and associated Figs. 3A-7A; instant claim 2).
It is held, absent evidence to the contrary, that, at the suggested conditions in Liang of, e.g.,100 mTorr (13 Pa) hydrogen plasma pressure, a microwave power of e.g. 1000 W or 2000 W or 3000 W, and an exposure time of e.g. 10 minutes, that the low-k dielectric material layer 74 is treated with H radicals equal to or higher than 25×1014 min-pcs/cm3—as required by feature [4]—as evidenced by the data in the Instant Application (supra). As such, the burden of proof is shifted to Applicant to prove the contrary. (See MPEP 2112(I)-(V).)
Because the dielectric constant of the low-k dielectric layer in Liang is lowered and there is some shrinkage with an increase in hardness (Liang: ¶ 20), it is held, absent evidence to the contrary, that the H radicals bind with “a component of the deposition material layer” 74—as required by feature [3]—that results in removal of whatever material allows the dielectric constant, k, of the low-k dielectric material to be lowered, along with some densification caused by the film shrinkage, as consistent with the same effects observed in the Instant Application (Instant Specification: ¶¶ 46-47, pp. 11-12; Fig. 1E).
With regard to claim 2,
2. (Original) The manufacturing method of the insulation film according to claim 1, wherein the radicals are provided to the surface of the deposition material layer by a forming of the plasma under a pressure equal to or higher than 5 Pa to equal to or lower than 50 Pa.
Again, Liang teaches a hydrogen plasma pressure of 1.3 Pa to 13 Pa which overlaps the claimed range.
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.)
With regard to claim 3,
3. (Currently Amended) The manufacturing method of the insulation film according to claim 1, wherein the radicals are hydrogen atoms H’s.
The limitation of this claim is inherent for the same reasons as explained under claim 1.
With regard to claim 9, Liang further discloses,
9. (Currently Amended) The manufacturing method of the insulation film according to claim 1, wherein the substrate 72 is a semiconductor substrate or a substrate formed with a semiconductor device pattern [¶ 26].
B. Claims 4 and 5 are rejected under 35 U.S.C. 103 as being unpatentable over Liang in view of US 2016/0013051 (“Zeng”).
Claims 4 and 5 read,
4. (Currently Amended) The manufacturing method of the insulation film according to any one of claim 1, wherein the film deposition material is a spin on glass (SOG), and wherein the SOG is coated and deposited on the substrate.
5. (Original) The manufacturing method of the insulation film according to claim 4, wherein the SOG includes one or more among a ladder-type hydrogen silsesquioxane, a hydrogen siloxane, and a silicate.
The prior art of Liang, as explained above, discloses each of the features of claim 1.
With regard to claim 4, Liang further discloses that the low-k dielectric material layer can be deposited by “spin-on deposition (SOD)” (Liang: ¶ 11).
Liang does not, however, state that the low-k dielectric materials (Liang: ¶ 9) that may be deposited by SOD are spin-on glasses (SOG), as required by claim 4, and also does not disclose the specific materials of claim 5 for an SOG.
Zeng, like Liang (at ¶ 1), teaches a method of depositing a dielectric material layer 105a/105b between conductive structures 101a that may be deposited using SOD (Zheng: ¶¶ 40, 46, 52; Figs. 3, 4). Also like Liang, Zeng teaches that the dielectric material layer 105a/105b, once deposited, may be further treated by curing, and annealing, e.g., microwave annealing (Zeng: ¶¶ 48, 56, 57; Fig. 5). Zeng further teaches that the dielectric material layer 105a/105b may be made of “may be formed through spin-on deposition (SOD) of one or more dielectric materials, such as SOD of one or more of silicates, siloxanes, methyl silsesquioxane (MSQ), hydrogen silsesquioxane (HSQ), MSQ-HSQ, perhydrosilazane (TCPS), and perhydro-polysilazane (PSZ)”—as required by claims 4 and 5.
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 dielectric material layer 74 of Liang by SOD with, e.g., a silicate, because Liang does not limit the dielectric material 74, and Zeng teaches that silicates are suitable for the same purpose as in Liang of filling the space between conductive structures in an integrated circuit substrate. As such, the selection of silicates amounts to obvious material choice. (See MPEP 2144.07.)
There is a reasonable expectation of success given that Zeng teaches that the SOG, after curing, are subsequently annealed by essentially the same processes as in Liang, i.e. thermal, UV, e-beam, and microwave annealing processes (Zeng: ¶ 57), thereby showing that the materials in Zeng, like those examples in Liang, also require the same kind of additional processing.
This is all of the features of claims 4 and 5.
C. Claims 6-8 are rejected under 35 U.S.C. 103 as being unpatentable over Liang in view of Zeng, as applied to claims 4 and 5 above, and further in view of US 5,922,411 (“Shimizu”).
Claims 6-8 read,
6. (Original) The manufacturing method of the insulation film according to claim 5, wherein the heating process is performed in an atmosphere of N2 or an inert gas.
7. (Original) The manufacturing method of the insulation film according to claim 6, wherein the SOG further includes a silazane.
8. (Original) The manufacturing method of the insulation film according to claim 7, wherein the heating process is performed in an atmosphere of one among H2O, O2, or H2O2.
The prior art of Liang in view of Zeng, as explained above, teaches each of the features of claims 4 and 5.
With regard to claim 7, Zeng further teaches,
7. (Original) The manufacturing method of the insulation film according to claim 6, wherein the SOG further includes a silazane .
Again Zeng states that the dielectric material layer deposited by SOD “may be formed through spin-on deposition (SOD) of one or more dielectric materials, such as SOD of one or more of silicates, siloxanes, methyl silsesquioxane (MSQ), hydrogen silsesquioxane (HSQ), MSQ-HSQ, perhydrosilazane (TCPS), and perhydro-polysilazane (PSZ)”.
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 dielectric material layer 74 of Liang by SOD with, e.g., a combination of a silicate and one of the silazanes, TCPS and PSZ, because Liang does not limit the dielectric material 74, and Zeng teaches that one or more of silicates and the two silazanes is suitable for the same purpose as in Liang of filling the space between conductive structures in an integrated circuit substrate. As such, the selection of silicates plus silazanes amounts to obvious material choice. (See MPEP 2144.07.)
With regard to claim 8, Zeng further teaches,
8. (Original) The manufacturing method of the insulation film according to claim 7, wherein the heating process is performed in an atmosphere of one among H2O, O2, or H2O2.
Liang does not disclose the atmosphere in which the thermal treatment step 34.
Zeng, like Liang, teaches a thermal treatment step in the form of the curing of the as-deposited SOD 105a/105b in similar temperature and pressure ranges, i.e. 200 ℃ to 450 ℃ and 10 Torr to 760 Torr in Liang (¶ 20) and 10 ℃ to 500 ℃ and 1 Torr to 760 Torr in Zeng (¶¶ 48, 56). Zeng further teaches that the curing atmosphere may be water, i.e. H2O, which would be steam at temperatures over 100 ℃ (Zeng: ¶¶ 48, 56).
It would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to further, to perform the thermal treatment step 34 of Liang/Zeng using water as steam, in the indicated pressure range and temperature range of Liang, because Liang is silent as to the atmosphere which is used to obtain the requisite pressure of 10 Torr to 760 Torr, while Zeng teaches that curing is a similar temperature range in a water atmosphere, again steam at temperatures over 100 ℃, is used to curing the dielectric material layer composition.
Then the only difference is with regard to claim 6,
6. (Original) The manufacturing method of the insulation film according to claim 5, wherein the heating process is performed in an atmosphere of N2 or an inert gas.
Neither of Liang and Zeng teaches that the thermal curing steps include nitrogen or an inert gas.
Shimizu teaches that it is known to bring steam into contact with a silazane polymer (Shimizu: col. 7, lines 48-54) for converting the Si-H bonds and Si-N bonds to Si-O bonds (Shimizu: col. 11, lines 23-33) by using a carrier gas that may be air or nitrogen (Shimizu: col. 11, lines 1-14; col. 13, lines 20-51; col. 15, lines 26-37), air being known to be about 78% nitrogen.
It would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to use air or nitrogen as the carrier gas for the water(steam) to bring the water(steam) to the dielectric material layer of Liang/Zeng for the curing process because Zeng is merely silent as to how the water(steam) is provided, such that one having ordinary skill in the art would use known methods, such as the air or nitrogen carrier gas taught to be very old and well known in Shimizu.
This is all of the features of claims 6-8.
D. Claims 1-3 and 9 are rejected under 35 U.S.C. 103 as being unpatentable over US 2019/0244803 (“Suzuki”).
With regard to claim 1, Suzuki discloses,
1. (Original) A manufacturing method of an insulating film, the method including a deposition process, heating process and an exposure process,
[1] wherein the deposition process includes depositing a film deposition material [silicon oxide] on a substrate to form a deposition material layer [silicon oxide] [¶ 53],
[2] wherein the heating process includes heating the deposition material layer [silicon oxide] on the substrate at a temperature equal to or higher than 85°C to equal to or lower than 450°C [e.g. 400 ℃ or lower” (¶ 53); see discussion below],
[3] wherein the exposure process includes irradiating a surface of the deposition material layer on the substrate with a plasma containing hydrogen radicals to make hydrogen diffuse into a structure of the deposition material layer and bind the hydrogen to a component of the deposition material layer [¶¶ 79-85; Figs. 13, 14(b), 16, 17, and especially Fig. 18 (¶¶ 58, 79, 82)], and
[4] wherein a product of an irradiation time and a density of radicals formed by the plasma is equal to or higher than 25×1014 min-pcs/cm3 [see discussion below].
With regard to feature [2] of claim 1, Suzuki teaches that “the silicon oxide film is deposited by PEALD … at a relatively low temperature (e.g., 400° C. or lower)” (¶ 53). Because the process of ALD form approximate monolayers sequentially, the underlying deposited layers are heated at the deposition temperature, which reads on the claimed heating process.
Although Suzuki does not give a lower bound of the temperature range, the claimed temperature range of 85 ℃ to 450 ℃ overlaps the range of 400° C. or lower disclosed in Suzuki.
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.)
With regard to feature [3] of claim 1, Suzuki (Suzuki: ¶¶ ¶¶ 79-85; Figs. 13, 14(b), 16, 17, and especially Fig. 18 (¶¶ 58, 79, 82)) observes the same effect as in the Instant Application (Instant Application: Fig. 1E) of reduction in the amount of hydrogen in the as-deposited silicon oxide film (Suzuki: ¶¶ 51, 83-85; Figs. 13, 14(b), 16, 17, and 18).
With regard to feature [4] of claim 1, Suzuki uses a microwave hydrogen plasma exposure process significantly overlapping the conditions used in the Instant Application. In this regard, Suzuki uses the following conditions: (1) hydrogen pressures of 20 Pa and 30 Pa (¶¶ 56, 83, 84), (2) power 1000 W to 3000 W (¶¶ 44, 56), e.g. 2000 W (¶¶ 79, 84), and (3) exposure time of preferably 3 min to 10 min (¶ 56), e.g. 10 min (¶¶ 80, 84).
The Instant Application uses a microwave hydrogen plasma at (1) a pressure of 5 Pa to 50 Pa, e.g. 20 Pa, (2) a microwave power ranging from 500 W to 1500 W, with 1000 W achieving the H radical density of 3×1015 pcs/cm3, and (3) exposure times of 1, 2, 3, 4, 5, 10, and 15 minutes at 1500 W (Instant Specification: ¶¶ 39-45 at pp. 8-12 and associated Figs. 3A-7A; instant claim 2).
It is held, absent evidence to the contrary, that the conditions in Suzuki of 20 Pa and 30 hydrogen plasma pressure, a microwave power of 2000 W, and an exposure time of e.g. 10 minutes, results in the silicon oxide film being irradiated with H radicals equal to or higher than 25×1014 min-pcs/cm3—as required by feature [4]—as evidenced by the data in the Instant Application (supra). As such, the burden of proof is shifted to Applicant to prove the contrary. (See MPEP 2112(I)-(V).)
Further with regard to feature [4] of claim 1, Suzuki, like the Instant Application, recognizes that the treatment conditions are a result effect variable, stating in this regard,
However, since a direct microwave plasma can penetrate the film from its surface to a depth of more than 10 nm, e.g., approximately 40 nm, by manipulating process parameters including the reforming step duration, pressure, temperature, and microwave power, the film can be reformed in its entirety without repeating the deposition step and reforming step.
(Suzuki: ¶ 52, last sentence; emphasis added )
As such the selection of “an irradiation time and a density of radicals formed by the plasma is equal to or higher than 25×1014 min-pcs/cm3” is prima facie obvious without showing that this range achieves unexpected results relative to the prior art range. In re Woodruff, 16 USPQ2d 1935, 1937 (Fed. Cir. 1990). See also In re Aller, 105 USPQ 233 (CCPA 1955) (selection of optimum ranges within prior art general conditions is obvious). See also In re Huang, 40 USPQ2d 1685, 1688(Fed. Cir. 1996)(claimed ranges of a result effective variable, which do not overlap the prior art ranges, are unpatentable unless they produce a new and unexpected result which is different in kind and not merely in degree from the results of the prior art).
“[U]nexpected results [relied upon to rebut a prima facie case of obviousness]… must be shown to be unexpected compared with the closest prior art.” In re Baxter Travenol Labs, 952 F.2d 388, 392 (Fed. Cir. 1991)(citation omitted). Such evidence must be commensurate in scope with the degree of patent protection desired. In re Grasselli, 713 F.2d 731,743 (Fed. Cir. 1983). In addition, the difference in results relied upon to establish nonobviousness must be shown to be truly unexpected by one of ordinary skill in the art. Pfizer Inc. v. Apotex Inc., 480 F.3d 1348, 1371 (Fed. Cir. 2007). Thus, it is not enough to merely show that there is a difference—even a significant difference. Rather, the difference in results must be shown to be unexpected by one of ordinary skill in the art. In re Harris, 409 F.3d 1339, 1344 (Fed. Cir. 2005).
Here, Suzuki is treating the same material (silicon oxide) in the same way (treatment using a hydrogen microwave plasma at generally the same conditions as in the Instant Application) and observes the same results (removal of at least some hydrogen from the silicon oxide film). As such, there does not appear to be an unexpected result relative to the prior art.
This is all of the features of claim 1.
With regard to claim 2, Suzuki further discloses,
2. (Original) The manufacturing method of the insulation film according to claim 1, wherein the radicals are provided to the surface of the deposition material layer by a forming of the plasma under a pressure equal to or higher than 5 Pa to equal to or lower than 50 Pa [20 Pa and 30 Pa (supra)].
With regard to claim 3, Suzuki further discloses,
3. (Currently Amended) The manufacturing method of the insulation film according to claim 1, wherein the radicals are hydrogen atoms H’s.
This limitation is inherent for the same reasons as explained under claim 1.
With regard to claim 9, Suzuki further discloses,
9. (Currently Amended) The manufacturing method of the insulation film according to claim 1, wherein the substrate is a semiconductor substrate or a substrate formed with a semiconductor device pattern [¶¶ 1, 2; Figs. 15, 16].
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to ERIK KIELIN whose telephone number is (571)272-1693. The examiner can normally be reached Mon-Fri: 10:00 AM-7:00 PM.
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Signed,
/ERIK KIELIN/
Primary Examiner, Art Unit 2814