DETAILED ACTION
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 .
Election/Restrictions
Applicant’s election without traverse of Group I/Species II and Claims 1-15 and 21-25 in the reply filed on 5/13/2026 is acknowledged.
Information Disclosure Statement
Acknowledgement is made of Applicant's Information Disclosure Statement (IDS) from PTO-1449. The IDS has been considered.
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claims 1-15 are rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
Claim 1 recites the limitation wherein “the variable resistance film comprises a first orthorhombic phase” and after “performing a laser anneal process”, “the variable resistance film comprises a second orthorhombic phase”. It is unclear if the “second orthorhombic phase” is referring to a new crystallographic structure within the orthorhombic space group, or is it referring to the same crystallographic structure as the “first orthorhombic phase” but with different phase fraction. Therefore, the claim is indefinite and hence, rejected. Additionally, it is also unclear what the application means by a “first fraction” and a “second fraction”. It can either mean a “phase fraction” or it can mean a fraction by volume/atomic weight. Claims 2-5 depend from claim 1 and are rejected at least for the reasons above. For examination purposes, the “second orthorhombic phase” will be treated as having the same crystallographic structure as the “first orthorhombic phase” but with different phase fraction. Furthermore, the “first fraction” and “second fraction” will be treated as a “first phase fraction” and “second phase fraction”.
Claim 6 recites the limitation wherein “the variable resistance film comprises a first tetragonal phase” and after “performing a laser anneal process”, “the variable resistance film comprises a second tetragonal phase”. It is unclear if the “second tetragonal phase” is referring to a new crystallographic structure within the tetragonal space group, or is it referring to the same crystallographic structure as the “first tetragonal phase” but with different phase fraction. Therefore, the claim is indefinite and hence, rejected. Additionally, it is also unclear what the application means by a “first fraction” and a “second fraction”. It can either mean a “phase fraction” or it can mean a fraction by volume/atomic weight. Claims 7-15 depend from claim 6 and are rejected at least for the reasons above. For examination purposes, the “second tetragonal phase” will be treated as having the same crystallographic structure as the “first tetragonal phase” but with different phase fraction. Furthermore, the “first fraction” and “second fraction” will be treated as a “first phase fraction” and “second phase fraction”.
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 21 is rejected under 35 U.S.C. 102(a)(1) as being anticipated by Hsiang et al. (US 2023/0422515 A1).
Re Claim 21, Hsiang teaches a method of forming a memory cell (“MD”, Fig. 1, para [0026]), comprising:
forming a bottom electrode layer (“BE”, Fig. 1, para [0026]) over a substrate (110, Fig. 1, para [0026]);
forming a variable resistance film (polarization switching layer “PS”, Fig. 1, para [0026]) over the bottom electrode layer (“BE”), wherein the variable resistance film comprises a plurality of phases comprising (Fig. 21B shows one embodiment where the “PS” layer is made of Hf0.25Zr0.75O2, para [0056]):
a tetragonal phase (Fig. 21B shows tetragonal phase, para [0056]); and
an orthorhombic phase (Fig. 21B shows orthogonal phase, para [0056])) with a fraction in the variable resistance film greater than a fraction of the tetragonal phase in the variable resistance film (orthogonal phase fraction is more than tetragonal phase fraction, Fig. 21B, para [0056]); and
forming a top electrode layer (“TE”, Fig. 1, para [0026]) over the variable resistance film (“PS”).
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 1-2, 6-7, 9-11, 21-22 and 24-25 are rejected under 35 U.S.C. 103 as being unpatentable over Lin et al. (US 2023/0380179 A1), and further in view of Vellianitis et al. (US 2023/0301114 A1).
Re Claim 1, Lin teaches a method of forming a memory cell (180a, Fig. 9, para [0053]), comprising:
forming a bottom electrode layer (182, Fig. 9, para [0053]) over a substrate (502, Fig. 1B, note that the device in Fig. 9 is formed over the topmost interconnect level 50B in Fig. 1B, paras [0037] - [0038]);
forming a variable resistance film (184, Fig. 9, paras [0056] – [0057]) over the bottom electrode layer (182), wherein the variable resistance film comprises a first orthorhombic phase with a first fraction in the variable resistance film (layer 184 can be made of Hf1-xZrxO2, and comprises of an orthorhombic phase with a phase fraction of 50%, para [0056]);
forming a top electrode layer (186, Fig. 9, para [0053]) over the variable resistance film (184); and
performing a laser anneal process to the substrate, the bottom electrode layer, the variable resistance film and the top electrode layer (laser annealing is performed on the structure to improve the quality of ferroelectric layer 184, para [0056]).
Lin does not explicitly discloses that after performing the laser anneal process, the variable resistance film comprises a second orthorhombic phase with a second fraction in the variable resistance film, and the second fraction is different from the first fraction. However, Lin discloses that the laser annealing can be performed to further improve the quality of ferroelectric layer 184 (para [0056]).
Related art Vellianitis discloses that an anneal process can be performed to increase the percentage of orthorhombic phase (para [0029]) in doped Hafnium oxide, similar to Lin.
It would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention, absent unexpected results, that annealing the ferroelectric layer of the device of Lin will increase the orthorhombic phase, thus improving the ferroelectric memory device, as disclosed by Vellianitis.
Re Claim 2, Lin modified by Vellianitis teaches the method of claim 1, wherein the second fraction is higher than the first fraction (orthorhombic phase will increase after annealing, see claim 1 above).
Re Claim 6, Lin teaches a method of forming a memory cell (180a, Fig. 9, para [0053]), comprising:
forming a bottom electrode layer (182, Fig. 9, para [0053]) over a substrate (502, Fig. 1B, note that the device in Fig. 9 is formed over the topmost interconnect level 50B in Fig. 1B, paras [0037] - [0038]);
forming a variable resistance film (184, Fig. 9, paras [0056] – [0057]) over the bottom electrode layer (182);
forming a top electrode layer (186, Fig. 9, para [0053]) over the variable resistance film (184); and
performing a laser anneal process to the bottom electrode layer, the variable resistance film and the top electrode layer (laser annealing is performed on the structure to improve the quality of ferroelectric layer 184, para [0056]).
Lin does not explicitly disclose the following:
wherein the variable resistance film comprises a first tetragonal phase with a first fraction in the variable resistance film; and
after performing the laser anneal process, the variable resistance film comprises a second tetragonal phase with a second fraction in the variable resistance film, and the second fraction is different from the first fraction.
However, Lin discloses that the variable resistance film (layer 184, Fig. 9) is made of Hf1-xZrxO2 (para [0056]), comprising a primary orthorhombic phase which is about 55% of the phase fraction (para [0056]). Related art, Vellianitis discloses that the doped Hafnium oxide like the material in the device of Lin, can have other crystalline phases like a tetragonal and monoclinic phase (paras [0028] – [0029], Vellianitis). Therefore, it would be obvious to one of ordinary skill in the art that the rest of the 45% of the material within the layer 184 of Lin, will likely consist other phases like tetragonal and monoclinic phases, and do not contribute to the ferroelectric behavior. Thus, the variable resistance film (layer 184, Fig. 9) of Lin will have a tetragonal phase with a first phase fraction, as disclosed by Vellianitis.
Furthermore, Lin discloses that the laser annealing can be performed to further improve the quality of variable resistance layer 184 (para [0056]). Related art Vellianitis discloses that an anneal process can be performed to increase the percentage of orthorhombic phase (para [0029]) in doped Hafnium oxide, similar to Lin.
It would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention, absent unexpected results, that annealing the variable resistance layer of the device of Lin will increase the orthorhombic phase, thus improving the ferroelectric memory device, as disclosed by Vellianitis. One of ordinary skill in the art would also realize that increasing the orthorhombic phase fraction, will result in a decrease of the tetragonal phase fraction after annealing. Hence, post-laser-annealing, the variable resistance layer of the device of Lin will have a tetragonal phase with a second fraction that is smaller than the first phase fraction.
Re Claim 7, Lin modified by Vellianitis teaches the method of claim 6, wherein the second fraction is lower than the first fraction (second fraction of the tetragonal phase is smaller than the first phase fraction of the tetragonal phase, see claim 6 above).
Re Claim 9, Lin modified by Vellianitis teaches the method of claim 6, wherein after performing the laser anneal process, the variable resistance film has a ferroelectric phase (layer 184 is a ferroelectric layer, and has a ferroelectric phase, para [0056]).
Re Claim 10, Lin modified by Vellianitis teaches the method of claim 6, wherein after performing the laser anneal process, the variable resistance film has an orthorhombic phase with a third fraction in the variable resistance film, and the third fraction is higher than the first fraction (the orthorhombic phase can be about 55% of phase fraction, para [0056], Lin, and hence will be higher than the first phase fraction of tetragonal phase, also see claim 6 above).
Re Claim 11, Lin modified by Vellianitis teaches the method of claim 6, wherein after performing the laser anneal process, the variable resistance film has an orthorhombic phase with a third fraction in the variable resistance film, and the third fraction is higher than the second fraction (the orthorhombic phase can be about 55% of phase fraction before annealing, para [0056], Lin, which can be further improved after annealing, see claim 6 above. Hence, the phase fraction of orthorhombic phase will be higher than the second phase fraction of tetragonal phase).
Re Claim 21, Lin teaches a method of forming a memory cell (180a, Fig. 9, para [0053]), comprising:
forming a bottom electrode layer (182, Fig. 9, para [0053]) over a substrate (502, Fig. 1B, note that the device in Fig. 9 is formed over the topmost interconnect level 50B in Fig. 1B, paras [0037] - [0038]);
forming a variable resistance film (184, Fig. 9, paras [0056] – [0057]) over the bottom electrode layer (182), wherein the variable resistance film comprises a plurality of phases (para [0056]) comprising:
an orthorhombic phase with a fraction in the variable resistance film (comprises of an orthorhombic phase fraction, para [0056]); and
forming a top electrode layer (186, Fig. 9, para [0053]) over the variable resistance film (184).
Lin does not explicitly disclose a tetragonal phase and that the phase fraction of the orthorhombic phase is greater than the phase fraction of the tetragonal phase.
However, Lin discloses that the variable resistance film (layer 184, Fig. 9) is made of Hf1-xZrxO2 (para [0056]), comprising a primary orthorhombic phase which can be about 75% of the phase fraction (para [0056]). Related art, Vellianitis discloses that the doped Hafnium oxide like the material in the device of Lin, can have other crystalline phases like a tetragonal and monoclinic phase (paras [0028] – [0029], Vellianitis). Therefore, it would be obvious to one of ordinary skill in the art that the rest of the 25% of the material within the layer 184 of Lin, will likely consist other phases like tetragonal and monoclinic phases, and do not contribute to the ferroelectric behavior. Thus, the variable resistance film (layer 184, Fig. 9) of Lin will have a tetragonal phase with a first phase fraction, as disclosed by Vellianitis, which will be smaller than the orthorhombic phase fraction.
Re Claim 22, Lin modified by Vellianitis teaches the method of claim 21, wherein the fraction of the orthorhombic phase in the variable resistance film is more than two times of the fraction of the tetragonal phase in the variable resistance film (the orthorhombic phase can have 75% phase fraction, see claim 21 above, and hence the tetragonal phase has to be less than 25% which is less than twice the phase fraction of orthorhombic phase).
Re Claim 24, Lin modified by Vellianitis teaches the method of claim 21, wherein the variable resistance film further comprises: a monoclinic phase with a fraction in the variable resistance film less than the fraction of the orthorhombic phase in the variable resistance film (the orthorhombic phase can have 75% phase fraction, see claim 21 above, and hence other phases like monoclinic phase has to be less than 25% which is less than the phase fraction of orthorhombic phase).
Re Claim 25, Lin modified by Vellianitis teaches the method of claim 21, wherein the fraction of the orthorhombic phase in the variable resistance film is greater than 50% of total phases present in the variable resistance film (the orthorhombic phase can have 75% phase fraction, see claim 21 above).
Claims 3-4 are rejected under 35 U.S.C. 103 as being unpatentable over Lin et al. (US 2023/0380179 A1) and Vellianitis et al. (US 2023/0301114 A1), and further in view of Lee et al. (International Conference on Solid State Devices and Materials, Mahukari, 2022, pages 399-400).
Re Claim 3, Lin modified by Vellianitis teaches the method of claim 1, but does not disclose performing the laser anneal process comprises: irradiating the top electrode layer using a laser beam having a pulse duration of about 1 nanoseconds to about 30 nanoseconds.
Related art Lee teaches a laser annealing process on a ferroelectric layer where the laser is irradiated on the top electrode layer using a pulse duration of 10 ns (Fig. 3, pg-399, Section-II, Device Fabrication and Simulation).
It would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention, absent unexpected results, to laser-anneal the ferroelectric layer of the device of Lin modified by Vellianitis, using 10 ns laser pulse as disclosed by Lee. The use of a known laser annealing process with a known laser pulse to yield predictable results is prima facie obvious. Also see KSR Int'l Co. v. Teleflex Inc., 550 U.S. 398, 415-421, 82 USPQ2d 1385, 1395-97 (2007).
Re Claim 4, Lin modified by Vellianitis and Lee teaches the method of claim 1, wherein performing the laser-anneal process comprises: irradiating the top electrode layer using a laser beam having a wavelength in a range from about 300 nm to about 400 nm (laser wavelength of 355 nm, pg-399, Section-II, Device Fabrication and Simulation, Lee).
Claim 5 is rejected under 35 U.S.C. 103 as being unpatentable over Lin et al. (US 2023/0380179 A1), Vellianitis et al. (US 2023/0301114 A1), as applied to claim 1 above and further in view of Gluschenkov et al. (US 2023/0051017 A1).
Re Claim 5, Lin modified by Vellianitis teaches the method of claim 1, but does not explicitly disclose that performing the laser anneal process comprises: irradiating the top electrode layer using a laser beam having a wavelength in a range from about 1000 nm to about 1100 nm.
Related art, Gluschenkov teaches that the laser annealing method can employ a variety of laser with different laser wavelengths, for example, using an excimer laser (similar to Lin, para [0056]) or a solid-state Nd:Yag laser emitting at 1064 nm, within the claimed range (para [0039], Gluschenkov).
It would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention, absent unexpected results, to substitute the excimer laser of Lin with a solid-state Nd:YAG laser with a wavelength of 1064 nm, as disclosed by Gluschenkov, as the substitution would yield predictable results. The substitution of a known material for its known purpose to yield predictable results is prima facie obvious. Also see KSR Int'l Co. v. Teleflex Inc., 550 U.S. 398, 415-421, 82 USPQ2d 1385, 1395-97 (2007).
Claim 8 is rejected under 35 U.S.C. 103 as being unpatentable over Lin et al. (US 2023/0380179 A1), and Vellianitis et al. (US 2023/0301114 A1), and further in view of Lin et al. (US 2020/0286685 A1, hereinafter “Lin-2”).
Re Claim 8, Lin modified by Vellianitis teaches the method of claim 6, but does not explicitly disclose that wherein prior to performing the laser anneal process, the variable resistance film has an antiferroelectric phase.
However, Lin modified by Vellianitis discloses that before the annealing process, there is a tetragonal phase (see claim 6 above). Related art Lin-2 discloses that the tetragonal phase is the anti-ferroelectric phase (para [0041]).
It would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention, absent unexpected results, that the variable resistance film of Lin modified by Vellianitis before the laser anneal process will have an anti-ferroelectric phase because the tetragonal phase is the anti-ferroelectric phase as disclosed by Lin-2 (para [0041], Lin-2).
Claims 12-13 are rejected under 35 U.S.C. 103 as being unpatentable over Lin et al. (US 2023/0380179 A1) and Vellianitis et al. (US 2023/0301114 A1), as applied to claim 11 above, and further in view of Lee et al. (International Conference on Solid State Devices and Materials, Mahukari, 2022, pages 399-400).
Re Claim 12, Lin modified by Vellianitis teaches the method of claim 6, but does not explicitly disclose that performing the laser anneal process comprises: irradiating the top electrode layer using a laser beam having a pulse duration of about 1 nanoseconds to about 30 nanoseconds.
Related art Lee teaches a laser annealing process on a ferroelectric layer where the laser is irradiated on the top electrode layer using a pulse duration of 10 ns (Fig. 3, pg-399, Section-II, Device Fabrication and Simulation).
It would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention, absent unexpected results, to laser anneal the ferroelectric layer of the device of Lin modified by Vellianitis, using 10 ns laser pulse as disclosed by Lee. The use of a known laser annealing process with a known laser pulse to yield predictable results is prima facie obvious. Also see KSR Int'l Co. v. Teleflex Inc., 550 U.S. 398, 415-421, 82 USPQ2d 1385, 1395-97 (2007).
Re Claim 13, Lin modified by Vellianitis and Lee teaches the method of claim 12, wherein the laser beam is generated from a solid state laser source, a liquid state laser source, a gas state laser source or a semiconductor laser source (Excimer-laser used for annealing which is a gas laser, para [0056], Lin).
Claims 14-15 are rejected under 35 U.S.C. 103 as being unpatentable over Lin et al. (US 2023/0380179 A1), Vellianitis et al. (US 2023/0301114 A1), and Lee et al. (International Conference on Solid State Devices and Materials, Mahukari, 2022, pages 399-400), and further in view of Gluschenkov et al. (US 2023/0051017 A1).
Re Claim 14, Lin modified by Vellianitis and Lee teaches the method of claim 12, but does not disclose that the laser beam is generated from a solid state laser source.
Related art, Gluschenkov teaches that the laser annealing method can employ a variety of laser like a solid-state Nd:YAG laser or a gas laser like excimer laser (para [0039]).
It would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention, absent unexpected results, to substitute the gas excimer laser of Lin with a solid-state Nd:YAG laser as disclosed by Gluschenkov, as the substitution would yield predictable results. The substitution of a known material for its known purpose to yield predictable results is prima facie obvious. Also see KSR Int'l Co. v. Teleflex Inc., 550 U.S. 398, 415-421, 82 USPQ2d 1385, 1395-97 (2007).
Re Claim 15, Lin modified by Vellianitis and Lee teaches the method of claim 13, but does not disclose a solid state laser source made of Nd:YAG.
Related art, Gluschenkov teaches that the laser annealing method can employ a variety of laser like a solid-state Nd:YAG laser or a gas laser like excimer laser (para [0039]).
It would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention, absent unexpected results, to substitute the gas excimer laser of Lin with a solid-state Nd:YAG laser as disclosed by Gluschenkov, as the substitution would yield predictable results. The substitution of a known material for its known purpose to yield predictable results is prima facie obvious. Also see KSR Int'l Co. v. Teleflex Inc., 550 U.S. 398, 415-421, 82 USPQ2d 1385, 1395-97 (2007).
Claim 23 is rejected under 35 U.S.C. 103 as being unpatentable over Lin et al. (US 2023/0380179 A1), and Vellianitis et al. (US 2023/0301114 A1), and further in view of Kao et al. (ACS Appl. Electron. Mater. 2022).
Re Claim 23, Lin modified by Vellianitis teaches the method of claim 21, wherein the variable resistance film further comprises: a monoclinic phase with a fraction in the variable resistance film (there can be monoclinic phase within the variable resistance film, see claim 21 above).
Lin modified by Vellianitis fails to explicitly teach that the phase fraction of monoclinic phase is less than the fraction of the tetragonal phase.
Lin discloses that the variable resistance film (layer 184, Fig. 9) is made of Hf1-xZrxO2 (para [0056]), comprising a primary orthorhombic phase which can be about 75% of the phase fraction (para [0056]). Related art Kao discloses that the 75% phase fraction of orthorhombic phase can be obtained at two different Zr concentrations, one at x~0.55 and the other at x~0.2 (see Fig. 6a, where x is the Zr concentration). For x~0.2, tetragonal phase fraction is less than monoclinic phase fraction, while for x~0.55, monoclinic phase fraction is less than tetragonal phase fraction, as recited in the claim limitation. One of ordinary skill in the art would realize that in Hf1-xZrxO2, an orthorhombic phase with 75% phase fraction can be obtained at two different concentrations of Zr, as disclosed by Kao, one at one at x~0.55 and the other at x~0.2, and a person of ordinary skill has good reason to pursue both the known options and reach the claimed limitation with anticipated success, where the monoclinic phase fraction is less than the tetragonal phase fraction, see KSR, 550 U.S. at 421, 82 USPQ2d at 1397.
Conclusion
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/P.D./Examiner, Art Unit 2898
/JULIO J MALDONADO/Supervisory Patent Examiner, Art Unit 2898
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