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 .
The response of the applicant has been read and given careful consideration. Rejection of the previous action, not repeated below are withdrawn. Responses to the arguments of the applicant are presented after the first rejection they are directed to. The rejection of claims over Imamura et al. WO 2022039216 alone is withdrawn as while the applicant’s sputtering from an HfO2 target in the presence of Ar alone results in HfO with 66 at% oxygen, Imamura et al. WO 2022039216 sputters in the presence of Ar and oxygen, which is unlikely to result in an oxygen deficient film. The same holds true for Rizzo et al., “The influence of ion mass and energy on the composition of IBAD oxide films”, Surface and coatings technology, Vol. 108-109 pp 297-302 (1998), so the rejection of claim 1 and those dependent upon it are withdrawn.
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 1-20 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.
In claim 1, the applicant has added “at least one of (i) a degree of orientation of m[11-1] is the largest among the orientations m[11-1],o[111] and m[111] in the thin film and (ii) a degree of orientation of o[111] is the smallest among each of the orientations m[11-1], o[111] and m[111] in the thin film”, but the language “wherein an X-ray diffraction profile of a diffraction angle 2Q between 25 degrees and 35 degrees has a maximum diffraction intensity angle 2Q between 28 degrees and 29 degrees”, so the first condition (i) must be met. (see prepub at [0066] which states “Regarding the above, m[11-1] and m[111] are [11-1] plane and [111] plane in a primitive monoclinic lattice, with diffraction angles 2θ of 28.589 degrees and 31.811 degrees, respectively. Further, o[111] is [111] plane in a primitive orthorhombic lattice”)
In claim 5, the applicant has added “at least one of (i) a degree of orientation of m[11-1] is the largest among the orientations m[11-1],o[111] and m[111] in the thin film and (ii) a degree of orientation of o[111] is the smallest among each of the orientations m[11-1], o[111] and m[111] in the thin film”, but the language “wherein an X-ray diffraction profile of a diffraction angle 2Q between 25 degrees and 35 degrees has a maximum diffraction intensity angle 2Q between 28 degrees and 29 degrees”, so the first condition (i) must be met. (see prepub at [0066] which states “Regarding the above, m[11-1] and m[111] are [11-1] plane and [111] plane in a primitive monoclinic lattice, with diffraction angles 2θ of 28.589 degrees and 31.811 degrees, respectively. Further, o[111] is [111] plane in a primitive orthorhombic lattice”)
In claim 9, the applicant has added “at least one of (i) a degree of orientation of m[11-1] is the largest among the orientations m[11-1],o[111] and m[111] in the thin film and (ii) a degree of orientation of o[111] is the smallest among each of the orientations m[11-1], o[111] and m[111] in the thin film”, but the language “wherein an X-ray diffraction profile of a diffraction angle 2Q between 25 degrees and 35 degrees has a maximum diffraction intensity angle 2Q between 28 degrees and 29 degrees”, so the first condition (i) must be met. (see prepub at [0066] which states “Regarding the above, m[11-1] and m[111] are [11-1] plane and [111] plane in a primitive monoclinic lattice, with diffraction angles 2θ of 28.589 degrees and 31.811 degrees, respectively. Further, o[111] is [111] plane in a primitive orthorhombic lattice”)
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.
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 1-4, 9-12,16,17 and 19-20 are rejected under 35 U.S.C. 102(a)(1)as being fully anticipated by Mohri et al. 5561009, as evidenced by Imamura et al. WO 2022039216.
Mohri et al. 5561009 in example 1 teaches the sputtering of 100 nm hafnium oxide from an HfO2 target using 6.7 x 10-1 Pa argon onto a quartz substrate (4/25-67). Example 2 coats this etch stopper with a, opaque Cr layer, which is patterned using a resist and then a spin on glass (SOG) phases shift layer which is fired at 300 degrees C and then patterned using a resist to form a patterned mask (5/1-6/2). The present invention relates generally to a photomask used for fabricating high-density integrated circuits such as LSIs and VLSIs and a photomask blank used for fabricating such a photomask, and more particularly to a phase shift photomask and a blank therefor (2/41-50).
Imamura et al. WO 2022039216 (machine translation attached) in manufacturing example 1, teaches a quartz substrate (20 degrees C) which is alternatingly sputtered with HfO2 and SiO2 in the presence of 100 sccm argon and 100 sccm oxygen and 40 kW to form a multilayer [0091]. The multilayered film was then heated at 500 degrees C for 60 minutes in the atmosphere. Other inventive films were also heated. Comparative examples 1-4 were not heat treated. [0102]. The X-ray diffraction of figure 2 shows the comparative example has the highest leak being at 28.4 degrees which is attributed to monoclinic [0102-0103]. FIG. 2 is a diagram showing X-ray diffraction spectra of the optical filters obtained in Example 2 and Comparative Example 1. As shown in FIG. 2, in the X-ray diffraction spectrum of Example 2, a diffraction peak due to the (1 1.1) crystal plane derived from the cubic hafnium oxide crystal is observed near 2θ = 30.7 °, and 2θ = Diffraction peaks due to the (-1 1.1) crystal plane derived from monoclinic Hafnium oxide crystals were observed around 28.4 °. On the other hand, in Comparative Example 1, no diffraction peak due to the (1.11) crystal plane derived from the cubic hafnium oxide crystal was observed [0103].
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Similarly, X-ray diffraction measurements were also performed on the optical filters of Examples 1, 3 to 7, 9 to 17 and Comparative Examples 2 to 4, and the crystal planes derived from cubic Hafnium oxide crystals (1 1 1). The peak area intensity Ic of the diffraction peak due to the above, the peak area intensity Im of the diffraction peak due to the (-1 1.1) crystal plane derived from the monoclinic hafnium oxide crystal, and the ratio Ic / Im were obtained. The results are shown in Table 3 below [0104]
It appears that the Xs for example 24 and comparative example 6 in table 6 (page 34) indicate that the HfO2 are also monoclinic [0128-0130]. Table 3 supports comparative examples 1-4 being monoclinic.
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Table 6 (below)
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The reference establishes that sputtered deposition using Ar/O2 in the sputtering gas yields a layer having a monoclinic crystalline structure (comparative examples 1-4), which is converted to a cubic structure when heated at 500-800 degrees C (inventive examples 1-27)
The applicant argues that the cited HfO films of Mohri et al. 5561009 do not meet the compositional limitation now recited in the claims or evidence the crystalline structure.
The examiner holds that Imamura et al. WO 2022039216 evidences that the sputtered deposition of the hafnium dioxide etch stop layer without subsequent heating above 300 degrees C in the examples of Mohri et al. 5561009 which uses 6.7 x 10-1 Pa argon (on oxygen) as the sputtering gas is monoclinic. The examiner notes that the annealing described in the instant specification is at least 450 degrees C.
The examiner notes that the comparative example of the instant specification supports the position that sputtering using and HfO2 target and only argon gas yields an oxygen content of ~64%, which is less than 66% or 65% recited in claims 1,16,17 and 19. The rejection stands.
In the response of 1/8/2026, the applicant argued that the composition of the sputtered film is not taught, so the examiner is in error to consider it oxygen deficient. In the instant application sputtering from an HfO2 target in the presence of Ar (layer 21,23) is disclosed as resulting in a HfO film with 66 at% oxygen content (see prepub at [0163, 01650]). The sputtering conditions in the cited example of Mohri et al. 5561009 are similarly form an HfO2 target in the presence of Ar alone. For layers 21 and 23 the refractive index n was 2.93 and the extinction coefficient k was 0.24 [0164]. If the applicant wishes to contest, the position of the examiner with respect to the HfO film being monoclinic as deposited, the examiner invites the applicant to provide declaration evidence.
Claims 1-4, 9-12,16,17 and 19-20 are rejected under 35 U.S.C. 102(a)(1)as being fully anticipated by KR 100335735, as evidenced by Imamura et al. WO 2022039216.
KR 100335735 (machine translation attached) teaches in embodiment 1, a substrate coated with a hafnium oxide etch stop layer using sputtering from a hafnium dioxide target in the presence of 3 Pa argon, this was then coated with a CrON light shielding film, which was then patterned using a resist, and an SOG layer which fired at 300 degrees C , planarized and patterned using a resist(page 7/line 8-page 8/line 37). The present invention relates to an image shifter type phase shift photomask capable of transferring a micro pattern by projection exposure to a wafer in a photomask used for fabricating a high density semiconductor integrated circuit of semiconductor devices such as ultra LSI and ultra ultra LSI. A phase shift photomask of at least one of a light shielding layer pattern and a light shielding layer pattern and a shifter layer is formed on a transparent substrate, and the shifter layer pattern is formed on a weight having the shifter layer formed thereon. The manufacturing method includes the step of planarizing by grinding | polishing removal of the unevenness | corrugation of the surface of the shifter layer which arises by the level difference by the light shielding layer pattern (abstract).
The examiner holds that Imamura et al. WO 2022039216 evidences that the sputtered deposition of the hafnium dioxide etch stop layer without subsequent heating above 300 degrees C in the examples of KR 100335735 is monoclinic.
The applicant argues that the cited HfO films of KR 100335735 do not meet the compositional limitation now recited in the claims.
The examiner holds that Imamura et al. WO 2022039216 evidences that the sputtered deposition of the hafnium dioxide etch stop layer without subsequent heating above 300 degrees C in the examples of KR 100335735 which use 3 Pa argon (on oxygen) as the sputtering gas is monoclinic. The examiner notes that the annealing described in the instant specification is at least 450 degrees C.
The examiner notes that the comparative example of the instant specification supports the position that sputtering using and HfO2 target and only argon gas yields an oxygen content of ~64%, which is less than 66% or 65% recited in claims 1,16,17 and 19. The rejection stands.
In the instant application sputtering from an HfO2 target in the presence of Ar (layer 22) is disclosed as resulting in a HfO film with 66 at% oxygen content (see prepub at [0128, 0130]). The sputtering conditions in the cited example of Kr 100335735 are similarly form an HfO2 target in the presence of Ar alone.
In the response of 1/8/2026, the applicant argued that the composition of the sputtered film is not taught, so the examiner is in error to consider it oxygen deficient. In the instant application sputtering from an HfO2 target in the presence of Ar (layer 21,23) is disclosed as resulting in a HfO film with 66 at% oxygen content (see prepub at [0163, 01650]). The sputtering conditions in the cited example of KR 100335735 are similarly form an HfO2 target in the presence of Ar alone. For layers 21 and 23 the refractive index n was 2.93 and the extinction coefficient k was 0.24 [0164]. If the applicant wishes to contest, the position of the examiner with respect to the HfO film being monoclinic as deposited, the examiner invites the applicant to provide declaration evidence.
Claims 1-8, 15 and 20 are rejected under 35 U.S.C. 102(a)(1)as being fully anticipated by Mori et al. JP 07-209849, as evidenced by Imamura et al. WO 2022039216.
Mori et al. JP 07-209849 (machine translation attached) in example 1, teaches a phase shift maskblank where a quartz substrate is sputtered to a thickness of 170 nm of a HfOx (0<x<2) film from a Hf metal target in the presence of 70 sccm Ar and 30 sccm oxygen to yield a phase shift of approximately 180 degrees [0031-0032]. Example 2 coats this with chrome and patterns the mask blank using a resist and electron beams exposure [0033-0035]. Example 3 forms a similar mask using a lift off, rather than etching [0036]. Field of the Invention The present invention relates to a photomask used for manufacturing high density integrated circuits such as LSI and VLSI, and a photomask blank for manufacturing the photomask. The present invention relates to a halftone phase shift photomask obtained, and a blank for a halftone phase shift photomask for manufacturing this phase shift photomask [0001]. The dependent of the spectral transmittance of the HfOx film exhibits a substantially constant transmittance across the mask inspection wavelength range for various degrees of oxidation [0016].
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The examiner holds that Imamura et al. WO 2022039216 evidences that the sputtered deposition of the hafnium dioxide etch stop layer without subsequent heating in the examples of Mori et al. JP 07-209849 is monoclinic.
The applicant argues that the cited HfO films of Mori et al. JP 07-209849 do not meet the compositional limitation now recited in the claims.
The examiner holds that Imamura et al. WO 2022039216 evidences that the sputtered deposition of the hafnium dioxide etch stop layer without subsequent heating in the examples of Mori et al. JP 07-209849 which uses a Hf metal target in the presence of 70 sccm Ar and 30 sccm oxygen as the sputtering gas is monoclinic. The examiner notes that the annealing described in the instant specification is at least 450 degrees C.
The position of the examiner is that even with the oxygen content of the sputtering gas, the oxygen content in the resulting film is 66% or less. The applicant may have data which could be presented in a proper declaration to refute the position that the composition is not within the more than 60 to less than 66% oxygen range based upon the 7:3 ratio of the Ar:oxygen in example 1 of the Mori et al. JP 07-209849. The examiner notes that the HfOx (O<x<2) is specifically described at [0016], which embraces the range of 60 (x=1.20) and 65% (1.30) or 66% (x=1.32). The rejection stands.
In the response of 1/8/2026, the applicant argues that Mori et al. does not teach the oxygen deficiency recited in claim 1. The reference clearly teaches HfOx ; 0 <x <2, so the compositions envisioned in the reference are all clearly substoichiometric (ie below 66.6%) and the range clearly embraces 1.20<x<1.28 (60at % and 64at% oxygen respectively.) . As discussed above, the examiner contends on the basis of evidence in Imamura et al. WO 2022039216 that the HfO layers are monoclinic as deposited. The orthorhombic crystalline structure occurs after annealing.
Claims 1-4,9-14,16,16 and 19-20 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Mori et al. JP H0736176, as evidenced by Imamura et al. WO 2022039216.
Mori et al. JP H0736176 (machine translation attached) sputters from a HfO2 target in the presence of argon to deposit a layer 100 nm thick without substrate heating [0025]. This was then used as an etch stop layers in a phase shift photomask which is useful with the i-line of a mercury lamp or KrF excimer [0029-0032]. In order to form a hafnium oxide layer by a sputtering method, a target mainly composed of metal hafnium or an oxide of hafnium is used, and a sputter gas such as argon, neon, xenon, or nitrogen is used alone, or with these sputter gases. An atmosphere in which oxygen, a carbon dioxide gas, a nitrogen oxide gas, water vapor, and a gas serving as an oxygen source are combined is maintained at an appropriate pressure, and a substrate is exposed to plasma generated by applying direct current or high frequency power [0016].
In the instant application sputtering from an HfO2 target in the presence of Ar (layer 21,23) is disclosed as resulting in a HfO film with 66 at% oxygen content (see prepub at [0163, 01650]). The sputtering conditions in the cited examples of Mori et al. JP H0736176 are similarly form an HfO2 target in the presence of Ar alone. For layers 21 and 23 the refractive index n was 2.93 and the extinction coefficient k was 0.24 [0164]. If the applicant wishes to contest, the position of the examiner with respect to the HfO film being monoclinic as deposited, the examiner invites the applicant to provide declaration evidence.
Claims 1-4, 9-12,14,16,17 and 19-20 are rejected under 35 U.S.C. 103 as being unpatentable over Mohri et al. 5561009, as evidenced by Imamura et al. WO 2022039216
The examiner holds that Imamura et al. WO 2022039216 evidences that the sputtered deposition of the hafnium dioxide etch stop layer without subsequent heating above 300 degrees C in the examples of Mohri et al. 5561009 is monoclinic.
It would have been obvious to extend the process of forming a photomask exemplified in
Mohri et al. 5561009 to the use of the photomask to in a photoresist exposure process based upon the use of resists in the examples for patterning and the direction to the use of the photomask to fabricate high-density integrated circuits such as LSIs and VLSIs at (2/41-50).
The rejection stands for the reasons above as no further arguments were directed at this rejection.
Claims 1-4, 9-12 14,16,17 and 19-20 are rejected under 35 U.S.C. 103 as being unpatentable over KR 100335735, as evidenced by Imamura et al. WO 2022039216
The examiner holds that Imamura et al. WO 2022039216 evidences that the sputtered deposition of the hafnium dioxide etch stop layer without subsequent heating above 300 degrees C in the examples of KR 100335735 is monoclinic.
It would have been obvious to extend the process of forming a photomask exemplified in
KR 100335735 to the use of the photomask to in a photoresist exposure process based upon the use of resists in the examples for patterning and the direction to the use of the photomask to fabricate semiconductor devices as ultra LSIs (abstract).
The rejection stands for the reasons above as no further arguments were directed at this rejection.
Claims 1-8,13,15,17-18 and 20 are rejected under 35 U.S.C. 103 as being unpatentable over Mori et al. JP 07-209849, as evidenced by Imamura et al. WO 2022039216
The examiner holds that Imamura et al. WO 2022039216 evidences that the sputtered deposition of the hafnium dioxide etch stop layer without subsequent heating in the examples of Mori et al. JP 07-209849 is monoclinic.
It would have been obvious to extend the process of forming a photomask exemplified in Mori et al. JP 07-209849 to the use of the photomask in a photoresist exposure process based upon the use of resists in the examples for patterning and the direction to the use of the photomask to fabricate semiconductor devices such as LSI and VLSI [0001].
Alternatively, it would have been obvious to one skilled in the art to modify the process of example 1 by reducing the oxygen content of the sputtering gas to decrease the oxygen content of the HfOx so that x is 1.2<x<1.30 based upon the disclosure of x being 0<x<2 and the disclosure that the degree of oxidation is not critical at [0016] which would result in the oxygen content being 60-65 at% with the recited monoclinic crystalline structure as the HfO layer is not heated. Further, it would have been obvious to use the resulting photomask in a photoresist exposure process based upon the use of resists in the examples for patterning and the direction to the use of the photomask to fabricate semiconductor devices such as LSI and VLSI [0001].
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure.
Maeda et al. WO 2022201816 (machine translation attached) in example 1 coats a translucent substrate 1 composed of synthetic quartz glass having a main surface dimension of approximately 152 mm×approximately 152 mm and a thickness of approximately 6.35 mm was prepared. The end faces and main surfaces of the translucent substrate 1 are polished to a predetermined surface roughness (Sq of 0.2 nm or less), and then subjected to predetermined cleaning and drying processes. When each optical characteristic of the translucent substrate 1 was measured using a spectroscopic ellipsometer (M-2000D manufactured by JA Woollam), the refractive index was 1.556 and the extinction coefficient was 0.556 for light with a wavelength of 193 nm. Next, the translucent substrate 1 was placed in a single-wafer RF sputtering apparatus, and an HfO .sub.2 target and a SiO .sub.2 target were alternately used to perform sputtering (RF sputtering) using argon (Ar) gas as the sputtering gas. A phase shift film 2 comprising a lower layer 21 composed of hafnium and oxygen, a lower layer 22 composed of silicon and oxygen, and an upper layer 23 composed of hafnium and oxygen was formed on an optical substrate 1 . .sub.The thickness D1 of the lowermost layer 21 was 38 nm, the thickness of the lower layer 22 was 16 nm, and the thickness of the upper layer 23 was 5 nm, all of which were 5 nm or more. The thickness of the phase shift film 2 was 59 nm, which was 90 nm or less. Next, the light-transmitting substrate 1 with the phase shift film 2 formed thereon was subjected to heat treatment for reducing the film stress of the phase shift film 2 . Using a phase shift measurement device (MPM193 manufactured by Lasertec), the transmittance and phase difference of the heat-treated phase shift film 2 with respect to light having a wavelength of 193 nm were measured. It was 177.2 degrees (deg). In addition, when each optical characteristic of the phase shift film 2 was measured using a spectroscopic ellipsometer (M-2000D manufactured by JA Woollam), the refractive index n of the bottom layer 21 and the top layer 23 for light with a wavelength of 193 nm was 2. .93, the extinction coefficient k was 0.24, the refractive index n of the lower layer 22 was 1.56, and the extinction coefficient k was 0.00. In addition, the oxygen content of the upper layer 23 of the phase shift film 2 was 66 atomic % or less, and oxygen deficiency occurred [0090-0091]
Any inquiry concerning this communication or earlier communications from the examiner should be directed to Martin J Angebranndt whose telephone number is (571)272-1378. The examiner can normally be reached 7-3:30 pm EST.
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If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Mark F Huff can be reached at 571-272-1385. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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MARTIN J. ANGEBRANNDT
Primary Examiner
Art Unit 1737
/MARTIN J ANGEBRANNDT/Primary Examiner, Art Unit 1737 February 12, 2026