DETAILED ACTION
This is in response to communication received on 8/18/26.
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
The text of those sections of AIA 35 U.S.C. code not present in this action can be found in previous office actions dated 10/23/25 and 2/18/26.
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and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114.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 8/18/26 has been entered.
Claim Rejections - 35 USC § 112
The claim rejection(s) under pre-AIA 35 U.S.C. 112 First Paragraph or AIA 35 U.S.C. 112(a) as being as failing to comply with the written description requirement on claims 1-20 is maintained. The rejection is updated below to meet the added claim limitations.
Examiner notes that the term ‘oxygen-and-not-hydrogen containing precursor’ does appear in the specification, specifically in paragraph 46.
For ease, Examiner provides the paragraph here:
[0046] In some embodiments, an oxygen-containing precursor can refer to a precursor that does not contain hydrogen. In some embodiments, an oxygen-containing precursor can be referred to an oxygen-and-not-hydrogen-containing precursor.
As for claim 1, and 16, Examiner notes that the claims have three issues that are shared as they all use the same language to describe these limitations.
Firstly, Examiner notes that the claim as written is performing first operations comprising: providing a silicon-containing precursor; providing an oxygen-and-not-hydrogen-containing precursor without hydrogen present in the semiconductor processing chamber. To be clear, this claim is claiming the scope of a first operation with an oxygen-and-not-hydrogen-containing precursor without hydrogen present in the semiconductor processing chamber.
There is no support for this in the specification.
In the specification, the first operation is performed with “The first operations may include providing an oxygen-and-hydrogen-containing precursor (708) as described herein” (paragraph 66) and also makes clear the first operation has the effect of “Providing the oxygen-and-hydrogen-containing precursor can cause a gap in the feature to close by causing a first side of the silicon-and-oxygen-containing material within the feature to bond with a second side of the silicon-and-oxygen-containing material within the feature as described in relation to at least FIGS. 3A-3B.”
In the specification, it is the second operation wherein the “The second operations may include providing an oxygen-containing precursor (808) as described herein” (paragraph 90). As established above, it is only the term an oxygen-containing precursor that can refer to an oxygen-and-not-hydrogen-containing precursor.
The specification makes clear the first operations have an oxygen-and-hydrogen-containing precursor and that it is the second operation that can have an oxygen-and-not-hydrogen-containing precursor. The claims require the opposite and are thereby not in line with the specification, instead presenting an embodiment that has no support.
Secondly, within the specification, there is a first operation and a second operation. There is nothing to suggest in the specification that the first operation can have two separate oxygen-containing precursors.
Specifically, the claims 1, and 16 define first operation as having a silicon-containing precursor, an oxygen-and-hydrogen-containing precursor and then an oxygen-and-not-hydrogen containing precursor. Within the specification, the first operation only has a silicon-containing precursor and an oxygen-and-hydrogen-containing precursor. Thus, the claim embodiment with a first operation with three precursors is not supported by the specification.
Examiner notes that this difference is illustrated in claim 4, which depends from claim 1. It defines a second operation in line with the specification (i.e. a second operation with a silicon-containing precursor and an oxygen-and-not-hydrogen-containing precursor), which also appears to be redundant with the oxygen-and-not-hydrogen containing precursor step of claim 1.
Thirdly, the language of without hydrogen present in the semiconductor processing chamber is not supported in the specification. Specifically, ‘hydrogen’ within the specification is used generically to describe the element, not a compound. Hydrogen, within the lexicon of the specification, then encompasses all compounds with hydrogen in it, and while there is support for an oxygen-and-not-hydrogen-containing precursor, there is no support for a processing chamber completely excluding any compound with the element of hydrogen. Examiner can guess that the Applicant is attempting to exclude hydrogen gas from inclusion in the gas mixture, but the language of the claim is too broad and would exclude any material with hydrogen as a compound, whether it be in the substrate, or a coating on the chamber walls, or as a component of the cooling mechanism within the substrate holder. The specification does not support that.
For purposes of compact prosecution, Examiner will interpret without hydrogen present in the semiconductor processing chamber to mean without hydrogen gas.
As for claim 2-9, 14-15 and 19-20, they depend from claims 1 and 16, they contain all the limitations thereof and are similarly rejected.
As for claim 10, there are three issues for this claim.
Firstly, the language of without hydrogen present in the semiconductor processing chamber is not supported in the specification. Specifically, ‘hydrogen’ within the specification is used generically to describe the element, not a compound. Hydrogen, within the lexicon of the specification, then encompasses all compounds with hydrogen in it, and while there is support for an oxygen-and-not-hydrogen-containing precursor, there is no support for a processing chamber completely excluding any compound with the element of hydrogen. Examiner can guess that the Applicant is attempting to exclude hydrogen gas from inclusion in the gas mixture, but the language of the claim is too broad and would exclude any material with hydrogen as a compound, whether it be in the substrate, or a coating on the chamber walls, or as a component of the cooling mechanism within the substrate holder. The specification does not support that.
Secondly, within the specification, there is a first operation and a second operation. There is nothing to suggest in the specification that the first operation can have two separate oxygen-containing precursors.
Specifically, the claim 10 defines the first operation as having a silicon-containing precursor, an oxygen-and-hydrogen-containing precursor and then an oxygen-and-not-hydrogen containing precursor. Within the specification, the first operation only has a silicon-containing precursor and an oxygen-and-hydrogen-containing precursor. Thus, the claim embodiment with a first operation with three precursors is not supported by the specification.
Examiner notes that this difference is illustrated in claim 12, which depends from claim 10. It defines a second operation in line with the specification (i.e. a second operation with a silicon-containing precursor and an oxygen-and-not-hydrogen-containing precursor), which also appears to be redundant with the oxygen-and-not-hydrogen containing precursor step of claim 1.
Thirdly, the limitations of providing an oxygen-and-hydrogen-containing precursor without
hydrogen present in the semiconductor processing chamber is not supported in the specification because it is physically impossible. An oxygen-and-hydrogen-containing precursor cannot be provided into a semiconductor processing chamber without hydrogen present because if the oxygen-and-hydrogen-containing precursor is present, there is hydrogen present in the chamber.
Based upon the other amendments to the independent claims, it appears this amendment was applied to the providing an oxygen-and-hydrogen-containing precursor limitation in error and it was meant to be modifying the language providing an oxygen-and-not-hydrogen-containing precursor.
For purposes of compact prosecution and based on the amendments to the other claims, this claim will be interpreted as reading providing an oxygen-and-not-hydrogen-containing precursor without hydrogen present in the semiconductor processing chamber.
As for claim 11, they depend from claim 10, they contain all the limitations thereof and are similarly rejected.
Appropriate correction is required.
Claim Rejections - 35 USC § 102
The claim rejection(s) under 35. U.S.C. 102(a)(1) as being anticipated by Go et al. USPGPub 2015/0235836 hereinafter GO on claims 1-4, 7, 10-12, 15-16, 19-20 are withdrawn because the independent claims 1, 10, 12 and 16 have been amended.
Claim Rejections - 35 USC § 103
The claim rejection(s) under AIA 35 U.S.C. 103 as being obvious over Go et al. US PGPub 2015/0235836 hereinafter GO on claim 13 is withdrawn because the independent claim 12 have been amended.
The claim rejection(s) under AIA 35 U.S.C. 103 as being obvious over Go et al. USPGPub 2015/0235836 hereinafter GO as applied to claim 1, 10 and 16 above, and further in view of Tang et al. US PGPub 2019/0348273 hereinafter TANG on claims 5-6, 8-9 and 17-18 are withdrawn because the independent claim 1, 10 and 16 have been amended.
The claim rejection(s) under AIA 35 U.S.C. 103 as being obvious over Go et al. USPGPub 201510235836 hereinafter GO as applied to claim 10 above, and further in view of Yamazaki et al. US PG Pub 202110320193 hereinafter YAMAZAKI on claim 14 is withdrawn because the independent claim 10 has been amended.
Claim(s) 1-12, 14-16, and 19-20 are rejected under 35 U.S.C. 103 as being unpatentable over Kang et al. US PGPub 2014/0106574 hereinafter KANG.
As for claim 1, KANG teaches “Provided herein are methods and apparatus for filling one or more gaps on a semiconductor substrate. The disclosed embodiments are especially useful for forming seam-free, void-free fill in both narrow and wide features. The methods may be performed without any intervening etching operations to achieve a single step deposition. In various implementations, a first operation is performed using a novel PEALD fill mechanism to fill narrow gaps and line wide gaps” (abstract, lines 1-8), i.e. a method of filling a feature on a semiconductor substrate, the method comprising: performing a process to fill the feature on the semiconductor substrate in a semiconductor processing chamber.
KANG teaches “In one aspect of the embodiments herein, a method is provided for filling a gap including (a) introducing a first reactant in vapor phase into a reaction chamber having the substrate therein, and allowing the first reactant to adsorb onto the substrate surface” (paragraph 5, lines 7-11), “(e) repeating operations (a) through (d) to form additional film layers” (paragraph 5, lines 18-19), and “In these cases, the silicon-containing reactant may be for example, a silane, a halosilane or an aminosilane” (paragraph 55, lines 2-4), i.e. wherein the process comprises repeatedly performing first operations comprising: providing a silicon-containing precursor.
KANG teaches “(b) introducing a second reactant in vapor phase into the reaction chamber and allowing the second reactant to adsorb onto the substrate surface” (paragraph 5, lines 12-15), and “In certain implementations, an oxygen-containing oxidizing reactant is used. Examples of oxygen-containing oxidizing reactants include oxygen, ozone, nitrous oxide, carbon monoxide, etc.” (paragraph 57), i.e. providing an oxygen-and-not-hydrogen-containing precursor without hydrogen present in the semiconductor processing chamber.
KANG further teaches “(c) exposing the substrate surface to plasma to drive a surface reaction between the first and second reactants on the substrate surface to form a film layer that lines the bottom and sidewalls of the gap” (paragraph 5, lines 14-17), i.e. contacting the semiconductor substrate with the silicon-containing precursor and the oxygen-and-not-hydrogen-containing precursor to form a silicon-and-oxygen-containing material within the feature defined on the semiconductor substrate.
KANG further teaches “(d) sweeping the reaction chamber without performing a pumpdown” (paragraph 5, lines 17-18), i.e. purging the semiconductor processing chamber of the silicon-containing precursor and the oxygen-and-not-hydrogen-containing precursor.
KANG further teaches “The first and second reactants may be the same as at least one of the third and fourth reactants. For example, the first and second reactants may each be the same as the third and fourth reactants. In other cases, there may be no overlap between the first and second reactants and the third and fourth reactants” (paragraph 10, lines 1-6), i.e. wherein the reactants can be different as the cyclic deposition continues such as providing a different oxidizing agent than the first oxidizing agent, i.e. providing a second oxygen-containing precursor.
Examiner notes that when KANG is describing their invention they list the following materials: “oxygen-containing oxidizing reactants include oxygen, ozone, nitrous oxide, carbon monoxide, etc” (paragraph 57), which are not an oxygen-and-hydrogen-containing precursor.
However, KANG does teach “Other precursors, such as will be apparent to or readily discernible by those skilled in the art given the teachings provided herein, may also be used” (paragraph 59) and, in a section describing the background of PEALD reactant lists “The other reactant is sometimes referred to as an auxiliary reactant or a co-reactant. Nonlimiting examples of co-reactants include oxygen, ozone, hydrogen, hydrazine, water, carbon monoxide, nitrous oxide, ammonia, alkyl amines, and the like. The co-reactant may also be a mix of reactants, as mentioned above” (paragraph 52, lines 8-13), i.e. oxygen-and-hydrogen-containing precursor.
In view of these two teachings, it would have been obvious to one of ordinary skill in the art to use one of the oxygen-and-hydrogen-containing precursor in the invention of KANG because KANG establishes that such precursors were known equivalents to the listed oxidizing agents and teaches using multiple different reactants in different reaction steps. It is a prima facie case of obviousness to substitute one known element for another to obtain predictable results.
KANG further teaches “where when opposing film layers on opposite sidewalls of the gap approach one another, surface groups present on the opposing film layers crosslink with one another to thereby fill the gap” (paragraph 5, lines 19-22) and “As deposition proceeds and the sidewalls close in towards one another, the terminal groups may crosslink with one another, thus avoiding any seam. In the case of a gap-filling silicon oxide film, for example, surface hydroxyls/silanols on one sidewall may crosslink with surface hydroxyls/silanols on the opposing wall, thereby liberating water and forming a silicon-oxide matrix. These terminal cross-linking groups may preferentially be found on the sidewalls of a gap” (paragraph 44, lines 3-11), i.e. contacting the semiconductor substrate with the oxygen-and-hydrogen-containing precursor to close a gap between portions of the silicon-and-oxygen-containing material on opposing sidewalls of the feature defined on the semiconductor substrate by hydroxylating oxygen atoms in the silicon-and-oxygen-containing material along opposing sidewalls of the feature.
As for claim 2, KANG further teaches “where when opposing film layers on opposite sidewalls of the gap approach one another, surface groups present on the opposing film layers crosslink with one another to thereby fill the gap” (paragraph 5, lines 19-22) and “As deposition proceeds and the sidewalls close in towards one another, the terminal groups may crosslink with one another, thus avoiding any seam. In the case of a gap-filling silicon oxide film, for example, surface hydroxyls/silanols on one sidewall may crosslink with surface hydroxyls/silanols on the opposing wall, thereby liberating water and forming a silicon-oxide matrix. These terminal cross-linking groups may preferentially be found on the sidewalls of a gap” (paragraph 44, lines 3-11), i.e. wherein providing the oxygen-and-hydrogen-containing precursor causes the gap to close by causing a first side of the silicon-and-oxygen-containing material within the feature to bond with a second side of the silicon-and-oxygen-containing material within the feature.
As for claim 3, KANG teaches “(b) introducing a second reactant in vapor phase into the reaction chamber and allowing the second reactant to adsorb onto the substrate surface” (paragraph 5, lines 12-15), and “In certain implementations, an oxygen-containing oxidizing reactant is used. Examples of oxygen-containing oxidizing reactants include oxygen, ozone, nitrous oxide, carbon monoxide, etc.” (paragraph 57). See rejection above for combination of two precursors such that it teaches wherein forming the silicon-and-oxygen-containing material within the feature includes forming an atomic layer of silicon on an exposed surface of the feature; and wherein forming the silicon-and-oxygen-containing material within the feature includes providing oxygen to the atomic layer of silicon using the oxygen-and-not-hydrogen containing precursor.
As for claim 4, as argued above, KANG teaches “In one aspect of the embodiments herein, a method is provided for filling a gap including (a) introducing a first reactant in vapor phase into a reaction chamber having the substrate therein, and allowing the first reactant to adsorb onto the substrate surface” (paragraph 5, lines 7-11), “(e) repeating operations (a) through (d) to form additional film layers” (paragraph 5, lines 18-19), and “In these cases, the silicon-containing reactant may be for example, a silane, a halosilane or an aminosilane” (paragraph 55, lines 2-4).
KANG further teaches “The first and second reactants may be the same as at least one of the third and fourth reactants. For example, the first and second reactants may each be the same as the third and fourth reactants. In other cases, there may be no overlap between the first and second reactants and the third and fourth reactants” (paragraph 10, lines 1-6), i.e. wherein the reactants can be different as the cyclic deposition continues such as providing a different oxidizing agent than the first oxidizing agent, i.e. providing a second oxygen-containing precursor.
However, KANG does teach “Other precursors, such as will be apparent to or readily discernible by those skilled in the art given the teachings provided herein, may also be used” (paragraph 59) and, in a section describing the background of PEALD reactant lists “The other reactant is sometimes referred to as an auxiliary reactant or a co-reactant. Nonlimiting examples of co-reactants include oxygen, ozone, hydrogen, hydrazine, water, carbon monoxide, nitrous oxide, ammonia, alkyl amines, and the like. The co-reactant may also be a mix of reactants, as mentioned above” (paragraph 52, lines 8-13), i.e. oxygen-and-hydrogen-containing precursor.
In view of these two teachings, it would have been obvious to one of ordinary skill in the art to use one of the oxygen-and-hydrogen-containing precursor in the invention of KANG such that the process includes an PEALD process with the first and second precursor and then a second process with the first and third precursor such that wherein the process to fill the feature further comprises repeatedly performing second operations prior to repeatedly performing first operations, wherein both the first operations and the second operations are done at about a first pressure level, the second operations comprising: providing the silicon-containing precursor; contacting the semiconductor substrate with the silicon-containing precursor to form a silicon-containing material within the feature defined on the semiconductor substrate; purging the semiconductor processing chamber; providing the oxygen-and-not-hydrogen-containing precursor without hydrogen present in the semiconductor processing chamber; and contacting the semiconductor substrate with the oxygen-and-not-hydrogen- containing precursor to form a silicon-and-oxygen-containing material within the feature defined on the semiconductor substrate because KANG establishes that such precursors were known equivalents to the listed oxidizing agents and teaches using multiple different reactants in different reaction steps. It is a prima facie case of obviousness to substitute one known element for another to obtain predictable results.
As for claim 5, KANG teaches “The pressure inside the reaction chamber during the PEALD process may be between about 1-10 Torr, or between about 3-7 Torr, for example about 6 Torr” (paragraph 69), i.e. a range that overlaps with wherein the first pressure level is greater than or about 2 Torr. 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, 191USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990); In re Geisler, 116 F.3d 1465, 1469-71, 43 USPQ2d, 1362, 1365-66 (Fed. Cir. 1997). See MPEP 2144.05.
As for claim 6, KANG teaches “This bottom-up fill mechanism helps achieve the void-free, seamfree fill, particularly in narrow gaps (e.g., gaps having a critical dimension (CD) of about 50 nm or less) and/or gaps having high aspect ratios ( e.g., depth to width aspect ratio of about 4:1 or higher)” (paragraph 30, lines 6-11), i.e. a range that overlaps with wherein the feature is characterized by an aspect ratio of greater than or about 10:1. 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, 191USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990); In re Geisler, 116 F.3d 1465, 1469-71, 43 USPQ2d, 1362, 1365-66 (Fed. Cir. 1997). See MPEP 2144.05.
As for claim 7, KANG further teaches “The first and second reactants may be the same as at least one of the third and fourth reactants. For example, the first and second reactants may each be the same as the third and fourth reactants. In other cases, there may be no overlap between the first and second reactants and the third and fourth reactants” (paragraph 10, lines 1-6), i.e. wherein the reactants can be different as the cyclic deposition continues such as providing a different oxidizing agent than the first oxidizing agent, i.e. providing a second oxygen-containing precursor.
Examiner notes that when KANG is describing their invention they list the following materials: “oxygen-containing oxidizing reactants include oxygen, ozone, nitrous oxide, carbon monoxide, etc” (paragraph 57), which are not an oxygen-and-hydrogen-containing precursor.
However, KANG does teach “Other precursors, such as will be apparent to or readily discernible by those skilled in the art given the teachings provided herein, may also be used” (paragraph 59) and, in a section describing the background of PEALD reactant lists “The other reactant is sometimes referred to as an auxiliary reactant or a co-reactant. Nonlimiting examples of co-reactants include oxygen, ozone, hydrogen, hydrazine, water, carbon monoxide, nitrous oxide, ammonia, alkyl amines, and the like. The co-reactant may also be a mix of reactants, as mentioned above” (paragraph 52, lines 8-13), i.e. oxygen-and-hydrogen-containing precursor comprises O2 and H2.
In view of these two teachings, it would have been obvious to one of ordinary skill in the art to use one of the oxygen-and-hydrogen-containing precursor comprises O2 and H2 in the invention of KANG because KANG establishes that such precursors were known equivalents to the listed oxidizing agents and teaches using multiple different reactants in different reaction steps. It is a prima facie case of obviousness to substitute one known element for another to obtain predictable results.
As for claim 9, KANG further teaches “The first and second reactants may be the same as at least one of the third and fourth reactants. For example, the first and second reactants may each be the same as the third and fourth reactants. In other cases, there may be no overlap between the first and second reactants and the third and fourth reactants” (paragraph 10, lines 1-6), i.e. wherein the reactants can be different as the cyclic deposition continues such as providing a different oxidizing agent than the first oxidizing agent, i.e. providing a second oxygen-containing precursor.
Examiner notes that when KANG is describing their invention they list the following materials: “oxygen-containing oxidizing reactants include oxygen, ozone, nitrous oxide, carbon monoxide, etc” (paragraph 57), which are not an oxygen-and-hydrogen-containing precursor.
However, KANG does teach “Other precursors, such as will be apparent to or readily discernible by those skilled in the art given the teachings provided herein, may also be used” (paragraph 59) and, in a section describing the background of PEALD reactant lists “The other reactant is sometimes referred to as an auxiliary reactant or a co-reactant. Nonlimiting examples of co-reactants include oxygen, ozone, hydrogen, hydrazine, water, carbon monoxide, nitrous oxide, ammonia, alkyl amines, and the like. The co-reactant may also be a mix of reactants, as mentioned above” (paragraph 52, lines 8-13), i.e. oxygen-and-hydrogen-containing precursor comprises H2O.
In view of these two teachings, it would have been obvious to one of ordinary skill in the art to use one of the oxygen-and-hydrogen-containing precursor comprises H2O in the invention of KANG because KANG establishes that such precursors were known equivalents to the listed oxidizing agents and teaches using multiple different reactants in different reaction steps. It is a prima facie case of obviousness to substitute one known element for another to obtain predictable results.
As for claim 10, KANG teaches “Provided herein are methods and apparatus for filling one or more gaps on a semiconductor substrate. The disclosed embodiments are especially useful for forming seam-free, void-free fill in both narrow and wide features. The methods may be performed without any intervening etching operations to achieve a single step deposition. In various implementations, a first operation is performed using a novel PEALD fill mechanism to fill narrow gaps and line wide gaps” (abstract, lines 1-8), i.e. a method of filling a feature on a semiconductor substrate, the method comprising: performing a process to fill the feature on the semiconductor substrate in a semiconductor processing chamber.
KANG teaches “In one aspect of the embodiments herein, a method is provided for filling a gap including (a) introducing a first reactant in vapor phase into a reaction chamber having the substrate therein, and allowing the first reactant to adsorb onto the substrate surface” (paragraph 5, lines 7-11), “(e) repeating operations (a) through (d) to form additional film layers” (paragraph 5, lines 18-19), and “In these cases, the silicon-containing reactant may be for example, a silane, a halosilane or an aminosilane” (paragraph 55, lines 2-4), i.e. wherein the process comprises repeatedly performing first operations comprising: providing a silicon-containing precursor, contacting the semiconductor substrate with the silicon-containing precursor to form a silicon-containing material within the feature defined on the semiconductor substrate.
KANG teaches “Next, at operation 103 the reaction chamber is purged, for example with an inert gas or a nitrogen carrier gas. This helps remove any remaining first reactant from the reaction chamber” (paragraph 46, lines 11), i.e. purging the semiconductor processing chamber.
KANG teaches “(b) introducing a second reactant in vapor phase into the reaction chamber and allowing the second reactant to adsorb onto the substrate surface” (paragraph 5, lines 12-15), “In certain implementations, an oxygen-containing oxidizing reactant is used. Examples of oxygen-containing oxidizing reactants include oxygen, ozone, nitrous oxide, carbon monoxide, etc.” (paragraph 57), and “(c) exposing the substrate surface to plasma to drive a surface reaction between the first and second reactants on the substrate surface to form a film layer that lines the bottom and sidewalls of the gap” (paragraph 5, lines 14-17), i.e. providing an oxygen-and-not-hydrogen-containing precursor without hydrogen present in the semiconductor processing chamber, contacting the semiconductor substrate with the oxygen-and-not-hydrogen-containing precursor to form a silicon-and-oxygen-containing material within the feature defined on the semiconductor substrate.
KANG further teaches “The first and second reactants may be the same as at least one of the third and fourth reactants. For example, the first and second reactants may each be the same as the third and fourth reactants. In other cases, there may be no overlap between the first and second reactants and the third and fourth reactants” (paragraph 10, lines 1-6), i.e. wherein the reactants can be different as the cyclic deposition continues such as providing a different oxidizing agent than the first oxidizing agent, i.e. providing a second oxygen-containing precursor; and contacting the silicon-and-oxygen-containing material with the second oxygen-containing precursor.
Examiner notes that when KANG is describing their invention they list the following materials: “oxygen-containing oxidizing reactants include oxygen, ozone, nitrous oxide, carbon monoxide, etc” (paragraph 57), which are not an oxygen-and-hydrogen-containing precursor.
However, KANG does teach “Other precursors, such as will be apparent to or readily discernible by those skilled in the art given the teachings provided herein, may also be used” (paragraph 59) and, in a section describing the background of PEALD reactant lists “The other reactant is sometimes referred to as an auxiliary reactant or a co-reactant. Nonlimiting examples of co-reactants include oxygen, ozone, hydrogen, hydrazine, water, carbon monoxide, nitrous oxide, ammonia, alkyl amines, and the like. The co-reactant may also be a mix of reactants, as mentioned above” (paragraph 52, lines 8-13), i.e. oxygen-and-hydrogen-containing precursor.
In view of these two teachings, it would have been obvious to one of ordinary skill in the art to use one of the oxygen-and-hydrogen-containing precursor in the invention of KANG because KANG establishes that such precursors were known equivalents to the listed oxidizing agents and teaches using multiple different reactants in different reaction steps. It is a prima facie case of obviousness to substitute one known element for another to obtain predictable results.
KANG teaches “In some embodiments, therefore, the process is conducted at a temperature between about 200-400° C. In other cases, however, the temperature may fall outside this range” (paragraph 68, lines 3-6), i.e. a range that overlaps with wherein the process is performed at a temperature greater than or about 400 °C. 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, 191USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990); In re Geisler, 116 F.3d 1465, 1469-71, 43 USPQ2d, 1362, 1365-66 (Fed. Cir. 1997). See MPEP 2144.05.
As for claim 11, KANG further teaches “where when opposing film layers on opposite sidewalls of the gap approach one another, surface groups present on the opposing film layers crosslink with one another to thereby fill the gap” (paragraph 5, lines 19-22) and “As deposition proceeds and the sidewalls close in towards one another, the terminal groups may crosslink with one another, thus avoiding any seam. In the case of a gap-filling silicon oxide film, for example, surface hydroxyls/silanols on one sidewall may crosslink with surface hydroxyls/silanols on the opposing wall, thereby liberating water and forming a silicon-oxide matrix. These terminal cross-linking groups may preferentially be found on the sidewalls of a gap” (paragraph 44, lines 3-11), i.e. wherein contacting the silicon-and-oxygen-containing material with the oxygen-and-hydrogen-containing precursor causes a gap in the feature to close by causing a first side of the silicon-and-oxygen-containing material within the feature to bond with a second side of the silicon-and-oxygen-containing material within the feature.
As for claim 12, as argued above, KANG teaches “In one aspect of the embodiments herein, a method is provided for filling a gap including (a) introducing a first reactant in vapor phase into a reaction chamber having the substrate therein, and allowing the first reactant to adsorb onto the substrate surface” (paragraph 5, lines 7-11), “(e) repeating operations (a) through (d) to form additional film layers” (paragraph 5, lines 18-19), and “In these cases, the silicon-containing reactant may be for example, a silane, a halosilane or an aminosilane” (paragraph 55, lines 2-4).
KANG also teaches “Next, at operation 103 the reaction chamber is purged, for example with an inert gas or a nitrogen carrier gas. This helps remove any remaining first reactant from the reaction chamber” (paragraph 46, lines 11), i.e. purging the semiconductor processing chamber after introducing the first precursor, i.e. contacting the semiconductor substrate with the silicon-containing precursor to form a silicon-containing material within the feature defined on the semiconductor substrate; purging the semiconductor processing chamber.
KANG further teaches “The first and second reactants may be the same as at least one of the third and fourth reactants. For example, the first and second reactants may each be the same as the third and fourth reactants. In other cases, there may be no overlap between the first and second reactants and the third and fourth reactants” (paragraph 10, lines 1-6), i.e. wherein the reactants can be different as the cyclic deposition continues such as providing a different oxidizing agent than the first oxidizing agent, i.e. providing a second oxygen-containing precursor.
However, KANG does teach “Other precursors, such as will be apparent to or readily discernible by those skilled in the art given the teachings provided herein, may also be used” (paragraph 59) and, in a section describing the background of PEALD reactant lists “The other reactant is sometimes referred to as an auxiliary reactant or a co-reactant. Nonlimiting examples of co-reactants include oxygen, ozone, hydrogen, hydrazine, water, carbon monoxide, nitrous oxide, ammonia, alkyl amines, and the like. The co-reactant may also be a mix of reactants, as mentioned above” (paragraph 52, lines 8-13), i.e. oxygen-and-hydrogen-containing precursor.
In view of these two teachings, it would have been obvious to one of ordinary skill in the art to use one of the oxygen-and-hydrogen-containing precursor in the invention of KANG such that the process includes an PEALD process with the first and second precursor and then a second process with the first and third precursor such that providing the oxygen-and-not-hydrogen-containing precursor without hydrogen present in the semiconductor processing chamber; and contacting the semiconductor substrate with the oxygen-and-not-hydrogen- containing precursor to form a silicon-and-oxygen-containing material within the feature defined on the semiconductor substrate because KANG establishes that such precursors were known equivalents to the listed oxidizing agents and teaches using multiple different reactants in different reaction steps. It is a prima facie case of obviousness to substitute one known element for another to obtain predictable results.
As for claim 14, KANG teaches “The gas used to generate the plasma may include an inert gas such as argon or helium. The gas will also typically include one of the reactants, for example an oxidizing reactant where an oxide film is being formed” (paragraph 71), i.e. wherein the oxygen-and-hydrogen containing precursor comprises a plasma.
As for claim 15, KANG teaches “The gas used to generate the plasma may include an inert gas such as argon or helium. The gas will also typically include one of the reactants, for example an oxidizing reactant where an oxide film is being formed” (paragraph 71), i.e. wherein the oxygen-and-hydrogen-containing precursor comprises a gas.
Claim(s) 8, 16 and 19-20 are rejected under 35 U.S.C. 103 as being unpatentable over Kang et al. US PGPub 2014/0106574 hereinafter KANG as applied to claim 1 above, and further in view of Tang et al. US PGPub 2019/0348273 hereinafter TANG.
As for claim 8, Examiner notes that when KANG is describing their invention they list the following materials: “oxygen-containing oxidizing reactants include oxygen, ozone, nitrous oxide, carbon monoxide, etc” (paragraph 57).
KANG is silent on wherein the oxygen-and-hydrogen-containing precursor comprises H2O2.
KANG does teach “Other precursors, such as will be apparent to or readily discernible by those skilled in the art given the teachings provided herein, may also be used” (paragraph 59)
TANG teaches "The present disclosure relates generally to methods for depositing an oxide film by a cyclical deposition process and particular methods for depositing an oxide film by a cyclical deposition process including a first sub-cycle and a second sub-cycle" (paragraph 2, lines 1-5) and "In some embodiments of the disclosure, the oxide films formed as disclosed herein may be utilized as gap-fill materials" (paragraph 90, lines 1-3).
TANG teaches "In some embodiments the oxygen precursor comprises at least one of water (H2O), hydrogen peroxide (H2O2), ozone (O3)," (paragraph 54, lines 4- 6), i.e. wherein H2O2 is a known oxidizer for applying oxide materials in ALD processes. It would have been obvious to one of ordinary skill in the art before the effective filing date to include wherein the oxygen-and-hydrogen-containing precursor comprises H2O2 in the process of KANG because TANG teaches that the material was a known oxidizing agent when forming layer by layer oxide materials and equivalent to the oxidizing materials listed by KANG. It is a prima facie case of obviousness to substitute one known element for another to obtain predictable results.
As for claim 16, KANG teaches “Provided herein are methods and apparatus for filling one or more gaps on a semiconductor substrate. The disclosed embodiments are especially useful for forming seam-free, void-free fill in both narrow and wide features. The methods may be performed without any intervening etching operations to achieve a single step deposition. In various implementations, a first operation is performed using a novel PEALD fill mechanism to fill narrow gaps and line wide gaps” (abstract, lines 1-8), i.e. a method of filling a feature on a semiconductor substrate, the method comprising: performing a process to fill the feature on the semiconductor substrate in a semiconductor processing chamber.
KANG teaches “In one aspect of the embodiments herein, a method is provided for filling a gap including (a) introducing a first reactant in vapor phase into a reaction chamber having the substrate therein, and allowing the first reactant to adsorb onto the substrate surface” (paragraph 5, lines 7-11), “(e) repeating operations (a) through (d) to form additional film layers” (paragraph 5, lines 18-19), i.e. wherein the process comprises repeatedly performing first operations.
KANG teaches “The pressure inside the reaction chamber during the PEALD process may be between about 1-10 Torr, or between about 3-7 Torr, for example about 6 Torr” (paragraph 69), i.e. at a first pressure level greater than or about 2 Torr.
KANG teaches “In one aspect of the embodiments herein, a method is provided for filling a gap including (a) introducing a first reactant in vapor phase into a reaction chamber having the substrate therein, and allowing the first reactant to adsorb onto the substrate surface” (paragraph 5, lines 7-11), “(e) repeating operations (a) through (d) to form additional film layers” (paragraph 5, lines 18-19), and “In these cases, the silicon-containing reactant may be for example, a silane, a halosilane or an aminosilane” (paragraph 55, lines 2-4), i.e. providing a silicon-containing precursor; contacting the semiconductor substrate with the silicon-containing precursor to form a silicon-containing material within the feature defined on the semiconductor substrate.
KANG teaches “Next, at operation 103 the reaction chamber is purged, for example with an inert gas or a nitrogen carrier gas. This helps remove any remaining first reactant from the reaction chamber” (paragraph 46, lines 11), i.e. purging the semiconductor processing chamber.
KANG teaches “(b) introducing a second reactant in vapor phase into the reaction chamber and allowing the second reactant to adsorb onto the substrate surface” (paragraph 5, lines 12-15), and “In certain implementations, an oxygen-containing oxidizing reactant is used. Examples of oxygen-containing oxidizing reactants include oxygen, ozone, nitrous oxide, carbon monoxide, etc.” (paragraph 57), i.e. providing an oxygen-and-not-hydrogen-containing precursor without hydrogen present in the semiconductor processing chamber.
KANG further teaches “(c) exposing the substrate surface to plasma to drive a surface reaction between the first and second reactants on the substrate surface to form a film layer that lines the bottom and sidewalls of the gap” (paragraph 5, lines 14-17), i.e. contacting the semiconductor substrate with the oxygen-and-not hydrogen- containing precursor to form a silicon-and-oxygen-containing material within the feature defined on the semiconductor substrate.
KANG further teaches “The first and second reactants may be the same as at least one of the third and fourth reactants. For example, the first and second reactants may each be the same as the third and fourth reactants. In other cases, there may be no overlap between the first and second reactants and the third and fourth reactants” (paragraph 10, lines 1-6), i.e. wherein the reactants can be different as the cyclic deposition continues such as providing a different oxidizing agent than the first oxidizing agent, i.e. providing a second oxygen-containing precursor.
Examiner notes that when KANG is describing their invention they list the following materials: “oxygen-containing oxidizing reactants include oxygen, ozone, nitrous oxide, carbon monoxide, etc.” (paragraph 57), which are not an oxygen-and-hydrogen-containing precursor.
However, KANG does teach “Other precursors, such as will be apparent to or readily discernible by those skilled in the art given the teachings provided herein, may also be used” (paragraph 59) and, in a section describing the background of PEALD reactant lists “The other reactant is sometimes referred to as an auxiliary reactant or a co-reactant. Nonlimiting examples of co-reactants include oxygen, ozone, hydrogen, hydrazine, water, carbon monoxide, nitrous oxide, ammonia, alkyl amines, and the like. The co-reactant may also be a mix of reactants, as mentioned above” (paragraph 52, lines 8-13), i.e. oxygen-and-hydrogen-containing precursor.
In view of these two teachings, it would have been obvious to one of ordinary skill in the art to use one of the oxygen-and-hydrogen-containing precursor in the invention of KANG such that it includes wherein the process to fill the feature further comprises repeatedly performing second operations at a second pressure level… after repeatedly performing first operations, the second operations comprising: providing an oxygen-and-hydrogen-containing precursor; and contacting the silicon-and-oxygen-containing material with the oxygen-and-hydrogen-containing precursor because KANG establishes that such precursors were known equivalents to the listed oxidizing agents and teaches using multiple different reactants in different reaction steps. It is a prima facie case of obviousness to substitute one known element for another to obtain predictable results.
TANG teaches "In addition to achieving a desired deposition temperature, i.e., a desired substrate temperature, the deposition process may also regulate the pressure within the reaction chamber during deposition to obtain desirable characteristics of the deposited film. For example, in some embodiments of the disclosure, the deposition process may be performed within a reaction chamber regulated to a reaction chamber pressure of greater than 9 Torr, or greater than 50 Torr, or greater than 75 Torr, or even greater than 100 Torr" (paragraph 47, lines 1-9), i.e. a range that overlaps with wherein the second pressure level is about atmospheric pressure. 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); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990); In re Geisler, 116 F.3d 1465, 1469-71, 43 USPQ2d, 1362, 1365-66 (Fed. Cir. 1997). See MPEP 2144.05.
It would have been obvious to one of ordinary skill in the before the effective filing date to operate the process of GO at a range that overlaps with wherein the second pressure level is about atmospheric pressure because TANG teaches that such a range is useful for producing the desired characteristics of oxide.
As for claim 19, as argued above, KANG teaches “In one aspect of the embodiments herein, a method is provided for filling a gap including (a) introducing a first reactant in vapor phase into a reaction chamber having the substrate therein, and allowing the first reactant to adsorb onto the substrate surface” (paragraph 5, lines 7-11), “(e) repeating operations (a) through (d) to form additional film layers” (paragraph 5, lines 18-19), and “In these cases, the silicon-containing reactant may be for example, a silane, a halosilane or an aminosilane” (paragraph 55, lines 2-4).
KANG also teaches “Next, at operation 103 the reaction chamber is purged, for example with an inert gas or a nitrogen carrier gas. This helps remove any remaining first reactant from the reaction chamber” (paragraph 46, lines 11), i.e. purging the semiconductor processing chamber after introducing the first precursor, i.e. contacting the semiconductor substrate with the silicon-containing precursor to form a silicon-containing material within the feature defined on the semiconductor substrate; purging the semiconductor processing chamber.
KANG further teaches “The first and second reactants may be the same as at least one of the third and fourth reactants. For example, the first and second reactants may each be the same as the third and fourth reactants. In other cases, there may be no overlap between the first and second reactants and the third and fourth reactants” (paragraph 10, lines 1-6), i.e. wherein the reactants can be different as the cyclic deposition continues such as providing a different oxidizing agent than the first oxidizing agent, i.e. providing a second oxygen-containing precursor.
However, KANG does teach “Other precursors, such as will be apparent to or readily discernible by those skilled in the art given the teachings provided herein, may also be used” (paragraph 59) and, in a section describing the background of PEALD reactant lists “The other reactant is sometimes referred to as an auxiliary reactant or a co-reactant. Nonlimiting examples of co-reactants include oxygen, ozone, hydrogen, hydrazine, water, carbon monoxide, nitrous oxide, ammonia, alkyl amines, and the like. The co-reactant may also be a mix of reactants, as mentioned above” (paragraph 52, lines 8-13), i.e. oxygen-and-hydrogen-containing precursor.
In view of these two teachings, it would have been obvious to one of ordinary skill in the art to use one of the oxygen-and-hydrogen-containing precursor in the invention of KANG such that the process includes an PEALD process with the first and second precursor and then a second process with the first and third precursor such that wherein the second operations, prior to providing the oxygen-and-hydrogen-containing precursor, further comprise: providing the silicon-containing precursor; contacting the silicon-and-oxygen-containing material with the silicon-containing precursor to form a silicon-containing material within the feature; and purging the semiconductor processing chamber because KANG establishes that such precursors were known equivalents to the listed oxidizing agents and teaches using multiple different reactants in different reaction steps. It is a prima facie case of obviousness to substitute one known element for another to obtain predictable results.
As for claim 20, KANG further teaches “where when opposing film layers on opposite sidewalls of the gap approach one another, surface groups present on the opposing film layers crosslink with one another to thereby fill the gap” (paragraph 5, lines 19-22) and “As deposition proceeds and the sidewalls close in towards one another, the terminal groups may crosslink with one another, thus avoiding any seam. In the case of a gap-filling silicon oxide film, for example, surface hydroxyls/silanols on one sidewall may crosslink with surface hydroxyls/silanols on the opposing wall, thereby liberating water and forming a silicon-oxide matrix. These terminal cross-linking groups may preferentially be found on the sidewalls of a gap” (paragraph 44, lines 3-11), i.e. wherein contacting the silicon-and-oxygen-containing material with the oxygen-and-hydrogen-containing precursor causes a gap in the feature to close by causing a first side of the silicon-and-oxygen-containing material within the feature to bond with a second side of the silicon-and-oxygen-containing material within the feature.
Response to Arguments
Applicant’s arguments with respect to claim(s) 1-12, 14-16, and 19-20 have been considered but are moot because the new ground of rejection does not rely on any reference applied in the prior rejection of record for any teaching or matter specifically challenged in the argument.
Conclusion
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/KRISTEN A DAGENAIS/ Examiner, Art Unit 1717
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