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 .
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.
Claim(s) 1, 2, 6, 8, 11-19 is/are rejected under 35 U.S.C. 103 as being unpatentable over US 20220246714 (Spanier et al) in view of US 6121647 (Yano et al).
Concerning claim 1, Spanier discloses a method of producing a high-crystallinity barium titanate film structure (Figs. 1 and 7), comprising: depositing, on a substrate (Si), a barium titanate layer (BTO) with a (001) or (111) crystal orientation ([0121]) by atomic layer deposition ([0114]) . . .and at a low temperature of 450°C or below ([0115]) . . .; and performing plasma annealing treatment on the barium titanate layer at a low temperature of 450°C or below without breaking vacuum to form a high-crystallinity barium titanate layer having the (001) or (111) crystal orientation ([0118]-[0119]).
Spanier does not disclose depositing the barium titanate film in a high vacuum environment or wherein a Ba/Ti ratio in the barium titanate layer is 0.9- 1.5. However, Yano discloses disclose depositing the barium titanate film in a high vacuum environment (col. 23 lines 11-26) and wherein a Ba/Ti ratio in the barium titanate layer is 0.9- 1.5 (col. 18 lines 32-37). Yano also discloses that the barium titanate film formed under these conditions provide a film structure having a ferroelectric thin film featuring a relatively low dielectric constant, great residual polarization, a low polarization reversing voltage, and minimal deterioration upon repetitive polarization reversal (col. 3 lines 5-10). Therefore it would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to modify the process of Spanier to deposit the barium titanate film under a high vacuum environment with a Ba/Ti ration in the barium titanate layer being 0.9-1.5 in order to form a film having a ferroelectric thin film featuring a relatively low dielectric constant, great residual polarization, a low polarization reversing voltage, and minimal deterioration upon repetitive polarization reversal.
Considering claim 19, Spanier discloses a high-crystallinity barium titanate film structure (Figs. 1 and 7), comprising: a substrate (Si) comprising or formed of silicon, sapphire, magnesium oxide with a , a high-crystallinity barium titanate layer (BTO) ([0121]). . . a top electrode layer (Pt) comprising or formed of Pt, Ta, TaN, TiN, Au, or Ag ([0053]) wherein the barium titanate layer is arranged on the substrate, and the top electrode layer is located on a s die of the barium titanate layer facing away from the substrate material (Fig. 7) wherein the barium titanate layer has a (001) or (111) crystal orientation ([0121]) and is deposited at a low temperature of 450°C or below ([0115]) through atomic layer deposition ([0114]) and wherein the barium titanate layer is subjected to plasma annealing treatment in vacuum ([0118]-[0119]).
Spanier does not disclose depositing the barium titanate film having a Ba/Ti ratio in the range 0.9- 1.5. However, Yano discloses disclose depositing the barium titanate film wherein a Ba/Ti ratio in the barium titanate layer is 0.9- 1.5 (col. 18 lines 32-37). Yano also discloses forming a stacked structure including a top and bottom electrode (col. 26 lines 22-28) and a barium titanate film formed under these conditions provide a film structure having a ferroelectric thin film featuring a relatively low dielectric constant, great residual polarization, a low polarization reversing voltage, and minimal deterioration upon repetitive polarization reversal (col. 3 lines 5-10). Therefore it would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to modify the process of Spanier to deposit the barium titanate film with a Ba/Ti ration in the barium titanate layer being 0.9-1.5 in order to form a film having a ferroelectric thin film featuring a relatively low dielectric constant, great residual polarization, a low polarization reversing voltage, and minimal deterioration upon repetitive polarization reversal.
Continuing to claim 2, Spanier in view of Yano discloses further comprising: forming a top electrode layer (Spanier Pt) on the barium titanate layer, optionally or preferably, by sputtering (Spanier [0053]).
Referring to claim 6, Spanier in view of Yano discloses wherein the top electrode layer is provided as a conductive layer formed of Pt, Ta, TaN, TiN, Au or Ag (Spanier [0053]).
Regarding claim 8, Spanier in view of Yano wherein, before depositing the barium titanate layer, the method further comprises: forming a bottom electrode layer on the substrate, optionally or preferably, by sputtering (Yano col. 26 lines 22-28).
Pertaining to claim 11, Spanier in view of Yano discloses wherein the deposition of the barium titanate layer is performed in a vacuum chamber with a base vacuum pressure of less than 10⁻⁷ Torr (Yano col. 23 lines 11-26).
As to claim 12, Spanier in view of Yano discloses wherein the plasma annealing treatment is performed in a vacuum chamber with a base vacuum pressure of less than 10⁻⁷ Torr (Yano col. 21 lines 23-35), and with a gas source of an inert gas and oxygen at a ratio of 1:19-4:1 (Yano col. 18 lines 32-53).
Concerning claim 13, Spanier in view of Yano discloses wherein the plasma annealing treatment is performed for 1-6 Hours at a set temperature of 300-450°C with a power of 200-400 W (Spanier [0118]-[0119]).
Considering claim 14, Spanier in view of Yano discloses wherein the substrate comprises or is formed of a silicon plate, sapphire, magnesium oxide with a (001) or (110) crystal orientation, or silicon carbide with a (0001) crystal orientation (Spanier [0120]).
Continuing to claim 15, Spanier in view of Yano discloses wherein the barium titanate layer has a thickness of 1-10 nm (Yano [0056], [0062], and [0069]).
Referring to claim 16, Spanier in view of Yano wherein the method steps are performed in one or more vacuum chambers without breaking vacuum (Spanier [0007]).
Regarding claim 17, Spanier in view of Yano discloses use of a high-crystalline barium titanate film structure obtained by the method according to claim 1 in any one or more of: a ferroelectric element, a ferroelectric tunnel junction, an energy storage element, a magnetic tunnel junction, a storage element and a supercapacitor (Spanier [0004]).
Pertaining to claim 18, Spanier in view of Yano discloses high-crystallinity barium titanate film structure produced by the method of claim 1 (Spanier Fig. 1).
Claim(s) 3-5 and 7 is/are rejected under 35 U.S.C. 103 as being unpatentable over US 20220246714 (Spanier et al) in view of US 6121647 (Yano et al) as applied to claims 1 and 19 above, and further in view of US 20120098589 (Spanier et al, hereafter referred to as Spanier’589).
As to claim 3, Spanier in view of Yano discloses forming a barium titanate structure and
Spanier in view of Yano does not disclose further comprising: forming a metal nitride layer or a metal alloy layer on the barium titanate layer; and forming a top electrode layer on the metal nitride layer or the metal alloy layer, and optionally or preferably, wherein the top electrode layer and the metal nitride layer or the metal alloy layer are formed by sputtering. However, Spanier’589 discloses the formation of an adhesion layer formed before the formation of a top electrode layer on a ferroelectric layer. Suitable adhesion layers may comprise a transition metal or transition metal alloy, including one or more of the following, Au/Cr, Au/Ni, Au/NiCr, Au/Ti, Pt/Cr, Au/Ni, Au/NiCr, Au/Ti, Pt/Cr, Pt/Ni, Pt/NiCr, Pt/Ti, Pd/Cr, Pd/Ni, Pd/NiCr, Pd/Ti, AuPd/Cr, AuPd/Ni, AuPd/NiCr, AuPd/Ti, and the like ([0052] and [0059]-[0060]). It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to modify the invention of Spanier in view of Yano form a metal alloy layer on the barium titanate layer (ferroelectric layer) before the formation of the top electrode layer in order to improve adhesion of the top electrode to the barium titanate layer.
Concerning claim 4, Spanier in view of Yano and Spanier’589 discloses wherein the metal nitride layer or the metal alloy layer has a thickness of 10-50 nm (Spanier’589 [0052]).
Considering claim 5, Spanier in view of Yano and Spanier’589 discloses wherein the metal nitride layer is provided as Mn₃AN or Cu₃PdN, wherein A comprises Ni, Sn, Ga, Cu or Pt, and the metal alloy layer is provided as Cu₃Pd, Pt₃Ni, Pt₃Fe or Pt₃Al (Spanier’589 [0059]-[0060]).
Continuing to claim 7, Spanier in view of Yano and Spanier’589 discloses wherein the top electrode layer (Spanier Pt) is provided as a conductive layer formed of Pt, Ta, TaN, TiN, Au or Ag (Spanier [0053]).
Claim(s) 9 is/are rejected under 35 U.S.C. 103 as being unpatentable over US 20220246714 (Spanier et al) in view of US 6121647 (Yano et al) as applied to claim 8 above, and further in view of US 20230065132 (Chen et al).
Referring to claim 9, Spanier in view of Yano disclose forming a top and bottom electrode (Spanier [0053] and [0009] and Yano col. 26 lines 49-56).
Spanier in view of Yano does not disclose wherein the bottom electrode layer is provided as a Pt layer, Au layer, Ag layer, conductive oxide layer, metal nitride layer or metal alloy layer, having a (001), (111) or mixed crystal orientation. However, Chen discloses that the top and bottom electrodes of the barium titanate layer structure ([0031]) can be made of a multi-layer structure. For example, each of the bottom electrodes (152) includes a first electrode layer 152a and a second electrode layer 152b over the first electrode layer 152a. The first electrode layer 152a may include a conductive material, such as tungsten (W), titanium (Ti), tantalum (Ta), platinum (Pt), ruthenium (Ru), aluminum (Al), copper (Cu), TiN, TaN, the like or combinations thereof ([0069]) similar to the top electrode layer ([0048]). Additionally, Yano discloses the use of a Pt(111) as the top electrode layer. The selection of a known material based on its suitability for its intended use supported a prima facie obviousness determination in Sinclair & Carroll Co. v. Interchemical Corp., 325 U.S. 327, 65 USPQ 297 (1945). See MPEP 2144.07. It would have been obvious to one of ordinary skill in the art to modify the materials of the top and bottom electrodes to be the same material (Pt (111)) as these materials are known in the art to be suitable for the use as electrodes in a ferroelectric (barium titanate ) layer structure.
Claim(s) 10 is/are rejected under 35 U.S.C. 103 as being unpatentable over US 20220246714 (Spanier et al) in view of US 6121647 (Yano et al) as applied to claim 8 above, and further in view of US 20220013288 (Spanier et al, hereafter referred to as Spanier’288).
Regarding claim 10, Spanier in view of Yano discloses wherein the bottom electrode layer has a thickness of 10-50 nm (Yano col. 26 lines 22-28).
Spanier in view of Yano does not disclose a roughness of less than 1 nm. However, Spanier’288 discloses the formation of a bottom electrode layer on a stacked structure, and that the films are formed with a roughness less than 2 nm ([0106]). 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). See MPEP 2144.05 I. Therefore absent evidence of criticality of the range, it would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to modify the roughness of the bottom electrode such that it is less than 1 nm as disclosed by Spanier’288.
Claim(s) 20 is/are rejected under 35 U.S.C. 103 as being unpatentable over US 20220246714 (Spanier et al) in view of US 6121647 (Yano et al) as applied to claim 19 above, and further in view of US 20230065132 (Chen et al) and US 20120098589 (Spanier et al, hereafter referred to as Spanier’589).
Pertaining to claim 20, Spanier in view of Yano discloses forming a top and bottom electrode (Spanier [0053] and [0009] and Yano col. 26 lines 49-56).
Spanier in view of Yano does not disclose wherein the bottom electrode layer is provided as a Pt layer, Au layer, Ag layer, conductive oxide layer, metal nitride layer or metal alloy layer, having a (001), (111) or mixed crystal orientation, or a metal nitride layer or a metal alloy layer arranged between the barium titanate layer and the top electrode layer, wherein the metal nitride layer is provided as Mn₃AN or Cu₃PdN, wherein A comprises Ni, Sn, Ga, Cu or Pt, and the metal alloy layer is provided as Cu₃Pd, Pt₃Ni, Pt₃Fe or Pt₃Al. However, Chen discloses that the top and bottom electrodes of the barium titanate layer structure ([0031]) can be made of a multi-layer structure. For example, each of the bottom electrodes (152) includes a first electrode layer 152a and a second electrode layer 152b over the first electrode layer 152a. The first electrode layer 152a may include a conductive material, such as tungsten (W), titanium (Ti), tantalum (Ta), platinum (Pt), ruthenium (Ru), aluminum (Al), copper (Cu), TiN, TaN, the like or combinations thereof ([0069]) similar to the top electrode layer ([0048]). Additionally, Yano discloses the use of a Pt(111) as the top electrode layer. The selection of a known material based on its suitability for its intended use supported a prima facie obviousness determination in Sinclair & Carroll Co. v. Interchemical Corp., 325 U.S. 327, 65 USPQ 297 (1945). See MPEP 2144.07. It would have been obvious to one of ordinary skill in the art to modify the materials of the top and bottom electrodes to be the same material (Pt (111)) as these materials are known in the art to be suitable for the use as electrodes in a ferroelectric (barium titanate ) layer structure.
Additionally, Spanier’589 discloses the formation of an adhesion layer formed before the formation of a top electrode layer on a ferroelectric layer. Suitable adhesion layers may comprise a transition metal or transition metal alloy, including one or more of the following, Au/Cr, Au/Ni, Au/NiCr, Au/Ti, Pt/Cr, Au/Ni, Au/NiCr, Au/Ti, Pt/Cr, Pt/Ni, Pt/NiCr, Pt/Ti, Pd/Cr, Pd/Ni, Pd/NiCr, Pd/Ti, AuPd/Cr, AuPd/Ni, AuPd/NiCr, AuPd/Ti, and the like ([0052] and [0059]-[0060]). It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to modify the invention of Spanier in view of Yano form a metal alloy layer on the barium titanate layer (ferroelectric layer) before the formation of the top electrode layer in order to improve adhesion of the top electrode to the barium titanate layer.
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure. US 20190164850 discloses the formation of barium titanate layers by atomic layer deposition ([0055]).
Any inquiry concerning this communication or earlier communications from the examiner should be directed to VALERIE N NEWTON whose telephone number is (571)270-5015. The examiner can normally be reached M-F 8-5.
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If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, CHAD DICKE can be reached at (571) 270-7996. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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/VALERIE N NEWTON/ Examiner, Art Unit 2897 05/02/26
/CHAD M DICKE/ Supervisory Patent Examiner, Art Unit 2897
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