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 .
Claim Rejections - 35 USC § 102
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.
Claims 1-5, 9-10, and 14-18 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Hirose et al (US 20140287597 A1). Hirose et al will be referenced to as Hirose henceforth.
Regarding Claim 1,
Hirose teaches:
“A method of processing a substrate, comprising: forming a film (SiBCN film, [0004], FIG. 13) containing silicon (SiBCN contains Si), a predetermined element (SiBCN contains C: the Examiner is interpreting C to be the predetermined element.), and nitrogen (SiBCN contains N) on the substrate by performing a cycle a predetermined number of times ([0004], FIG. 13), the cycle including:
(a) forming a first layer (SiCN layer, [0189]) by supplying a first gas which contains silicon (3DMAS gas, [0185], [0189]: The order in which the 3DMAS gas and the HCDS gas may be flipped. Therefore, the first gas may be the 3DMAS gas and the second gas may be the HCDS gas.) and does not contain a Si-Si bond (3DMAS doesn’t contain a Si-Si bond.), to the substrate ([0189]: the SiCN layer is formed on the wafer.);
(b) forming a second layer (a SiBCN layer, [0189]) by supplying a second gas (HCDS gas [0189]: The second layer is described as being finally formed after the application of the TMB gas, however the second layer is formed from the first layer. The HCDS gas was used to form the first layer and therefore the second layer too.), which is a chlorosilane gas containing a Si-Si bond ([0040]: HCDS contains chlorine and a Si-Si bond. HCDS is a chlorosilane gas.) and differs in a molecular structure from the first gas, to the substrate ([0189]: 3DMAS gas is not HCDS gas. HCDS gas is used to form the second layer and is therefore applied to the wafer.);
(c) supplying a third gas containing the predetermined element to the substrate (C3H6 gas, [0179], FIG. 13 (2) modification 2);
and (d) modifying the first layer and the second layer by supplying a fourth gas containing nitrogen to the substrate (a nitriding gas NH3, [0189]), wherein an element capable of forming defects in the film is used as the predetermined element ([0107]: C3H6 gas reacts with Cl in the first layer. This forms defects in the film, the defects being Cl2 or H2 which are then removed from the process chamber.), and wherein in the cycle, (a) to (d) are performed in an order of: (a), (c), (b), and (d);
(c), (a), (b), and (d);
or (c), (a), (c), (b), and (d) ([0179], FIG. 13 (2) modifications 2: the cycle is performed in the order of (a), (c), (b), (d)).”
Regarding Claim 2,
Hirose teaches:
“The method of Claim 1, wherein at least a portion of an execution period of (a) overlaps with at least a portion of an execution period of (c) (FIG. 13 (2) modification 2). ”
Regarding Claim 3,
Hirose teaches:
“The method of Claim 2, wherein the execution period of (c) does not overlap with an execution period of (b) (FIG. 13 (2) modification 2).”
Regarding Claim 4,
Hirose teaches:
“The method of Claim 2, wherein the execution period of (c) does not overlap with an execution period of (d) (FIG. 13 (2) modification 2).”
Regarding Claim 5,
Hirose teaches:
“The method of Claim 1, wherein in the cycle, (a) to (d) are performed in the order of (a), (c), (b), and (d) ([0179], FIG. 13 (2) modifications 2: the cycle is performed in the order of (a), (c), (b), (d)).”
Regarding Claim 9,
Hirose teaches:
“The method of Claim 1, wherein at least one selected from the group of carbon and boron is used as the predetermined element (SiBCN contains C: The Examiner is interpreting C to be the predetermined element.).”
Regarding Claim 10,
Hirose teaches:
“The method of Claim 1, wherein at least one gas selected from the group of a hydrocarbon-based gas, an amine-based gas, a boron chloride-based gas, and a borohydride-based gas is used as the third gas (C3H6 gas, [0179], FIG. 13: C3H6 is a hydrocarbon gas.).”
Regarding Claim 14,
Hirose teaches:
“The method of Claim 1, wherein the cycle further includes (e) supplying a fifth gas containing a second predetermined element to the substrate (TMB gas [0178], FIG. 13: the gas is supplied on the substrate), and wherein at least a portion of an execution period of (c) overlaps with at least a portion of an execution period of (e) ([0178]: Hirose makes clear that C3H6 may be supplied before, after, and during the supplying of the TMB gas.).”
Regarding Claim 15,
Hirose teaches:
“The method of Claim 1, wherein the cycle further includes (e) supplying a fifth gas containing a second predetermined element ([0044]: TMB gas stands for trimethylborazine gas which contains a second predetermined element: boron.) to the substrate ([0178]), and wherein an execution period of (c) is continuous with an execution period of (e) ([0178]: The supply of the C3H6 gas may be the same as the supply period of the TMB gas or during a portion of the supply of the TMB gas.).”
Regarding Claim 16,
Hirose teaches:
“The method of Claim 1, wherein, when the first gas alone exists in a space where the substrate is placed ([0077]: the first gas exists alone before the other gases are introduced), a temperature of the substrate in (a) is set to a temperature lower than the temperature at which the first gas is substantially thermally decomposed ([0079]: the temperature of the substrate is such that 3DMAS may be chemisorbed in the wafer.), and wherein, when the second gas alone exists in the space where the substrate is placed ([0091-0092]: Hirose supplies an inert gas along with the HCDS gas. The second gas comprises both the inert gas and the HCDS gas. Applicant also provides an inert gas with their second gas in paragraph [0071] of their application.), the temperature of the substrate in (b) is set to a temperature at which the second gas is substantially thermally decomposed ([0091-0092]: The given temperature and pressure are such that the HCDS gas reacts with the silicon containing layer. Thus, the chemical decomposition of the HCDS gas is caused by heat and the interaction of the HCDS gas with the silicon containing layer.).”
Regarding Claim 17,
Hirose teaches:
“The method of Claim 16, wherein the temperature of the substrate in (a) and (b) is 450 degrees C or higher and 750 degrees C or lower ([0079]: the temperature of the substrate is between 350 to 600 degrees).”
Regarding Claim 18,
Hirose teaches:
“A method of manufacturing a semiconductor device, comprising the method of Claim 1 (see the rejection of Claim 1.).”
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, 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.
Claims 11-12 are rejected under 35 U.S.C. 103 as being unpatentable over Hirose as applied to claims 1-5, 9-10, and 14-18 above, and further in view of Nakatani et al (US 20180363138 A1). Nakatani et al will be referenced to as Nakatani henceforth.
Hirose doesn’t substantially teach:
“wherein a gas that does not contain a Si-Si bond is used as the first gas, and wherein a gas that contains the Si-Si bond is used as the second gas .”
Regarding Claim 11,
Hirose teaches:
“The method of Claim 1,”
Hirose doesn’t substantially teach:
“wherein a concentration of the predetermined element in the film is 5 atom% or less.”
However, Nakatani teaches:
“wherein a concentration of the predetermined element in the film is 5 atom% or less (Nakatani: FIG. 8 (b): The concentration of carbon in film C7 can be determined to be a fraction of 20%. The carbon layer in FIG. 8 is 21 pixels tall. 20 at% is equivalent to 98 pixels. Therefore, the amount of carbon is about 4%. The figure is to scale as can be seen by the amount of O in C8 at 15%, Nakatani: [0145]).”
It would have been obvious to one with ordinary skill in the art before the effective filing
date of the invention to recognize that the device of Hirose is modifiable in view of Nakatani.
This is because Hirose does not explicitly teach the claimed range. However, Hirose teaches that the carbon concentration of the SiBCN film affects the properties of a SiBCN film as a film for a side wall spacer. The carbon concentration of the SiBCN film is therefore a result effective variable. It would therefore have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to vary, through routine optimization, the concentration of carbon in the SiBCN to arrive at the claimed range. See MPEP 2144.05.II.B.
.
Regarding Claim 12,
Hirose/Nakatani teaches:
“The method of Claim 11, wherein the concentration of the predetermined element in the film is 1 atom% or more (Nakatani: FIG. 8 (b): The concentration of carbon in film C7 can be determined to be a fraction of 20 at%. The carbon layer in FIG. 8 is 21 pixels tall. 20 at% is equivalent to 98 pixels. Therefore, the amount of carbon is about 4%).”
Claim 13 is rejected under 35 U.S.C. 103 as being unpatentable over Hirose as applied to claims 1-5, 9-10, and 14-18 above, and further in view of Xie et al (US 20200279858 A1). Xie et al will be referenced to as Xie henceforth.
Regarding Claim 13,
Hirose teaches:
“The method of Claim 1,”
Hirose doesn’t substantially teach:
“wherein the film is a charge trap film of a nonvolatile memory cell.”
However, Xie teaches:
“wherein the film is a charge trap film of a nonvolatile memory cell (Xie: surface of the contact 602, [0092] FIG.13B: The charge storage stack 1102/1104/1106 [Xie: 0091] forms the charge trap. The surface of the contact 602 may include SiBCN.).”
It would have been obvious to one with ordinary skill in the art before the effective filing
date of the invention to recognize that the device of Hirose is modifiable in view of Xie.
This is because Xie teaches a covering of the surface of 602 with SiBCN in order to electrically isolate the charge trap. One of ordinary skill in the art would recognize the electrical isolation of the charge to be desirable because a lack of electrical isolation may result in charge leakage from the conduction of charges outside the trap through a non-insulating material.
Claim 21 is rejected under 35 U.S.C. 103 as being unpatentable over Hirose as applied to claims 1-5, 9-10, and 14-18 above, and further in view of Saido et al (US 20180033645 A1). Saido et al will be referenced to as Saido henceforth.
Regarding Claim 21,
Hirose teaches:
“The method of Claim 1,”
Hirose doesn’t substantially teach:
“wherein the first gas is a halosilane-based gas.”
However, Saido teaches:
“wherein the first gas is a halosilane-based gas. (Saido: [0089]: The source gas may be a DCS gas instead of a 3DMAS gas. DCS is a halosilane-based gas.)”
It would have been obvious to one with ordinary skill in the art before the effective filing
date of the invention to recognize that the device of Hirose is modifiable in view of Hirose 2.
This is because Hirose teaches using a 3DMAS gas as a source gas. Hirose doesn’t substantively teach using DCS as a source gas. Saido teaches using a 3DMAS gas as a source gas . Saido further teaches using a DCS gas instead of a 3DMAS gas as a source gas. Because both Hirose and Saido have a 3DMAS gas as a source gas, one of ordinary skill in the art would have deemed it obvious to substitute the 3DMAS gas of Hirose for a DCS gas of Saido for the predictable result of providing a silicon source to the formation of a SiBCN layer.
Response to Arguments
Applicant’s amendments to the Claims have overcome the Examiner’s 103 rejection.
Applicant substantively argues:
“1. There is No Motivation to Replace Hirose's Second Gas with Nakatani's Disilane. The Office Action asserts that while Hirose does not disclose using a gas having a Si-Si bond as the second gas, Nakatani discloses using a disilane gas or an aminosilane gas as a second gas. The Office concludes that a person of ordinary skill in the art would have been motivated to replace the 3DMAS gas (i.e., an aminosilane gas), which is the second gas of Hirose, with a disilane gas having a Si-Si bond.Applicant respectfully submits that this modification would destroy the fundamental chemistry of Hirose's process.
In Hirose, after the supply of a first gas (e.g., HCDS gas), a second gas (e.g., 3DMAS gas) is supplied. Crucially, Hirose requires the second gas to be an aminosilane gas containing nitrogen to act as a nitrogen source]. By supplying the nitrogen-containing aminosilane gas as the second gas, Hirose forms a SiCN layer (a first layer containing nitrogen) from the reaction of the first gas and the second gas].That is, in Hirose, the second gas is essentially required to contain nitrogen in order to form the nitrogen-containing first layer. Then, after the formation of this first layer, a gas containing a borazine compound (e.g., TMB gas) is supplied to form a SiBCN layer as a second layer].
However, if the second gas of Hirose were replaced with the disilane gas of Nakatani as asserted in the Office Action, a first layer containing nitrogen (i.e., the SiCN layer) could not be formed because the disilane gas of Nakatani lacks nitrogen (describing disilane as $Si_2H_6$)]. Therefore, considering the specific purpose of supplying the second gas in Hirose (to provide nitrogen), a person of ordinary skill in the art would not have been motivated to replace the nitrogen-containing second gas of Hirose with the nitrogen-free disilane gas of Nakatani. Such a change cannot be considered obvious to a person of ordinary skill in the art.
”
The Examiner notes that the above argument is moot with regards to the new rejection of claim 1 as this new rejection does not reference Nakatanii. However, this argument is relevant to the rejection of claim 21, in which a 3DMAS gas (which contains nitrogen), is replaced with a DCS gas (which does not contain nitrogen).
The Examiner finds this argument is not persuasive because the 3DMAS gas of Hirose does not need to be the nitrogen source for the first layer. From Saido [0090], NH--3 may be the nitrogen source for a SiCN film. Therefore, one of ordinary skill in the art would recognize that were they to combine Hirose and Saido, the lack of nitrogen from the DCS gas could be made up for using NH-3 to form the first layer.
Further Applicant substantively argues:
“2. The Cited Art Fails to Teach a "Chlorosilane" Second Gas. Amended Claim 1 further recites that the second gas is "a chlorosilane gas containing a Si-Si bond."In this regard, Hirose discloses an aminosilane gas as the second gas and discloses a 3DMAS gas as an example of the aminosilane gas, but does not disclose a chlorosilane gas]. Nakatani also discloses a disilane gas and an aminosilane gas as examples of the second gas, but does not disclose a chlorosilane gas containing a Si- Si bond, [0105]]. While Nakatani [0105] mentions halosilanes such as $SiH_3Cl$ or $SiH_2C1_2$, these specific examples lack the Si-Si bond required by the claim, whereas the Si-Si bonded gas taught by Nakatani (Disilane) is not a chlorosilane. Thus, neither Hirose nor Nakatani discloses or suggests using a chlorosilane gas containing a Si-Si bond as the second gas.”
Applicant’s above argument, with respect to the rejection(s) of claim(s) has been fully considered and is persuasive. Therefore, the rejection has been withdrawn. However, upon further consideration, a new ground(s) of rejection is made in view of another embodiment of Hirose.
In the interest of compact prosecution, if the Applicant were to amend an independent claim with the following limitation:
“wherein the first gas does not contain nitrogen”
It would overcome the current rejections for claim 1. The Examiner is available for interview at Applicant’s convenience for discussion of claim amendments.
Conclusion
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to ALEXANDRE XAVIER RAMIREZ whose telephone number is (571)272-2715. The examiner can normally be reached Monday - Friday 8:30 AM to 6:00 PM.
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/ALEXANDRE X RAMIREZ/Examiner, Art Unit 2812
/William B Partridge/Supervisory Patent Examiner, Art Unit 2812