DETAILED ACTION
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Specification
The title of the invention is not descriptive. A new title is required that is clearly indicative of the invention to which the claims are directed.
The following title is suggested: Method of Forming High-k Dielectric Film Using Bi-Metallic Compounds.
Claim Rejections - 35 USC § 102
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless –
(a)(1) the claimed invention was patented, described in a printed publication, or in public use, on sale, or otherwise available to the public before the effective filing date of the claimed invention.
(a)(2) the claimed invention was described in a patent issued under section 151, or in an application for patent published or deemed published under section 122(b), in which the patent or application, as the case may be, names another inventor and was effectively filed before the effective filing date of the claimed invention.
Claim(s) 1-3 is/are rejected under 35 U.S.C. 102(a)(1)(2) as being anticipated by Park et al. US 2019/0152996 A1.
Regarding claim 1, Park discloses A method of forming a dielectric film (Park Fig 2 shows method of forming lanthanum-oxide film, which may be used for purposes such as dielectric film [Col 18 line 20-25]), the method (flowchart Fig 2) comprising: a step of supplying a first source gas (operation P40-P42, supplying vaporized lanthanum compound onto substrate); a step of supplying a first purge gas (operation P44); a step of supplying a first reaction gas (operation P46, supplying reactive gas); and a step of supplying a second purge gas (operation P48),
wherein the step of supplying the first source gas (P40, lanthanum compound) comprises supplying a compound containing at least one metal selected from the group consisting of lanthanum (La), cerium (Ce), strontium (Sr), gadolinium (Gd), hafnium (Hf), and zirconium (Zr) (a lanthanum compound may be used, as shown in Fig 2, or a different precursor may be used such as “any one selected from silicon and a metal. … the metal may include, e.g., strontium (Sr), zirconium (Zr), hafnium (Hf), cerium (Ce), gadolinium (Gd), … “[Col 15 line 60 – Col 16 line 10] into a vacuum deposition apparatus (Fig 3-6 reaction chamber 254), and
wherein the step of supplying the first reaction gas (Park Fig 2 operation P46) comprises supplying a compound selected from the group consisting of O.sub.3 and H.sub.2O (“the oxidizing gas may include, e.g., oxygen, ozone, water vapor, …” [Col 17 line 20-22]) into the vacuum deposition apparatus (reaction chamber 254 Fig 3).
Regarding claim 2, Park discloses, The method of forming a dielectric film of claim 1, wherein the step of supplying the first source gas (operation P40-42) comprises supplying a first compound (first compound for producing the lanthanum oxide film contains any one of the lanthanum compound structures shown in Park Chemical Formula 1 – 4 [Col 4- 5]), containing a first metal selected from the group consisting of lanthanum (La), cerium (Ce), strontium (Sr), gadolinium (Gd), hafnium (Hf), and zirconium (Zr) (the first metal consists of lanthanum, explicitly disclosed in Fig 2), and a second compound different from the first compound and including a second metal selected from the group consisting of lanthanum (La), cerium (Ce), strontium (Sr), gadolinium (Gd), hafnium (Hf), and zirconium (Zr) (the use of lanthanum is disclosed in Fig 2, and other suitable precursors may be used independently or together with the lanthanum compound such as: Hf, Zr, Sr, Ce, Gd [Col 15 – 16]).
Regarding claim 3, Park discloses, The method of forming a dielectric film of claim 2, wherein the first metal is selected from the group consisting of lanthanum (La), cerium (Ce), strontium (Sr), and gadolinium (Gd) (the first metal compound is lanthanum), and the second metal is selected from the group consisting of hafnium (Hf) and zirconium (Zr) (second metal compound may be Hf or Zr [Col 15 – 16]).
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 (i.e., changing from AIA to pre-AIA ) 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, 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.
Claim(s) 4-5 is/are rejected under 35 U.S.C. 103 as being unpatentable over Park in view of Karbasian et al. US 2019/0393029 A1, hereinafter “Karbasian”.
Regarding claim 4, Park discloses, The method of forming a dielectric film of claim 1 (discussed above), but Park does not disclose the method further comprising: a step of supplying a second source gas between the step of supplying the first purge gas and the step of supplying the first reaction gas; and a step of supplying a third purge gas between the step of supplying the second source gas and the step of supplying the first reaction gas; wherein the step of supplying the first source gas comprises supplying a first compound containing a first metal selected from the group consisting of lanthanum (La), cerium (Ce), strontium (Sr), gadolinium (Gd), hafnium (Hf), and zirconium (Zr) into a vacuum deposition apparatus, wherein the step of supplying the second source gas comprises supplying a second compound containing a second metal different from the first metal and selected from the group consisting of lanthanum (La), cerium (Ce), strontium (Sr), gadolinium (Gd), hafnium (Hf), and zirconium (Zr) into the vacuum deposition apparatus, and wherein the step of supplying the first reaction gas comprises supplying a compound selected from the group consisting of O3 and H2O into the vacuum deposition apparatus.
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The addition of the second source gas and third purge gas in claim 4, creates a single cycle of deposition as shown in the instant application, Figure Instant 2, inserted below for clarity.
Figure Instant 2: Figure 2 from the instant application, inserted to clarify the order of steps as described by claim 4.
However, in the same field of endeavor, Karbasian discloses a method of forming a doped dielectric film (Karbasian Fig 1, second deposition cycle 130), comprising: a step of supplying a second source gas (dopant precursor, step 136 Fig 1) between the step of supplying the first purge gas (first purge gas, 134) and the step of supplying the first reaction gas (first reaction gas in the second deposition cycle 130, is the second oxidant in step 140); and a step of supplying a third purge gas (third purge gas is the second purge gas in the cycle 130, step 138) between the step of supplying the second source gas (136) and the step of supplying the first reaction gas (140);
wherein the step of supplying the first source gas (step 132) comprises supplying a first compound containing a first metal selected from the group consisting of lanthanum (La), cerium (Ce), strontium (Sr), gadolinium (Gd), hafnium (Hf), and zirconium (Zr) (step 132, “expose substrate to hafnium precursor”[0041] Fig 1) into a vacuum deposition apparatus (deposition cycles occur in a processing chamber [0008] connected to a pressure control system 809 in Fig 4 [0082]), wherein the step of supplying the second source gas (Fig 1 step 136 dopant precursor) comprises supplying a second compound containing a second metal different from the first metal (hafnium is different from the suitable dopants listed below) and selected from the group consisting of lanthanum (La), cerium (Ce), strontium (Sr), gadolinium (Gd), hafnium (Hf), and zirconium (Zr) (“the dopant is selected from one or more of aluminum, silicon, zirconium, yttrium, lanthanum, gadolinium, or strontium” [0052]) into the vacuum deposition apparatus (chamber [0008]), and wherein the step of supplying the first reaction gas (step 140) comprises supplying a compound selected from the group consisting of O3 and H2O into the vacuum deposition apparatus (“the second oxidant is selected from H2O, O2, O3, direct O2 plasma, or remote O2 plasma” [0055]).
Therefore, it would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to modify the deposition cycle as disclosed in Park with the addition of the step of introducing a second source gas and third purge step before the first reaction gas to create a doped high-k dielectric with the ability to use “dopant adjustability, in turn, advantageously provides superior control over the ferroelectricity of the doped hafnium oxide film” [Karbasian 0038].
Claim(s) 5 is/are rejected under 35 U.S.C. 103 as being unpatentable over Park in view of Karbasian, further in view of Kim et al. (2009) Characteristics of High-k Dielectric ECR-ALD lanthanum hafnium oxide (LHO) films. “Thin Solid Films”, 517, 14, pp 3900-3903, doi:10.1016/j.tsf.2009.01.159, hereinafter “Kim”.
Regarding claim 5, Park in view of Karbasian discloses, The method of forming a dielectric film of claim 4, however, neither explicitly discloses wherein the first metal is selected from the group consisting of lanthanum (La), cerium (Ce), strontium (Sr), and gadolinium (Gd), and the second metal is selected from the group consisting of hafnium (Hf) and zirconium (Zr).
However, in the same field of endeavor, Kim discloses advantageous effects in high-k dielectrics formed through the method of depositing “alternating LA2O3 and HfO2 layers” repeatedly [Kim section 2]. Kim, in the section 2, describes the first step of the experimental deposition process including a lanthanum precursor, while the second step included a hafnium precursor. Kim found the lowest leakage current and highest dielectric constant of 16.3 “for the LHO film with a La/(La+Hf) of 49.1%” [Kim section 4].
Therefore it would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to maintain the sequence of deposition as disclosed in Park and Karbasian, but modify the materials of the first metal to be one such as lanthanum and the second material to be one such as hafnium to control the ratio of each metallic compound used to suppress high leakage current [Kim section 1].
Claim 6 rejected under 35 U.S.C 102(a)(1)(2) as being anticipated by Ivanova et al. US2020/0266055 A1, hereinafter “Ivanova”.
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The method of claim 6, as disclosed by the instant application, and Ivanova is simplified in the instant application Fig 3, inserted below as Figure Instant 3 for clarity.
Figure Instant 3: Figure 3 from the instant application, inserted to clarify the order of steps as described by claim 6.
Regarding claim 6, Ivanova discloses, The method of forming a dielectric film (hafnium lanthanum oxide film formed by the method of Figs 1-3) of claim 1 (Ivanova Fig 2 discloses the entire method of claim 1: A method of forming a dielectric film (abstract), the method comprising: a step of supplying a first source gas (Fig 2, hafnium vapor precursor in step 210); a step of supplying a first purge gas (“purging the reaction” [0084]); a step of supplying a first reaction gas (Fig 2 220, first oxidizer); and a step of supplying a second purge gas (“and again purging the reaction chamber” [0084]), wherein the step of supplying the first source gas comprises supplying a compound containing at least one metal selected from the group consisting of lanthanum (La), cerium (Ce), strontium (Sr), gadolinium (Gd), hafnium (Hf), and zirconium (Zr) into a vacuum deposition apparatus (first source vapor is hafnium precursor, Fig 2), and wherein the step of supplying the first reaction gas comprises supplying a compound selected from the group consisting of O.sub.3 and H.sub.2O (“first oxidizer precursor, e.g., water” [0082]) into the vacuum deposition apparatus, (for the following limitations of claim 6, see Ivanova Fig 3, depositing lanthanum vapor be the first source gas, and Fig 2 shows the method of depositing hafnium vapor as the second source gas, the deposition of lanthanum may proceed hafnium according to [0103]), further comprising:
a step of supplying a second source gas (Fig 2, showing sub-cycle block 120, supplies the second source gas, hafnium vapor, step 210) after the step of supplying the second purge gas (hafnium vapor, step 210, occurs after the end of the sub-cycle block 130 in Fig 3 that follows this process-flow, “a unit deposition cycle, of the second sub-cycle 130 may comprise: contacting the substrate with the lanthanum vapor phase reactant, purging the reaction chamber, contacting the substrate with the second oxidizer precursor, and purging the reaction chamber again” [0097], so the sub-cycle 130, ended with the second purge gas);
a step of supplying a third purge gas (Fig 2, after step 210 supplying the second source gas of hafnium, the steps of the entire cycle 120 include, “contacting the substrate with a hafnium precursor, purging the reaction chamber, contacting the substrate with water, and purging the reaction chamber again” [0080], so the third purge gas is supplied after the hafnium precursor contacts the substrate);
a step of supplying a second reaction gas (the oxidizer precursor used in the hafnium cycle is water [0077]);
and a step of supplying a fourth purge gas (fourth purge gas occurs after the reaction of contacting the substrate with water [0080]),
wherein the step of supplying the first source gas comprises supplying a compound containing at least one metal selected from the group consisting of lanthanum (La), cerium (Ce), strontium (Sr), gadolinium (Gd), hafnium (Hf), and zirconium (Zr) into a vacuum deposition apparatus (first source gas may be lanthanum according to Fig 3 and sub-cycle 130 [0097], this may be performed in “a conventional ALD apparatus” [0031] using a vacuum to assist with purging [0041]),
wherein the step of supplying the second source gas comprises supplying a compound containing at least one metal selected from the group consisting of lanthanum (La), cerium (Ce), strontium (Sr), gadolinium (Gd), hafnium (Hf), and zirconium (Zr) into the vacuum deposition apparatus (second source gas may contain hafnium as disclosed by the sub-cycle 120 in Fig 2),
wherein the second source gas is different from the first source gas (lanthanum and hafnium are different), and
wherein each of the step of supplying the first reaction gas and the step of supplying the second reaction gas comprises supplying a compound selected from the group consisting of O.sub.3 and H.sub.2O into the vacuum deposition apparatus (the second oxidizer precursor” [0097] which may be one of hydrogen peroxide, ozone, water, molecular oxygen, etc., according to [0092]); while the second reaction gas is explicitly stated to be water [0080], both being supplied in the same chamber as the first and second source gases, a single chamber is used [0008]).
Claim 7 rejected under 35 USC 103 as being anticipated by Ivanova in view of Lim et al. KR 2020/0115693 A, hereinafter “Lim”.
Regarding claim 7, Ivanova discloses, The method of forming a dielectric film of claim 6 (discussed above, Ivanova Fig 2 and 3), however, Ivanova does not disclose the method wherein the first source gas is a compound with 2 metals, and the second source gas is also a compound with 2 metals. The limitation of claim 7 follows: wherein the step of supplying the first source gas comprises supplying a first compound containing a first metal selected from the group consisting of lanthanum (La), cerium (Ce), strontium (Sr), gadolinium (Gd), hafnium (Hf), and zirconium (Zr) and a second compound containing a second metal selected from the group consisting of lanthanum (La), cerium (Ce), strontium (Sr), gadolinium (Gd), hafnium (Hf), and zirconium (Zr) into the vacuum deposition apparatus, the second compound being different from the first compound, and wherein the step of supplying the second source gas comprises supplying a third compound containing a third metal selected from the group consisting of lanthanum (La), cerium (Ce), strontium (Sr), gadolinium (Gd), hafnium (Hf), and zirconium (Zr) and a fourth compound containing a fourth metal selected from the group consisting of lanthanum (La), cerium (Ce), strontium (Sr), gadolinium (Gd), hafnium (Hf), and zirconium (Zr) into the vacuum deposition apparatus, the fourth compound being different from the third compound.
However, in the same field of endeavor, Lim discloses a method of forming stacked high-k dielectric films wherein the step of supplying the first source gas (first source gas used to create first ferroelectric layer 210 in Lim Fig 2a) comprises supplying a first compound containing a first metal selected from the group consisting of lanthanum (La), cerium (Ce), strontium (Sr), gadolinium (Gd), hafnium (Hf), and zirconium (Zr) (“when the first single metal oxide film is a hafnium oxide film, …” [0031], therefore the first source gas must include a hafnium precursor) and a second compound containing a second metal selected from the group consisting of lanthanum (La), cerium (Ce), strontium (Sr), gadolinium (Gd), hafnium (Hf), and zirconium (Zr) (“… the dopant is gadolinium, silicon, aluminum, yttrium, lanthanum, scandium, cerium, strontium, …” [0031]) into the vacuum deposition apparatus (it is well-known in the art that this deposition would occur in a vacuum deposition apparatus), the second compound being different from the first compound (hafnium is a different metal compound than the second list of dopant compounds given in [0031], the first source gas may also be made of a bi-metallic compound of hafnium and zirconium, “the first binary metal oxide film may be a hafnium zirconium oxide film (HfZrO)” [0038], in a different embodiment, which also discloses the limitation of the claim),
Lim further discloses and wherein the step of supplying the second source gas (source gas used for creating film 260, which may include “for example, a second single metal oxide film or a first binary metal oxide film” [0035-0038]) comprises supplying a third compound containing a third metal selected from the group consisting of lanthanum (La), cerium (Ce), strontium (Sr), gadolinium (Gd), hafnium (Hf), and zirconium (Zr) (the first binary metal oxide film may be hafnium zirconium oxide film [0038], so the third compound may be one of Hf or Zr) and a fourth compound containing a fourth metal selected from the group consisting of lanthanum (La), cerium (Ce), strontium (Sr), gadolinium (Gd), hafnium (Hf), and zirconium (Zr) (the fourth compound may be the other of Hf or Zr) into the vacuum deposition apparatus (well-known in the art that a vacuum deposition apparatus would be used) , the fourth compound being different from the third compound (the fourth compound may be Zr, while the third compound is Hf, or vice versa).
Therefore, it would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to modify the deposition cycle as disclosed in Ivanova to be performed with the bimetallic compound sources as disclosed in Lim to create a first single metal oxide film that is stabilized by doping [0030] as well as a first bimetal oxide, so that the total capacitance of the capacitor, shown in Fig 2A, may increase [0002].
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure:
Hung et al US 2013/0288427 A1 discloses a method of forming high-k dielectric films using metal co-reactants which can flow into an ALD chamber simultaneously or through an oscillating gas flow nozzle [0047-0049]
Rui et al US 2015/0228710 A1 discloses a method of forming stacked high-k dielectrics which may be lightly doped, non-doped, or highly doped, with suitable materials listed in [0047-0061].
Any inquiry concerning this communication or earlier communications from the examiner should be directed to TERESA MICKEY whose telephone number is (571)270-3109. The examiner can normally be reached M-F, 8am to 5pm ET.
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/TERESA N MICKEY/Examiner, Art Unit 2897
/VU A VU/Primary Examiner, Art Unit 2897
