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 Rejection of the previous action, not repeated below are withdrawn.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 amendment to the specification are approved. The proper TD filed 11/28/2025 obviates the ODP rejection.
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 1-7,9-16 and 18-19 are rejected under 35 U.S.C. 103 as being unpatentable over Lee et al. 20220397819, as evidenced by Fukushima et al. JP 61-221361, Inazuki et al. 20180224737 and Jeong et al. 20230135037.
Lee et al. 20220397819 in example 1 teaches a mask blanks formed of two light shielding layers. A transparent substrate of quartz material with a width of 6 inches, a length of 6 inches, and a thickness of 0.25 inches was disposed in a chamber of a DC sputtering device. A chrome target was disposed in the chamber to form a T/S distance of 255 mm and an angle of 25 degrees between the substrate and the target. Thereafter, an atmosphere gas, in which Ar of 21 volume %, N.sub.2 of 11 volume %, CO.sub.2 of 32 volume %, and He of 36 volume % had been mixed, was introduced into the chamber, the electric power supplied to the sputtering target was 1.85 kW, the rotation speed of a magnet 113 rpm, and a sputtering process was performed for 250 seconds, thereby forming a first light shielding layer. After forming the first light shielding layer, an atmosphere gas, in which Ar of 57 volume % and N.sub.2 of 43 volume % had been mixed, was introduced into the chamber, the electric power supplied to a sputtering target was 1.5 kW, a sputtering process was performed for 25 seconds, and a blank mask sample, in which a second light shielding layer had been formed, was manufactured. The sample after forming the second light shielding layer was disposed in a thermal treatment chamber, and thermal treatment was performed for 15 minutes at the atmosphere temperature of 200° C. A cooling plate, to which a cooling temperature had been applied to be 23° C., was installed on the lower side of the transparent substrate of the sample after thermal treatment. The distance between the substrate and the cooling plate of the sample was adjusted to have a cooling rate of 36° C./min measured at the upper surface of the light shielding film of the sample, and after that, the cooling operation was performed for 5 minutes. After the cooling treatment, the sample was left at an atmosphere of 20 to 25° C. and stabilized for 15 minutes [0184-0189]. Figure 3 illustrates a mask blank comprising a substate (10), a phase shift layer (30) and a light shielding layer (20) [0053]. Figure 2 illustrates the embodiment including a substrate (10),m a first light shielding layer (21) and a second light shielding layer (22) [0087]. In such a case, it is possible to help the light shielding film 20 to shield an exposure light substantially with a phase shift film 30 together [0092]. The phase shift film 30 may be disposed between the transparent substrate 10 and the light shielding film 20. The phase shift film 30 is a thin film, which attenuates the strength of an exposure light transmitting the phase shift film 30, adjusts the phase shift, and thereby substantially suppresses a diffraction light occurring at the edge of a pattern. The phase shift film 30 may have a phase difference of 170 to 190° with respect to a light with a wavelength of 193 nm. The phase shift film 30 may have a phase difference of 175 to 185° with respect to a light with a wavelength of 193 nm. The phase shift film 30 may have a transmittance of 3 to 10% with respect to a light with a wavelength of 193 nm. The phase shift film 30 may have a transmittance of 4 to 8% with respect to a light with a wavelength of 193 nm. In such a case, the resolution of a photomask 200 including the phase shift film 30 may be improved. The phase shift film 30 may include a transition metal and silicon. The phase shift film 30 may include a transition metal, silicon, oxygen, and nitrogen. The transition metal may be molybdenum [0113-0115].
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The light shielding film 20 may have shielding characteristics against at least some of the exposure light transmitting the transparent substrate 10. Additionally, when a phase shift film 30 (refer to FIG. 3) and the like is disposed between the transparent substrate 10 and the light shielding film 20, the light shielding film 20 can be used as an etching mask in a process of etching the phase shift film 30 and the like to have a pattern shape [0053]. A hard mask (not shown) may be disposed on the light shielding film 20. The hard mask may function as an etching mask film when a pattern of the light shielding film 20 is etched. The hard mask may include silicon, nitrogen, and oxygen [0117]. A method of manufacturing the semiconductor element according to another embodiment of the present disclosure includes a preparing operation of disposing a light source, a photomask, and a semiconductor wafer, on which a resist film have been applied, an exposure operation of selectively transmitting a light incident from the light source through the photomask on the semiconductor wafer to be transferred, and a developing operation of developing a pattern on the semiconductor wafer. The photomask includes a transparent substrate and a light shielding pattern film disposed on the transparent substrate [0173-0174]. Claims 1-15 are to the (unpatterned) mask blank and claims 16-19 are to the (patterned) photomask .
Inazuki et al. 20180224737 teaches in example 1, a MoSiON film with 6% transmittance coated to a thickness of 75 nm, which is then coated with a Cr40O50N10 layer with a thickness of 44 nm. The composition of the Cr target was determined. This was inspected for defects [0092-0095]. Comparative example 1 was formed similarly and the composition of the Cr target used was determined using glow discharge mass spectrometry (GD-MS). The Cr target composition in table 1 is reproduced below.
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566
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404
577
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Also, since iron (Fe) is a metal contained in the raw material for metallic chromium, the metallic chromium target contains a certain content of iron. Although iron is not the metal impurity that positively induces migration as mentioned above, it is recommended that the iron content be so low as not to affect the optical and physical properties of a chromium-containing film to be deposited on a transparent substrate. Therefore, the iron content of the metallic chromium target is preferably up to 30 ppm, more preferably up to 20 ppm [0079]. Among metal impurities in the metallic chromium target, the contents of lead (Pb), copper (Cu), tin (Sn) and gold (Au) are preferably up to 1 ppm, more preferably up to 0.1 ppm, even more preferably up to 0.01 ppm. Lead (Pb) and tin (Sn) are metal impurities in the metallic chromium target although they are not transition metals. These four species of metals are susceptible to migration (as mentioned above) and precipitate on the silicon-containing film. For preventing these metal impurities from precipitation, it is more effective to reduce the contents of these metals in the metallic chromium target at or below the predetermined level [0078].
Fukushima et al. JP 61-221361 (cited by applicant, machine translation attached) teaches Cr sputtering targets typically contain 70-5000 ppm Fe, which reduces the adhesion of Cr films. Controlling the Fe content to be 0.5-45 ppm improves the adhesion (page 1/right column-page 2/left column). The use of the Cr thin films on plastics for vehicle handles and the like, as a mirror, or when patterned using a resist as a photomask (page 1). When the Fe content is more than 45 ppm, the adhesion is reduced, but when it is 0.5 ppm or less, the target is expensive to produce. Within the range the chromium film can be used without an undercoat, which reduces the cost (page 2/left column). In the examples, films with various Fe contents were sputtered onto different substates (5 microns on ABS plastic and 0.5 microns of glass) with different thicknesses as in table 1. .
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Jeong et al. 20230135037 teaches in example 1 A transparent substrate made from quartz in the size of 6-inched width, 6-inched length, and 0.25 inched thickness was disposed in a chamber of DC sputtering apparatus. A chrome target was disposed in the chamber to have the T/S distance of 255 mm and the angle of 25 degrees between the substrate and the target. A first light shielding film is formed on the transparent substrate. In detail, the atmospheric gas mixed in the volume ratio of Ar:N.sub.2:CO.sub.2=3:2:5 was introduced in a chamber, the electric power of 1.85 kW was supplied to a sputtering target, the rotation speed of 10 RPM for the substrate was applied, and thereby a sputtering process proceeded for a time of 200 seconds to 250 seconds to form a lower light shielding layer. After completion of the first light shielding film, the formation of a second light shielding film comprising an adhesion enhancing layer and an upper light shielding layer is performed. In detail, the atmospheric gas mixed in the volume ratio of Ar:N.sub.2=6.5:3.5 was introduced in a chamber, the electric power of 1.85 kW was supplied to a sputtering target, the rotation speed of 10 RPM for the substrate was applied, a sputtering process proceeded for 5 seconds, and thereby an adhesion enhancing layer was formed on the first light shielding film. In the process of forming the adhesion enhancing layer, an electric power was supplied to the sputtering target after 20 seconds from the time when the formation of the first light shielding film had been completed, and the atmospheric gas was injected within 5 seconds from the time when the atmospheric gas applied to the formation of the first light shielding film had been exhausted completely from the chamber. After completion of the formation of the adhesion enhancing layer, an atmospheric gas mixed in the volume ratio of Ar:N.sub.2=6.5:3.5 was introduced in the chamber, the electric power of 1.5 kW was supplied to a sputtering target, the rotation speed of 10 RPM for the substrate was applied, and thereby a sputtering process was performed for a time of 10 seconds to 30 seconds on the top side of the adhesion enhancing layer to form an upper light shielding layer. In the process of forming first and second light shielding films, the atmospheric gas was supplied through an inlet placed in the bottom side of the inner space of the sputtering chamber [0290-0295].
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Lee et al. 20220397819 does not exemplify a mask blank or patterned mask including a phase shift layer and the recited first and second light shielding layers and does not disclose the Cr, N, C or trace metal content of the light shielding layers, the thickness of the light shielding layers, the patterning of the mask blank or the use of the patterned photomask in an exposure process.
With respect to claims 1-7 and 9, it would have been obvious to one skilled in the art to modify formation of the mask blanks in example 1 of Lee et al. 20220397819 by forming a phase shift layer on the substrate prior to the formation of the light shielding layers based upon the direction of figure 3 and [0092] to reduce the diffraction of light at the edges and improve the resolution of the photomask [0113-0115] with a reasonable expectation of forming a useful photomask blank. The position of the examiner is that sputtering targets used contain at least trace amounts of a metals from the group 7-12. This is determined to be the source of the Fe in the instant specification (See table 1) as well as the teachings of Fukushima et al. JP 61-221361 and Inazuki et al. 20180224737, which clearly establish that trace elements are typically found in the Cr sputtering targets.. The examiner notes that the claims embrace amounts outside the 0.01-0.010 wt% used in the inventive examples of table 1 and therefore any showing is not commensurate with the scope of coverage sought. The applicant has chosen to describe their invention in terms of the spectral power density, which is not commonly reported and therefore must shoulder the burden of establishing that this is not due to the presence of impurities commonly found in sputtering targets and the amorphous stature the layer. Jeong et al. 20230135037 evidences that the language describing the 250 second sputtering time for the first light shielding layer and a 25 second sputtering time for the second light shielding layer yield a 46 nm (460 angstrom) thick first light shielding layer and a 6 nm (60 angstrom) second light shielding layer (see table 2 of Jeong et al.) with Cr43O38C9N10 and Cr67O10C3N20 compositions respectively (see table 6 of Jeong et al.) and that the language describing the introduction of the Ar/N2 gas mixture after the formation of the first light shielding layer describes the mere addition of the Ar/N2 gas to the gasses already in the sputtering chamber, which results in the carbon and oxygen content of the second light shielding layer. The heating and rapid cooling inherently yield the roughness and power spectrum density values of the claims
With respect to claims 1-7.9-16 and 18-19, it would have been obvious to one skilled in the art to modify formation of the mask blanks in example 1 of Lee et al. 20220397819 by forming a phase shift layer on the substrate prior to the formation of the light shielding layers based upon the direction of figure 3 and [0092] to reduce the diffraction of light at the edges and improve the resolution of the photomask [0113-0115] and to pattern the mask blank to form the mask of claims 16-19, which is then used in the exposure process forming semiconductor devices discussed at [0173-0174] with a reasonable expectation of forming a useful mask blank, patterned mask and semiconductor device. The position of the examiner is that sputtering targets used contain at least trace amounts of a metals from the group 7-12. This is determined to be the source of the Fe in the instant specification (See table 1) as well as the teachings of Fukushima et al. JP 61-221361 and Inazuki et al. 20180224737, which clearly establish that trace elements are typically found in the Cr sputtering targets.. The examiner notes that the claims embrace amounts outside the 0.01-0.010 wt% used in the inventive examples of table 1 and therefore any showing is not commensurate with the scope of coverage sought. The applicant has chosen to describe their invention in terms of the spectral power density, which is not commonly reported and therefore must shoulder the burden of establishing that this is not due to the presence of impurities commonly found in sputtering targets and the amorphous stature the layer. Jeong et al. 20230135037 evidences that the language describing the 250 second sputtering time for the first light shielding layer and a 25 second sputtering time for the second light shielding layer yield a 46 nm (460 angstrom) thick first light shielding layer and a 6 nm (60 angstrom) second light shielding layer (see table 2 of Jeong et al.) with Cr43O38C9N10 and Cr67O10C3N20 compositions respectively (see table 6 of Jeong et al.) and that the language describing the introduction of the Ar/N2 gas mixture after the formation of the first light shielding layer describes the mere addition of the Ar/N2 gas to the gasses already in the sputtering chamber, which results in the carbon and oxygen content of the second light shielding layer. The heating and rapid cooling inherently yield the roughness and power spectrum density values of the claims
Claims 1-6,8-16 and 18-19 are rejected under 35 U.S.C. 103 as being unpatentable over Shin et al. KR 20210147391, in view of Fukushima et al. JP 61-221361 and Inazuki et al. 20180224737.
Shin et al. KR 20210147391 (machine translation attached) teaches in example 1 , a MoSiN phase shift layer, which was heat treated at 350 degrees C for 20 minutes, this was then overcoated with a 46.5 nm of Cr39.4 C17.1 O20.4 N23.1 sputtered at a power or 0.75 kW and a 4.2 nm Cr44.3 C13.5 O10.4 N31.8 layer sputtered with a power of 1.40 kW and a 4.3 nm Cr41.5 C16.6 O19 N22.9 layer and then heated to 250 degrees C in a rapid thermal process and then coated with a resist [0058-0070]. Examples 2-4 are similar [0071-0090]. The blank mask 100 according to the present invention includes a phase shift film 102 , a light blocking film 103 , and a resist film 110 sequentially stacked on a transparent substrate 101 [0001]. In detail, the chromium (Cr) content of the first light blocking layer 104 and the third light blocking layer 106 is 30 to 50 at%, the oxygen (O) content is 5 to 40 at%, and the nitrogen (N) content is 0 to 50at%, the carbon (C) content is 0-50at%, the chromium (Cr) content of the second light blocking layer 105 is 50-100at%, the oxygen (O) content is 0-30at%, the nitrogen (N) content It is preferable that the silver is 0 to 50 at%, and the carbon (C) content is 0 to 40 at% [0041]. Today, in order to manufacture a photomask having high resolution and excellent quality, thinning of the resist film is required. Accordingly, in the photolithography technology, the exposure wavelength is shortened from I-Line of 365 nm to ArF of 193 nm. ), from a hardmask binary blankmask having a hardmask film and a light-shielding film to a hardmask on phase shifting blankmask in recent years [0003]
Shin et al. KR 20210147392 does not teach the smoothness, the presence of group 7-12 metals in the sputtering target or the difference in chromium content between the lower layer and the uppermost layer.
With respect to claims 1-7 and 9, it would have been obvious to one skilled in the art to modify the process of forming a mask of examples 1-4 by reducing the Cr content of the lower/first light shielding layer to 30-31.5 at% based upon the disclosure at [0041] and using a Cr target containing at least trace amounts of Zn, Mn, Co, Ni, Cu as is typical as evidenced in Inazuki et al. 20180224737 and 5-30 ppm of Fe as taught in Fukushima et al. JP 61-221361 and Inazuki et al. 20180224737 to form Cr layers with good adhesion without excessive expense with a reasonable expectation of forming a useful mask blank.
With respect to claims 1-7,9-16 and 18-19, it would have been obvious to one skilled in the art to modify the process of forming a mask of examples 1-4 by reducing the Cr content of the lower/first light shielding layer to 30-31.5 at% based upon the disclosure at [0041] and using a Cr target containing at least trace amounts of Zn, Mn, Co, Ni, Cu as is typical as evidenced in Inazuki et al. 20180224737 and 5-30 ppm of Fe as taught in Fukushima et al. JP 61-221361 and Inazuki et al. 20180224737 to form Cr layers with good adhesion without excessive expense and to use the resist coated in the example to pattern the mask blank and use the resulting patterned mask in an exposure process with 193 nm as discussed at [0003] with a reasonable expectation of forming a useful mask blank, patterned mask and electronic device
The examiner points out that the difference in the nitrogen content of the layers is at least 1%, and that the rapid thermal treatment inherently results in an amorphous layer with a surface roughness of 0.25 to 0..55 nm. Additionally, there is ample evidence that conventional target used would have trace amounts of the group 7-12 metals and that the use of Cr targets having Fe content in the 5-30 ppm range improves the adhesion of the layers.
The applicant argues that the examiner has used the applicant’s specification as a roadmap. The examiner points out that as the Cr layers are formed by sputtering from a Cr target in a vacuum, there is only one likely source of any trace elements. The applicant argues that Fukushima et al. teaches a desirability of keeping the Fe content below 45 ppm. The examiner points out that the instant claims embrace amounts of less than 45 ppm and that Inazuki et al. 20180224737 teaches a variety of trace elements found in Cr sputtering targets used in forming Cr light shielding layers. The applicant has chosen to describe their invention in terms of the spectral power density, which is not commonly reported and therefore must shoulder the burden of establishing that this is not due to the presence of impurities commonly found in sputtering targets and the amorphous stature the layer.
In the response of 12/24/2025, the applicant argues against the combination of Shin et al. KR 20210147391, in view of Fukushima et al. JP 61-221361 and Inazuki et al. 20180224737 by arguing the chromium difference is not taught in Inazuki et al. 20180224737. The Cr difference relied upon by the examiner is found in the 30-50 at% range taught for the first and third light shielding layers in Shin et al. KR 20210147391 at [0041]. Inazuki et al. 20180224737 is relied upon the establish the trace metal content of Cr sputtering targets. The ratio of 4/3/46.5 nm is 0.13, which is within the recited range of 0.05-0.3. The rapid thermal processing is held to result in amorphous/non-crystalline structure, the smoothness and power spectrum density. The applicant is invited to provide evidence to refute this. The rapid thermal treatment appears to be the same treatment as used in the instant application.
Claims 1-6,8-16 and 18-19 are rejected under 35 U.S.C. 103 as being unpatentable over Shin et al. KR 20210147391, in view of Fukushima et al. JP 61-221361 and Inazuki et al. 20180224737, further in view of Nam et al. KR 20130051879.
Nam et al. KR 20130051879 (machine translation attached) teaches a substrate with a Cr
metal layer which is sputtered in a Ar/N2/NO atmosphere and then overcoated with a Cr metal
antireflection layer sputtered in an atmosphere containing 0-30% methane (CH4) as described in
table 1 to form a chromium carbide gradient within the antireflection layer [0037-0041]. Figure 2
illustrates a mask blank including a substrate (10), a phase shift layer (60), a light shielding metal
film (20), a antireflection film (30) and a photoresist (50) [0029].
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In examples 8,10,12,14 and 15, a rapid heat treatment apparatus (RTP) was used to perform surface heat treatment for 20 minutes at a pressure of 10 mTorr to 2 mTorr and a temperature of 350 0 C. (examples 7,9,11,13 and 15 are comparative, not being heat treated, in table 2. The heat treated examples exhibit reduced etching due to ozone exposure (table 3, reproduced below).
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In recent years, in order to solve the problem of washing I cleaning using sulfuric acid, the ozone washing process containing ozone water washing I cleaning or an ultraviolet-ray has attracted much attention. However, in the cleaning process using the ozone water, for example, when the light shielding film and the antireflection film are formed of chromium (Cr), the phenomenon that the chromium is dissolved or corroded occurs in the ozone water, which reduces the reflectivity of the metal layer/antireflective layer [0004-0006]. In addition, it can be seen that the smaller the difference in the injection ratio of the reactive gas containing carbon (C) for forming the anti-reflection film 30, the smaller the difference in thickness change after cleaning [0049-0057]. The light shielding film 20 and the antireflection film 30 include chromium (Cr), titanium (Ti),vanadium (V), cobalt (Co), nickel (Ni), zirconium (Zr), niobium (Nb), and palladium (Pd). , Zinc (Zn), chromium (Cr), aluminum (Al), manganese (Mn), cadmium (Cd), magnesium (Mg),
lithium (Li), selenium (Sc), copper (Cu), molybdenum (Mo) And at least one or more transition
metals of hafnium (Hf), tantalum (Ta), and tungsten (W). In addition, the light shielding film 20
and the antireflection film 30 may include at least one of silicon (Si), oxygen (O), nitrogen (N),
carbon (C), hydrogen (H), and fluorine (F). It is configured to include. The light blocking film 20
and the antireflection film 30 may include, for example, chromium (Cr) in the transition metal.
The light shielding film 20 and the antireflection film 30 include carbon (C), and in particular,
the antireflection film essentially includes carbon (C) [0031]. The metal film formed of the light
shielding film 20 and the anti-reflection film 30 may be heat treated, and the heat treatment
process may include a rapid thermal process (RTP), a vacuum hot-plate bake, a plasma and
Furnace can be carried out by one or more methods. The heat treatment process is preferably
carried out in a vacuum of 10 .sup.-3 torr or less. The heat treatment step is preferably performed
for 10 to 60 minutes at a temperature of 200 °C to 500 °C. Cooling after the heat treatment may
be performed by a method using natural cooling or a rapid cooling device [0034]. A phase
inversion film 60 may be further provided between the transparent substrate 10 and the metal
film 40. The phase inversion film 60 includes chromium (Cr), titanium (Ti), vanadium (V),
cobalt (Co), nickel (Ni), zirconium (Zr), niobium (Nb), palladium (Pd), and zinc (Zn). ),
Chromium (Cr), aluminum (Al), manganese (Mn), cadmium (Cd), magnesium (Mg), lithium
(Li), selenium (Se), copper (Cu), molybdenum (Mo), hafnium (Hf) ), Tantalum (Ta), tungsten
(W) and silicon (Si). In addition, the phase inversion film 60 includes at least one of oxygen (O),
nitrogen (N), carbon (C), hydrogen (H), and fluorine (F) in the material. The phase inversion
layer 60 may be formed of a material having an etching selectivity of 10 or more with respect to
the metal film 40 with respect to the etching material, and may be formed of, for example, a
molybdenum silicide (MoSi) compound [0035].
In addition to the basis above, the examiner cites Nam et al. KR 20130051879 to establish that the rapid thermal treatment used in the processing of photomasks rendered obvious by the combination of Shin et al. KR 20210147391, in view of Fukushima et al. JP 61-221361 and Inazuki et al. 20180224737 includes cooling, such as the rapid colling device disclosed at [0034] of Nam et al. KR 20130051879 and that either rapid cooling was used or it would have been obvious to do so based upon the teachings of Nam et al. KR 20130051879.
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 March 18, 2026