Detailed Correspondence
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 .
Continued Examination Under 37 CFR 1.114
A request for continued examination under 37 CFR 1.114, including the fee set forth in 37 CFR 1.17(e), was filed in this application after final rejection. Since this application is eligible for continued examination under 37 CFR 1.114, and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114. Applicant's submission filed on 05/04/2026 has been entered.
Response to Amendment
Applicants’ amendment of the claim, filed on 04/24/2026, in response to the rejection of claims 1-2, 5-6, 9-16, and 18 from the final office action (03/25/2026), by amending claims 1, 15, and 19 is entered and will be addressed below.
Election/Restrictions
Claims 3-4, 7-8, and 19-20 remain withdrawn from further consideration pursuant to 37 CFR 1.142(b), as being drawn to a nonelected Invention Group II and Species A1-A3 and B1-B3, there being no allowable generic or linking claim.
Claim Interpretations
The limitation “a back electrode on the convex curved back face, the back electrode comprising a back electrode edge (225) connected to a back electrode center (220) via one or more electrode bridges (227)“ of claim 1, these 225, 220, 227 are three portions of the back electrode. A back electrode that contains these three portions is considered read into the claim.
The ”a quartz crystal microbalance (QCM) comprising a coating that selectively reacts with radicals of a target gas and does not react to stable molecules of the target gas to measure an amount of the radicals of the target gas … a controller, connected to the sensor device and to the plasma source, configured to adjust one or more parameters of the plasma source responsive to the amount of radicals of the target gas measured by the sensor device“ of claim 15, the QCM measured the resonant frequency that correlates to an amount of the radicals (Abstract and throughout Applicants’ Specification), amongst other factors (for example, coating thickness). The QCM does not measure the amount of radicals directly, nor does the controller has a way to distill the amount of radicals from the QCM signal. Therefore, a controller that connect the sensor and the plasma source is considered “… to adjust one or more parameters of the plasma source responsive to the amount of radicals of the target gas measured by the sensor device”.
The followings are considered an intended use of the apparatus
“a material that reacts with the radicals of the target gas to form a gaseous byproduct and reduce a thickness of the coating” of claim 2,
“wherein the target gas comprises fluorine“ of claim 5,
“a material that absorbs the radicals of the target gas to increase a mass of the coating” of claim 9,
“wherein responsive to application of a second gas to the sensor device the radicals of the target gas desorb from the material” of claim 10,
“wherein the target gas is a constituent of a gas flow comprising a plurality of gases, and wherein the coating does not react to radicals of any gases of the plurality of gases other than the radicals of the target gas” of claim 11,
the target gas (or its mixture) is not part of the apparatus. The material that is capable of reaction with fluorine is considered read into the claim.
It has been held that claim language that simply specifies an intended use or field of use for the invention generally will not limit the scope of a claim (Walter, 618 F.2d at 769, 205 USPQ at 409; MPEP 2106). Additionally, in apparatus claims, intended use must result in a structural difference between the claimed invention and the prior art in order to patentably distinguish the claimed invention from the prior art. If the prior art structure is capable of performing the intended use, then it meets the claim (In re Casey, 152 USPQ 235 (CCPA 1967); In re Otto, 136 USPQ 458, 459 (CCPA 1963); MPEP2111.02). When the structure recited in the reference is substantially identical to that of the claims, claimed properties or functions are presumed to be inherent (In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433 (CCPA 1977); MPEP 2112.01).
Claim Rejections - 35 USC § 103
The text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
Claims 1-2, 5-6, and 9-13 are rejected under 35 U.S.C. 103 as being unpatentable over Fujii (US 20160146761, hereafter ‘761), in view of Lee et al. (US 20060144335, hereafter ‘335). (Gillchriest, US 3717697, hereafter ‘697, is evidenced that tungsten oxide reacted with fluorine).
‘761 teaches some limitations of:
Claim 1: Devices, films, and methods for the detection of target molecules are provided. The devices, films and methods can include sensitive films and a vibration detecting unit (abstract, includes the claimed “A sensor device comprising”):
the convex vibration detecting unit can be a quartz crystal microbalance (QCM) ([0028], includes the claimed “a quartz crystal microbalance (QCM)”);
A sensitive film including equal parts tungsten oxide and zinc oxide is deposited onto a single quartz substrate having 25 vibration-detecting portions using a sputtering system ([0125]), the target can be a gas component. In some embodiments, the target can include at least one of ammonia ([0051], includes the clamed “and a coating on at least a portion of a surface of the QCM, wherein the coating selectively reacts with radicals of a target gas but does not react with stable molecules of the target gas”, QCM intrinsically monitor resonant frequency, “wherein the QCM is configured such that a resonant frequency of the QCM changes in response to reaction of the radicals of the target gas to the coating, and wherein the change in the resonant frequency of the QCM correlates to an amount of the radicals of the target gas that has reacted with the coating”, see Applicants’ submitted NPL 09/13/2023 for discussion of resonance frequency. See evidence ‘697 for “the tungsten oxide may be reacted with gaseous fluorine to form tungsten hexafluoride, which is a gas at ambient temperatures”, col. 4, lines 28-30. Note also the target gas is not part of the apparatus, see claim interpretation above),
FIG. 1A depicts some embodiments of a vibration detecting unit 110 having a convex shape. The support 210 of the vibration detecting unit can be made of a variety of materials ([0026]), the support for the convex vibration detecting unit can include AT-cut quartz crystal ([0029], includes the claimed “wherein the QCM comprises: a quartz crystal having a front face and a convex back face“, therefore, the bottom concave surface of the support 210 in Fig. 1B is the front face by this definition and the top convex surface is the back face);
FIG. 1B depicts some embodiments of an array 250 of vibration detecting units 110 that include an inverse mesa shape. One or more electrodes 260, 270, and 280 can be associated with the support of the vibration detecting units 110 ([0031], the electrode 280 at the top/front of the quartz substrate 210 reads into the claimed “a front electrode on the front face“; and the electrode 270 includes three portions, center, edge and bridging electrode, the electrode 270 reads into the claimed “a back electrode on the convex back face, the back electrode comprising a back electrode edge connected to a back electrode center via one or more electrode bridges“).
‘761 does not teach the other limitations of:
Claim 1: (a quartz crystal having a front face and a convex) curved (back face);
(a back electrode on the convex) curved (back face).
‘335 is analogous art in the field of Devices For Monitoring And Controlling Thin Film Processing (title), SC-cut quartz crystal microbalance sensors capable of excitation of at least two different resonant modes (abstract), compared to AT-cut quartz crystal ([0056]). ‘335 teaches that Useful sensors in the present methods include, but are not limited to, crystal sensors such as quartz crystal microbalance sensors, … Sensing surfaces of the present invention include flat surfaces and contoured surfaces, such as, curved, convex and/or concave surfaces. Use of contoured sensing surfaces is useful in applications of the present invention for processing substrates also having contoured surfaces. In these embodiments, it is often desirable to utilize a contoured sensing surface characterized by the same shape, such as radius of curvature, as a contoured substrate surface undergoing processing ([0031]).
Before the effective filing date of the claimed invention, it would have been obvious to a person of ordinary skill in the art to have changed the shape of the vibration detecting unit 110 of ‘761 from convex to curved convex shape, as taught by ‘335, for the purpose of matching contoured substrate surface, as taught by ‘335 ([0031]).
‘761 further teaches the limitations of:
Claims 2 and 5: ‘697 is evidenced for the claimed “wherein the coating comprises a material that reacts with the radicals of the target gas to form a gaseous byproduct and reduce a thickness of the coating” of claim 2 and “wherein the target gas comprises fluorine, and wherein the material comprises silicon dioxide (SiO2), tungsten, or an oxide of tungsten”.
Claim 6: In some embodiments, the film includes TiO2, ZrO2, and/or WO3, and any combination thereof ([0053], 2nd last sentence, includes the claimed “wherein the material comprises tungsten(III) oxide (W2O3)”).
Claim 9: the resonance can be altered by the addition or removal of a mass at or near a surface of the sensitive film ([0056], 2nd sentence), a change in signal for the vibration detecting unit will indicate the presence of the target species that is absorbed by the film above the vibration detecting unit ([0040], 4th last sentence, includes the claimed “wherein the coating comprises a material that absorbs the radicals of the target gas to increase a mass of the coating”).
Claim 10: absorbed gas intrinsically can be desorbed by flow inert gas over the QCM “wherein responsive to application of a second gas to the sensor device the radicals of the target gas desorb from the material”, note gas is not part of the apparatus structure.
Claim 11: for detecting the presence or absence of molecules in the environment ([0002], includes the claimed “wherein the target gas is a constituent of a gas flow comprising a plurality of gases, and wherein the coating does not react to radicals of any gases of the plurality of gases other than the radicals of the target gas”, again, the gas is not part of the apparatus).
Claim 12: the two or more overlapping sensitive films have a maximum thickness of about 1,000,000 nm or less, for example, 1,000,000, 100,000, 10,000, 1,000, 500, 200, 190, 180, 170, 160, 155, 150, 145, 140, 135, 130, 120, 100, 50, 25, 10, 5, or 1 nm ([0075], the three bold-faced specific examples read into the claimed “wherein the coating has a thickness of 1-100 microns”).
Claim 13: The film is deposited in a triangular area (16 mm on each side) including 7 electrode portions on a square quartz substrate with sides of 16 mm (see FIG. 4A for the front of the vibration detection units 401, 402, 403, 404, 405, 407, and 406 and FIG. 4B for the back of the electrodes 425, 424, 423, 422, 421, 427, and 426) ([0132], includes the claimed “wherein the surface of the QCM comprising the coating corresponds to the front electrode of the QCM”).
Alternatively, claim 6 is rejected under 35 U.S.C. 103 as being unpatentable over ‘761 and ‘335, as being applied to claim 5 rejection above, further in view of Saito (US 20210080426, hereafter ‘426).
In case Applicants argue that ‘761 teaches WO3, not W2O3 as required by claim 6.
‘426 is analogous art in the field of sensor (title), including QCM ([0044], last sentence), The sample 8 may be a gas. The gaseous sample is not particularly limited, but it may be, for example, atmospheric air, expiration, some other gas produced from a living body or an object to be analyzed, or the surrounding air of an object to be analyzed. The target material 9 in the gaseous sample is not particularly limited, but it may be, for example, a volatile organic compound (VOC) such as an aromatic substance or a pheromone substance (Fig. 4, [0066]). ‘426 teaches that Usable examples of the blocking agent 11 are a metal oxide (such as W2O3) ([0038], 3rd sentence), for the purpose of detecting a target material at high sensitivity ([0003], last sentence).
Note blocking one chemical is increasing sensitivity to another chemical.
Before the effective filing date of the claimed invention, it would have been obvious to a person of ordinary skill in the art to have replaced WO3 of ‘761 with W2O3 of ‘426, for the purpose of detecting a target material at high sensitivity, as taught by ‘426 ([0003], last sentence).
Alternatively, claim 10 is rejected under 35 U.S.C. 103 as being unpatentable over ‘761 and ‘335, as being applied to claim 9 rejection above, further in view of Smith et al. (US 6189367, hereafter ‘367).
In case Applicants argue that application of a second gas is not an intended use and part of the apparatus structure of claim 10.
‘367 is analogous art in the field of quartz crystal microbalances (abstract). ‘367 teaches that After the aliquot of methanol had flushed through the sample chamber and was replaced by pure flowing nitrogen gas, the methanol adsorbed on the quartz crystal microbalance desorbed, and the heat flow sensor exhibited a corresponding slow endothermic signal while the quartz crystal microbalance signal returned to its value before the introduction of methanol (col. 16, line 65 to col. 17, line 4).
Before the effective filing date of the claimed invention, it would have been obvious to a person of ordinary skill in the art to have added nitrogen gas desorption step to QCM, as taught by ‘367, to the QCM of ‘761, for the purpose of returned the QCM to original state, as taught by ‘367 (col. 17, lines 3-4).
Claim 14 is rejected under 35 U.S.C. 103 as being unpatentable over ‘761 and ‘335, as being applied to claim 1 rejection above, further in view of HUBICKA et al. (CZ 25867, hereafter ‘867).
‘761 does not teach the limitations of:
Claim 14: further comprising: a charged grid over the coating, wherein the charged grid repels ions of the target gas such that only neutral radicals of the target gas reach the coating.
‘867 is analogous art in the field of System For Measuring Flows Of Neutral And Ionized Deposition Particles Impinging Onto A Substrate During Growth Of Thin Layers (title). ‘867 teaches that Many different plasma sources are currently known and have been developed which are used for thin film deposition … to check the parameters of the deposition process, there has been a requirement to measure the flow of ionized and neutral deposition particles separately from other interacting particles with the substrate that are not incorporated into the layer material. To this end, a combination of a quartz crystal microbalance (QCM) system equipped with a charged particle grille system (Grid Energy Analyzer) was first developed by … (bridging paragraph between pages 1-2), In front of the input aperture of the QCM detector there are several grids with defined electrical voltage against the reference potential of the whole system, such as the reactor frame etc. The negative potential grating serves for electron repulsion and the grating with a suitable positive potential value. they cannot hit the mostly grounded measuring crystal collection electrode. Thus, the QCM detector only measures the value of the neutral flux of the deposition particles to the collecting electrode. When the same electrical potential as the collecting electrode potential of the measuring crystal is applied to the ion braking grid, both the positively charged deposit particles and the neutral deposit particles fall on the crystal (1st complete paragraph of P2).
Before the effective filing date of the claimed invention, it would have been obvious to a person of ordinary skill in the art to have added grids with defined electrical voltage with defined electrical voltage to measure neutral flux or in combination with positive ions, as taught by ‘867, to the QCM of ‘761, for the purpose of separating neutral particle from ions, as taught by ‘867 (P1).
Claims 15-16 and 18 are rejected under 35 U.S.C. 103 as being unpatentable over Smith et al. (US 20180182634, hereafter ‘634), in view of ‘761 and ‘335.
‘634 teaches some limitations of:
Claim 15: ATOMIC LAYER ETCHING METHODS AND APPARATUS (title, includes the claimed “A manufacturing system, comprising”):
The showerhead 282 dispenses process gases into the wafer cavity. There can be multiple gas inlets (e.g. dual plenum). The showerhead may have RF capability (e.g. dual frequency) from an RF source 284 (Fig. 2E, [0082], includes the claimed “a plasma source to generate a plasma”);
a small volume chamber 272 within a larger chamber 270 … an RF source 284 …By way of example without limitation, cleaning can be accomplished using a remote plasma source or in situ (Fig. 2E, [0080]-[0083], includes the claimed “a process chamber connected to the plasma source via one or more delivery lines”);
to characterize an ALE process, a quartz crystal microbalance can be used to measure weight in situ. This enables determination of weight loss of a thin film as a function of dose ([0151]), Examples of sensors that may be monitored during processing include, but are not limited to, .. Appropriately programmed feedback and control algorithms may be used with data from these sensors to maintain desired process conditions ([0200]), The power supply 304 is controlled by a control module 310, e.g., a controller (Fig. 3, [0087], 5th sentence, includes the claimed “and a sensor device connected to at least one of the plasma source, the process chamber or the one or more delivery lines, wherein the sensor device comprises a quartz crystal microbalance (QCM)”),
FIG. 20 shows a control module 2000 for controlling the systems described above … The control module 2000 may be employed to control devices in the system based in part on sensed values. For example only, the control module 2000 may control one or more of valves 2002, filter heaters 2004, pumps 2006, and other devices 2008 based on the sensed values and other control parameters. The control module 2000 receives the sensed values from, for example only, pressure manometers 2010, flow meters 2012, temperature sensors 2014, and/or other sensors 2016, The control module 2000 may also be employed to control process conditions during reactant delivery and plasma processing ([0193]), ALE systems include integrated metrology system for providing closed-loop monitoring of etch performance. The integrated metrology can be used, e.g., for determining whether the surface film has been etched to the desired thickness ([0184], includes the claimed “and a controller, connected to the sensor device and to the plasma source, configured to adjust one or more parameters of the plasma source responsive to the amount of radicals of the target gas measured by the sensor device“, metrology clearly is used to end the plasma ALE process when desired thickness is reached. See also claim interpretation above).
‘634 also teaches plasma sources of F (e.g. HF—NF3 plasma) (plasma can be generated in situ or remotely), and other F sources (e.g. ClF3, SF6) ([0125], last sentence).
‘634 does not teach the other limitations of:
Claim 15: (a quartz crystal microbalance) comprising a coating that selectively reacts with radicals of a target gas and does not react to stable molecules of the target gas to measure an amount of the radicals of the target gas;
wherein the QCM further comprises:
a quartz crystal having a front face and a convex curved back face;
a front electrode on the front face; and
a back electrode on the convex curved back face, the back electrode comprising a back electrode edge connected to a back electrode center via one or more electrode bridges.
‘761 is analogous art in the field of Devices, films, and methods for the detection of target molecules are provided. The devices, films and methods can include sensitive films and a vibration detecting unit (abstract), the convex vibration detecting unit can be a quartz crystal microbalance (QCM) ([0028]). ‘761 teaches that A sensitive film including equal parts tungsten oxide and zinc oxide is deposited onto a single quartz substrate having 25 vibration-detecting portions using a sputtering system ([0125]), In some embodiments, the film includes TiO2, ZrO2, and/or WO3, and any combination thereof ([0053], 2nd last sentence, i.e., tungsten oxide without zinc oxide), the target can be a gas component. In some embodiments, the target can include at least one of ammonia ([0051]), for the purpose of high-accuracy and high-reliability detection ([0122], last sentence). As evidenced by ‘697, tungsten oxide is reactive to fluorine.
‘335 is analogous art as discussed above.
Before the effective filing date of the claimed invention, it would have been obvious to a person of ordinary skill in the art to have adopted QCM with a sensitive film tungsten oxide, as taught by ‘761, as the QCM of ‘634; furthermore, to have changed the shape of the vibration detecting unit 110 of ‘761 from convex to curved convex shape, as taught by ‘335, for the purpose of high-accuracy and high-reliability detection, as taught by ‘761 ([0122], last sentence), particularly for the F sources of ‘634 and for the purpose of matching contoured substrate surface, as taught by ‘335 ([0031]).
‘761 further teaches the limitations of:
Claim 16: the resonance can be altered by the addition or removal of a mass at or near a surface of the sensitive film ([0056], 2nd sentence), the target can be a gas component. In some embodiments, the target can include at least one of ammonia ([0051], includes the claimed “wherein the QCM is configured such that a resonant frequency of the QCM changes in response to reaction of the radicals of the target gas to the coating, and wherein the change in the resonant frequency of the QCM correlates to an amount of the radicals of the target gas that have reacted with the coating”).
‘634 further teaches the limitations of:
Claim 18: to characterize an ALE process, a quartz crystal microbalance can be used to measure weight in situ. This enables determination of weight loss of a thin film as a function of dose ([0151]), Examples of sensors that may be monitored during processing include, but are not limited to, .. Appropriately programmed feedback and control algorithms may be used with data from these sensors to maintain desired process conditions ([0200]), The power supply 304 is controlled by a control module 310, e.g., a controller (Fig. 3, [0087], 5th sentence, includes the claimed “wherein the controller is to increase a plasma power responsive to a determination that the amount of radicals of the target gas is below a target threshold” of claim 18 because of the feedback control).
Response to Arguments
Applicant's arguments filed 04/24/2026 have been fully considered but they are not convincing in light of the new grounds of rejection above.
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure. WO 8903016 is cited for a convex curved back face of QCM (Fig. 1, see also middle of P2).
US 20160084783 is cited for QCM sensing OH radical ([0008]).
US 20140076716 is cited for QCM grids with adjustable voltage (Fig. 28A). KR 101261188 is cited for feedback controller 370 connected to QCM 110 and power 400 (Fig. 1).
Any inquiry concerning this communication or earlier communications from the examiner should be directed to KEATH T CHEN whose telephone number is (571)270-1870. The examiner can normally be reached 8:30am-5:00 pm.
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/KEATH T CHEN/Primary Examiner, Art Unit 1716
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