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 .
DETAILED ACTION
Status of the Claims
Claims 1, 2, 7, 9-12, 18-20, and 24-28 are pending and rejected. Claims 22-23 are withdrawn. Claims 1, 7, and 25 are amended. Claims 3-6, 8, 13-17, and 21 are cancelled. Claim 28 is newly added.
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and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114.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 6/12/2025 has been entered.
Claim Rejections - 35 USC § 103
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 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.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claims 1, 2, 7, 9, 10, 12, 18-20, 24, and 28 are rejected under 35 U.S.C. 103 as being unpatentable over Singh, WO 2018/109459 A1 in view of Storey, US 2014/0141221 A1 (provided on the IDS of 7/7/2021), Edelstein, US 2008/0233366 A1, Rogers, US 2002/0032073 A1, and Hall, “Variations in graded organosilicone microwave PECVD coatings modify stress and improve the durability on plastic substrates”, 2014.
Regarding claims 1, 7, 9, 24, and 28, Singh teaches a plasma polymerization method for coating a substrate with a polymer layer (a plasma deposited protective coating, pg. 1, where layers of the coating include polymeric organosilicon layers and polymeric hydrocarbon layers, pg. 2-3, pg. 6, pg. 12, and pg. 30-31), which method comprises:
providing a substrate to be coated within a plasma chamber (where the substrate is placed in the chamber of a reactor that generates plasma so as to provide a plasma chamber, pg. 5 and pg. 31, Example 4a);
introducing a flow of a first polymer precursor to the plasma chamber (injecting one or more precursor compounds such as HMDSO into the chamber, pg. 5 and pg. 31-32, Examples 4a and 4e);
applying a power at a level greater than zero Watts (W) and converting the first polymer precursor to a first polymer precursor plasma (igniting plasma with a power density of 0.057 W/cm2, pg. 5 and pg. 31, Example 4a, indicating that a power greater than 0 W is applied to ignite plasma so as to form plasma from the first polymer precursor);
exposing the substrate to the first polymer precursor plasma (where the substrate is in the chamber with the plasma so that the precursor compounds are decomposed in the plasma to form active species that are deposited onto and form a layer on the exposed surface of the substrate, pg. 5 and pg. 31, Example 4a);
introducing a flow of a second polymer precursor to the plasma chamber (where intermediate sublayer [ii] is formed by introducing a flow of a precursor having a formula X such as 1,4-dimethylbenzene to the PECVD deposition chamber, pg. 21-22 and pg. 32, Examples 4d and 4e);
applying a power at a level greater than zero Watts (W) and converting the second polymer precursor to a second polymer precursor plasma (plasma is ignited with a power density of 0.057 W/cm2 to provide a CmHn layer, pg. 32, Examples 4d and 4e); and
exposing the substrate to the second polymer precursor plasma (where the substrate is in the chamber so that the film is deposited on the surface, indicating that it is exposed to the second polymer precursor plasma, pg. 5 and pg. 32, Examples 4d and 4e),
wherein exposing the substrate to the first polymer precursor plasma forms a first polymer layer thereon and exposing the substrate to the second polymer precursor plasma forms a second polymer layer thereon (where the exposure to the first polymer precursor provides a first layer of SiOxCyHz and the exposure to the second polymer precursor provides a second layer of CmHn, pg. 31-32, Examples 4a, 4d, and 4e).
Singh teaches that forming the layer of CmHn from hydrocarbons having the formula X (pg. 12). They teach that suitable compounds include 1,4-dimethylbenzene as well as 1,4-divinyl benzene, 1,3-divinyl benzene, and 1,2-divinyl benzene (pg. 13), i.e., compounds meeting the requirements of claimed formula VIII, where R30-R35 are hydrogen and the position of the side groups it ortho, meta, or para, as required by claims 1 and 28. They teach that the precursor mixture containing a hydrocarbon compound of formula (X) optionally further comprises reactive gases such as C3H6 (pg. 13).
They teach that the substrate comprises the moisture-barrier layer, a mechanical protective layer which is inorganic, and a gradient layer interposing the moisture-barrier layer and the mechanical protective layer (pg. 15).
Singh does not teach pre-treating the surface.
Storey teaches method for the deposition of polymer coatings on substrates, where the coating comprises an electrically insulating layer and/or a hydrophobic layer (abstract). They teach forming a first and second polymer layer on the substrate (0004). They teach forming the coatings by PECVD (0024). They teach cleaning the substrate prior to coating to remove contaminants (0044). They teach plasma cleaning the substrate using oxygen, ozone, argon, nitrogen, or helium (0045). After cleaning, the polymer coating is deposited on the substrate by PECVD (0046). They provide an example of cleaning under oxygen at a pressure of about 50 mTorr with a plasma power density of 7.5 W/L (0059). They teach a pulsing cycle comprising a pressurization phase, a soak phase, and an evacuation phase, where the number of pulse cycles can be selected based on the desired thickness (0053). They teach that plasma may be maintained through each pulse cycle and between cycles, which is more efficient rather than letting it extinguish and re-ignite in the subsequent pulse (0057).
From the teachings of Storey, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have modified the process of Singh to have performed a plasma cleaning step prior to film deposition because Storey teaches that such a step is desirable for removing contaminants from a surface before depositing a polymer coating. Therefore, in the process of Singh in view of Storey, a pre-treatment precursor (oxygen, ozone, argon, nitrogen, or helium) will be introduced into the chamber, a power level greater than 0 W will be applied to generate the cleaning plasma, and the substrate will be exposed to the pre-treatment precursor plasma for removing contaminants from the surface.
They do not teach maintaining the power at a level greater than zero between the treatment steps.
Edelstein teaches a method for forming a structure that includes a substrate having an oxide layer having essentially no carbon, a graded transition layer on the oxide layer, the graded transition layer having essentially no carbon at the interface with the oxide layer and gradually increasing carbon towards a porous SiCOH layer, and a porous SiCOH layer on the graded transition layer, the porous pSiCOH layer having a homogeneous composition throughout the layer (abstract). They teach placing the substrate into a reactor chamber of a PECVD reactor (0062 and Fig. 8). They teach subjecting the surface to a pretreatment step in which at least one surface pretreatment gas is flown in the reactor such as argon, helium, etc. (0063). They teach that an RF power source is used to generate a plasma of the surface pretreatment gas (0064). They teach that in the next step a flow of precursor gases for the formation of the carbon depleted layer of oxide are introduced to the reactor, which still contains a plasma of the surface pretreatment gases still present and active in the chamber (0065 and Fig. 8). They teach that the next step is forming the carbon graded transition layer, where the substrate remains in the chamber and step 46 is performed without interruption of the plasma in the reactor (0066 and Fig. 8). They teach that the precursor gases of oxygen and SiCOH are adjusted for the formation of this layer while the porogen precursor gas is introduced into the reactor chamber (0066). They teach that the last step 48 is forming a porous SiCOH layer on the graded transition layer (0067 and Fig. 8). They teach that in transitioning between step 46 and 48, the substrate is maintained in the plasma in the chamber, but the plasma parameters and precursor gases of oxygen, dielectric precursor, and porogen precursor are adjusted to form the porous SiCOH layer (0067). Therefore, Edelstein provides a process of plasma pretreating a substrate surface, depositing a first layer, depositing a transition layer, and depositing a second layer where the plasma is maintained throughout the process.
From the teachings of Edelstein, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have modified the process of Singh in view of Storey to have maintained the plasma between the pretreatment step, the first polymer deposition step, and the second polymer deposition step because Storey teaches that it is more efficient to maintain plasma between cycles or steps in a plasma deposition process and Edelstein teaches that a plasma can be maintained between a plasma treatment step and the deposition a first layer, a transition layer, and a second layer such that by maintaining plasma throughout the process is expected to be more efficient while providing the desired precursors for forming the layers and supplying the required plasma.
Further, since Singh teaches applying the power with a power density of 0.057 W/cm2, where there is no indication that the plasma is pulsed, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have provided a continuous plasma with the expectation of successfully depositing the polymer layers (pg. 31-32). Additionally, Storey teaches using a continuous field to deposit the polymer layer having improved hydrophobicity (0035), indicating that a continuous field is desirable when forming polymer layers.
As to the second polymer precursor, as noted above Singh teaches using C3H6 as a reactive gas that is included with the compound of formula (X) (pg. 13).
Storey teaches forming a hydrophobic polymer layer by PECVD (abstract and 0024). They teach forming the coatings from monomers that provide a surface with a desired degree of surface energy (0026). They teach that the term monomer refers to a molecule group that can combine with others of the same kind to form a polymer, where vinylic monomer groups are generally useful in plasma-based polymerization processes (0032). They teach that the term vinylic refers to the functional group C=C (0032). They teach that vinyl compounds can be represented by the formula R1R2C=CR3R4, where each R individually can be hydrogen, halogen, an organic group, such as a hydrocarbon group or a substituted hydrocarbon group (0046). They teach that the organic groups can comprise linear or branched (saturated or unsaturated) hydrocarbon chains generally with 1-20 carbons atoms, 1-8 carbon atoms, or 2-6 carbon atoms (0046).
From the teachings of Singh and Storey, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have selected propene (CH2=CH-CH3) as the reactive gas included in the gas mixture with compound X because Singh teaches using C3H6 as a reactive gas and Storey teaches that desirable monomers for polymerization by plasma in forming a polymer film have a vinyl group with a formula R1R2C=CR3R4, where each R individually can be hydrogen or an organic group, such as a hydrocarbon group with 1-20 carbons atoms (such that propene with a C3H6 formula would meet the formula of Storey) such that it will be expected to provide a reactive gas having the formula taught by Singh and the vinyl groups that Storey teaches are desirable during plasma polymerization in forming a polymer film. Therefore, in the process of Singh in view of Storey and Edelstein, the second polymer precursor will comprise a compound having the general formula VIII and the general formula IX, where R36, R37, and R38 are hydrogen and R39 is a C1 alkyl group as required by claims 1 and 24.
Therefore, the first and second precursors are different as required by claim 9, i.e., the first compound is an organosilicon compound such as HMDSO and the second has a formula meeting the claimed requirements.
Singh further teaches that the first layer of SiOxCyHz is deposited with a pressure of 0.140 mbar (0.105 Torr), the layer of CmHn is deposited with a pressure of 0.048 mbar (0.036 Torr) (pg. 31-32, Examples 4a, 4d, and 4e). Therefore, the pressure in the plasma chamber is set to a first polymer precursor operating pressure for converting the first polymer precursor to the first polymer precursor plasma and then set to a second polymer precursor operating pressure for converting the second polymer precursor to the second polymer precursor plasma.
Singh teaches that the boundary between each sub-layer may be discrete or graded (pg. 17). They teach that a graded boundary between two layers can be achieved by switching gradually over time during the plasma deposition process from the precursor mixture required to form the first of the two sub-layers to the precursor mixture required to form the second of the two sub-layers (pg. 17). They teach that a discrete boundary between two sub-layers can be achieved by switching immediately during the plasma deposition process from the precursor mixture required to form the first of the two sub-layers to the precursor mixture required to form the second of the two sub-layers (pg. 17).
Edelstein teaches ramping down a dielectric precursor while ramping up the oxygen concentration to provide a structure with a carbon graded transition layer formed during the transition time (0058 and Fig. 4).
From the teachings of Singh and Edelstein, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have reduced the flow of the first polymer precursor to the plasma chamber while increasing the flow of the second polymer precursor to the plasma chamber because Singh teaches that it is desirable to form the sub-layers to have graded boundaries between the sub-layers by gradually changing the precursor composition and Edelstein teaches reducing a first precursor while increasing a second provides a graded transition layer such that it will be expected to provide the graded boundary as desired.
They do not teach changing the pressure from the first polymer precursor operating pressure to the second polymer precursor operating pressure without reducing the pressure to base pressure.
Rogers teaches forming a composite diamond-like carbon coating consisting of at least a first layer of Si-DLC comprising C, H, Si, and possibly O and N (abstract). They teach that an additional coating containing layer of Si-DLC containing C, H, Si, and possibly O and N and a coating containing layers of DLC containing C, H, and possibly N may be applied over top of the first Si-DLC layer (abstract). They teach that the deposition process parameters such as precursor gas composition, plasma power, pressure, and substrate bias voltage are adjusted to produce coatings with different elemental composition and refractive indexes, which change the properties of the coating (abstract). They teach that the substrate is first cleaned to remove contaminants and then activated by sputter-etching (0061). They teach depositing the first layer of Si-DLC by CCP RF plasma deposition from carbon and silicon-containing precursor gas compounds, where after the first Si-DLC layer is deposited an additional coating consisting of at least one layer of DLC or Si-DLC may be deposited by CCP RF plasma deposition (0061). They teach that the additional layer of DLC or Si-DLC is deposited immediately after completion of the first coating layer, in the same vacuum chamber and in the same vacuum cycle because it eliminates the added cost of additional pumpdown cycles, and improves the quality of the interface between the first coating layer and the second coating (0080). They provide an example where the chamber is first evacuated to less than 1x10-3 Torr, and then argon is introduced to increase the pressure to 22x10-3 Torr (0085). They teach initiating plasma by applying RF power, where the power is increased to 6360 W until a -625 V substrate bias was achieved (0085). They teach sputter-etching in argon plasma and then adding tetramethylsilane to the argon gas flow, increasing the pressure to 28x10-3 Torr, increasing the power to 400 W to maintain the -625 V bias to deposit the first layer of Si-DLC (0085). After the thickness of the Si-DLC layer was 0.5 microns, cyclohexane was introduced, and the argon and tetramethylsilane flows were shut off, to initiate deposition f DLC (0085). They teach decreasing the pressure to 27x10-3 Torr and adjusting the power to 390 W to maintain the -625 V bias to deposit the DLC layer (0085). After deposition of the DLC layer, RF power and the cyclohexane flows were turned off (0085). Therefore, Rogers teaches depositing a coating by plasma deposition where the pressure, power, and gas compositions are changed without pumping down to a base pressure and without extinguishing the plasma, where they teach that performing the coating process in the same vacuum cycle eliminates that added cost of additional pumpdown cycles and improves the quality of the interface between the coatings.
Hall teaches PECVD with tetramethyldisiloxane and oxygen to deposit transparent organosilicone coatings (abstract). They teach varying the oxygen flow rate during deposition so as to deposit a chemically graded coating (abstract). They teach that grading offers the ability to change the chemical and mechanical properties of a coating from a substrate to the surface (abstract). They teach simultaneously increasing the power and the oxygen flowrate during coating, where the pressure varied between 0.2 mbar and 0.6 mbar (pg. 617, section 2.1 and Fig. 2). They indicate that the pressure increases with increasing gas flow (Fig. 1). Therefore, Hall teaches forming a graded coating by changing the gas flows, pressure, and power during deposition, where pressure is not reduced to base pressure.
From the teachings of Rogers and Hall, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have modified the process of Singh in view of Storey and Edelstein to have changed the pressure from the first polymer precursor operating pressure to the second polymer precursor operating pressure without reducing the pressure to base pressure because Rogers provides a plasma deposition where the pressure, power, and gas compositions are changed without pumping down to a base pressure and without extinguishing the plasma, where they teach that performing the coating process in the same vacuum cycle eliminates that added cost of additional pumpdown cycles and improves the quality of the interface between the coatings and Hall teaches that pressure, power, and gas flows can be changed during forming a graded coating without reducing to base pressure such that it will be expected to provide the desired change in pressure for depositing the coatings while providing the benefits described by Rogers. Further, since Singh teaches changing the precursor mixture during plasma deposition, this suggests that the pressure during deposition is not returned to a base pressure because this would stop deposition.
Further, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have changed the pressure from the first pressure to the second pressure concurrent with introducing the second precursor to the chamber, as required by claim 7, because Rogers teaches changing the pressure and the gas flows during deposition, where there is no indication that the steps are performed separately, Singh teaches that the boundary between films can be graded by gradually changing precursors such that by changing the pressure while concurrently introducing the second precursor, and Hall teaches changing the pressure while changing the gas flows such that it will be expected to provide the desired change in pressure while also providing the graded boundary between the films.
Regarding claim 2, Singh in view of Storey, Edelstein, Rogers, and Hall suggest the process of claim 1. Singh teaches depositing the SiOxCyHz layer and the CmHn layer using a power density of 0.057 W/cm2 (pg. 31-32, Examples 4a, 4d, and 4e). They teach depositing other SiOxCyHz layers with a power density of 0.225, 0.382, 0.573, and 0.637 W/cm2 (pg. 20, Example 3a).
They teach that the hydrogen content of the layer formed with organosilicon compounds can be reduced by increasing the RF power density and decreasing the plasma pressure, where decreased hydrogen content results in a denser and harder coating (pg. 6 and pg. 16). They teach that a skilled person can easily adjust the ratio of reactive gas to organosilicon compounds at any applied power density in order to achieve the desired modification of the resulting layer deposited (pg. 11). They teach that the carbon content in a sublayer formed with the organosilicon compound can be controlled by modifying the RF power (pg. 16).
They teach that a skilled person can easily adjust the ratio of reactive gas to compound of formula X at any applied power density in order to achieve the desired modification of the resulting layer deposited (pg. 13). They teach that the values of m and n in the CmHn layer can be tuned by varying the applied power to generate the plasma, where, by increasing the power, the concentration of aromatic rings can be reduced and the density of the polymer can be increased (pg. 17).
As noted above, Rogers and Hall teach changing the gas mixture, pressures, and powers during deposition without pumping down to base pressure.
From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have optimized the RF power when forming the silicon-containing sublayer and when forming the hydrocarbon polymer layer to be different while changing the pressures and gases without pumping down to base pressure because Singh teaches that the plasma power used to form the layers can be modified to tune the desired properties where they indicate that SiOxCyHz can be formed using varying RF power densities and Rogers and Hall teach that the power, pressure, and gas mixture can be adjusted during plasma deposition such that it will be expected to provide SiOxCyHz and CmHn sublayers with optimized and desirable properties. According to MPEP 2144.05 II A, “[W]here the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation.” In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955).
Regarding claims 10 and 12, Singh in view of Storey, Edelstein, Rogers, and Hall suggest the process of claim 1. Singh further teaches that the first polymer precursor comprises Si, i.e., a metalloid element (pg. 21-22 and pg. 31-32, Examples 4a, 4d, and 4e).
Regarding claim 18, Singh in view of Storey, Edelstein, Rogers, and Hall suggest the process of claim 1. Singh teaches that the first layer of SiOxCyHz is deposited with a pressure of 0.140 mbar (0.105 Torr), the layer of CmHn is deposited with a pressure of 0.048 mbar (0.036 Torr) (pg. 31-32, Examples 4a, 4d, and 4e). Therefore, the pressure in the plasma chamber is set to a first polymer precursor operating pressure for converting the first polymer precursor to the first polymer precursor plasma.
Edelstein teaches subjecting a substrate to a surface plasma pretreatment step by flowing a pretreatment gas into the plasma at a chamber pressure in the range of 0.05 to 20 Torr, more preferably 1 to 10 torr (0063-0064). They teach using gases such as argon, helium, oxygen, etc. (0063).
From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have set the pressure in the chamber to a pre-treatment precursor operating pressure for converting the pre-treatment precursor to the pre-treatment precursor plasma in the range of 0.05 to 20 Torr or 1 to 10 Torr because Edelstein teaches that such as pressure is suitable for forming a plasma for a pretreatment form the gases suggested by Storey (oxygen) such that it will be expected to provide a pressure suitable for forming the plasma.
Therefore, the pressure will be set to the pre-treatment precursor operating pressure for converting the pre-treatment precursor to the pre-treatment precursor plasma and then set to the first polymer precursor operating pressure for converting the first polymer precursor to the first polymer precursor plasma.
Regarding claims 19 and 20, Singh in view of Storey, Edelstein, Rogers, and Hall suggest the process of claim 18, where the pressure of the pretreatment is suggested to be in the range of 0.05 to 20 torr or 1 to 10 torr and the pressure for the first deposition process is about 0.105 Torr or 0.140 mbar. Singh teaches that the boundary between each sub-layer may be discrete or graded (pg. 17). They teach that a graded boundary between two layers can be achieved by switching gradually over time during the plasma deposition process from the precursor mixture required to form the first of the two sub-layers to the precursor mixture required to form the second of the two sub-layers (pg. 17). They teach that a discrete boundary between two sub-layers can be achieved by switching immediately during the plasma deposition process from the precursor mixture required to form the first of the two sub-layers to the precursor mixture required to form the second of the two sub-layers (pg. 17).
As discussed above for claim 1, Rogers teaches performing a plasma treatment and depositing a coating by plasma deposition where the pressure, power, and gas compositions are changed without pumping down to a base pressure and without extinguishing the plasma. Hall teaches changing pressure, gas flows, and power during deposition.
From the teachings of Rogers and Hall, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have modified the process of Singh in view of Storey, Edelstein, Rogers, and Hall to have changed the pressure from the pretreatment precursor operating pressure to the first polymer precursor operating pressure without reducing the pressure to base pressure because Rogers provides a plasma pre-treatment and deposition process where the pressure, power, and gas compositions are changed without pumping down to a base pressure and without extinguishing the plasma, where they teach that performing the coating process in the same vacuum cycle eliminates that added cost of additional pumpdown cycles and Hall indicates that gas flows and pressure can be changed during deposition such that it will be expected to provide the desired change in pressure for pretreatment and deposition while providing the benefits described by Rogers.
Further, for claim 20, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have changed the pressure from the pre-treatment pressure to the first polymer coating pressure concurrent with introducing the first polymer precursor to the chamber because Rogers teaches changing the pressure and the gas flows during plasma processing, where there is no indication that the steps are performed separately and Hall teaches changing pressure and gas flows simultaneously such that by changing the pressure while adding the precursor polymer it will be expected to provide the desired change in pressure while also providing precursor needed for deposition while improving the efficiency of the process by not requiring two separate steps.
Claim 11 is rejected under 35 U.S.C. 103 as being unpatentable over Singh in view of Storey, Edelstein, Rogers, and Hall as applied to claim 1 above, and further in view of Durandeau, US 2009/0202817 A1.
Regarding claim 11, Singh in view of Storey, Edelstein, Rogers, and Hall suggest the process of claim 1. Singh teaches that the coating acts as a moisture barrier (abstract and pg. 2-3). They teach using various organosilicon precursors, including perfluorinated precursors (pg. 10). They teach that the precursor mixture containing an organosilicon compound optionally further comprises reactive gases such as SiF4, NH3, etc., and/or hexafluoropropylene (pg. 10-11).
They do not teach that the first polymer precursor comprises a metal element.
Durandeau teaches a method for synthesizing a hydrophobic coating on a substrate by bringing the substrate into contact with a mixture of an excited gas originating from a device generating an atmospheric pressure plasma and of a gas containing at least one fluoro compound (abstract). They teach that the fluoro compound precursor may be selected from perfluorosilanes, polyether perfluorosilanes, mixtures that include a fluorocarbon and a precursor of silicon or of another metal chosen from the group including Al, Sn, Fe, Co, etc. (0021).
From the teachings of Durandeau, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have used a mixture of a fluorocarbon and a precursor of Al, Sn, Fe, or Co as the first precursor monomer in addition to the organosilicon monomer because Durandeau teaches that such precursors are used to form hydrophobic coatings by plasma deposition and Singh teaches using a mixture of different reactive gases for providing the moisture barrier coating such that it will be expected to provide the desired and predictable result of forming the hydrophobic coating as desired.
Claim 25 is rejected under 35 U.S.C. 103 as being unpatentable over Singh in view of Storey, Edelstein, Rogers, and Hall as applied to claim 1 above, and further in view of Ito, US 2015/0030792 A1.
Regarding claim 25, Singh in view of Storey, Edelstein, and Rogers suggest the process of claim 1. As noted above, Singh teaches using a compound of formula X, where the compound can be toluene (pg. 12-13). Singh also teaches using reactive gases such as C3H6, where the reactive gas can include a mixture of gases (pg. 13).
Storey teaches using vinyl compounds represented by the formula R1R2C=CR3R4, where each R individually can be hydrogen, halogen, an organic group, such as a hydrocarbon group or a substituted hydrocarbon group (0046). They teach that the organic groups can comprise linear or branched (saturated or unsaturated) hydrocarbon chains generally with 1-20 carbons atoms, 1-8 carbon atoms, or 2-6 carbon atoms (0046).
They do not teach using a compound having the general formula X as the second polymer precursor.
Ito teaches a polylactic acid base material that is coated with a hydrocarbon film by plasma CVD (abstract). They teach that the hydrocarbon film has a first layer with a high CH2 content and a second layer with a low CH2 content (abstract). They teach that the hydrocarbon film provides a water-barrier property (0024 and 0027), such that the film is expected to be hydrophobic because it has a water barrier property and is a hydrocarbon film similar to that of Singh. They teach that the hydrocarbon film is vapor-deposited by a continuous plasma CVD using, as the reaction gas, a gas of a hydrocarbon compound such as an aliphatic unsaturated hydrocarbon or an aromatic hydrocarbon (0044 and 0046). They teach that the aliphatic unsaturated hydrocarbon can be alkenes such as ethylene, propylene, butene, and pentene, alkynes such as acetylene and methylacetylene, alkadienes such as butadiene and pentadiene, and cycloalkenes such as cyclopentene and cyclohexene (0047). They teach that the aromatic hydrocarbon can be benzene, toluene, xylene, etc. (0047). Therefore, they teach using acetylene or methylacetylene as a monomer in forming a hydrophobic film in a plasma CVD process as an alternative to propylene and toluene.
From the teachings of Ito, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have modified the process of Singh in view of Storey, Edelstein, Rogers, and Hall to have used acetylene or methylacetylene as a reactive gas in the second precursor mixture as an alternative to or in addition to propylene because Ito teach that such gases are desirable for use as monomers in a PECVD process for forming a hydrocarbon polymer film as alternatives or mixtures with the compounds used by Singh and suggested by Storey such that it will be expected to provide a desirable reactive gas or gas mixture for forming a hydrophobic polymer film. Therefore, the second polymer precursor will comprise a compound having the general formula X, where R40 and R41 are hydrogen for acetylene and R40 is hydrogen and R41 is a C1 alkyl group for methylacetylene.
Claim 26 is rejected under 35 U.S.C. 103 as being unpatentable over Singh in view of Storey, Edelstein, Rogers, and Hall as applied to claim 1 above, and further in view of Zong, EP 3674438 A1.
Regarding claim 26, Singh in view of Storey, Edelstein, Rogers, and Hall suggest the process of claim 1. As noted above, Singh teaches using a compound of formula X, where the compound can be toluene or 1,4-divinyl benzene (p-divinyl benzene) and styrene derivatives (pg. 12-13). Singh also teaches using reactive gases such as C3H6, where the reactive gas can include a mixture of reactive gases and compounds of formula X (pg. 13).
Storey teaches using vinyl compounds represented by the formula R1R2C=CR3R4, where each R individually can be hydrogen, halogen, an organic group, such as a hydrocarbon group or a substituted hydrocarbon group (0046). They teach that the organic groups can comprise linear or branched (saturated or unsaturated) hydrocarbon chains generally with 1-20 carbons atoms, 1-8 carbon atoms, or 2-6 carbon atoms (0046).
They do not teach using a compound having the general formula XI as the second polymer precursor.
Zong teaches a method for preparing a highly insulating nano-protective coating with a modulation structure using plasma polymerization (abstract and 0011). They teach that the coating provides water resistance (abstract). They teach using organic monomers with low dipole moment and high chemical inertness, where the free volume and compactness of the coating are adjusted by a polyfunctional monomer, so that the coating has high insulation and excellent protection (0008). They teach that the low-dipole moment organic coating and organic silicon coating are alternately prepared to form a multi-layer compact structure (0008). They teach using a composition of monomer A that includes at least one low-dipole moment organic monomer and at least on polyfunctional unsaturated hydrocarbon (0010). They teach that the low-dipole moment organic monomer includes paraxylene, benzene, toluene, methylstyrene, etc. (0019). They teach that the polyfunctional unsaturated hydrocarbons include 1,4-pentadiene, etc. (0019).
From the teachings of Zong, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have modified the process of Singh in view of Storey, Edelstein, Rogers, and Hall to have included 1,4-pentadiene with the compound of formula X because Zong teaches that it is desirable to include low-dipole moment monomer similar to those of formula X with a polyfunctional unsaturated hydrocarbon such as 1,4-pentadiene in forming a water resistant film because it will provide both high insulation and excellent protection such that it will be expected to also impart the film of Singh with such properties. Therefore, the second polymer precursor will include a compound having the general formula XI, i.e., 1,4-pentadiene, where R42, R43, R44, R46, R47, and R48 are hydrogen and R45 is a C1 alkyl.
Claim 27 is rejected under 35 U.S.C. 103 as being unpatentable over Singh in view of Storey, Edelstein, Rogers, and Hall as applied to claim 1 above, and further in view of Weikert, US 2008/0225378 A1 and Lang, US 6,709,715.
Regarding claim 27, Singh in view of Storey, Edelstein, Rogers, and Hall suggest the process of claim 1. As noted above, Singh teaches using a compound of formula X, where the compound can be toluene or 1,4-divinyl benzene (p-divinyl benzene) and styrene derivatives (pg. 12-13). Singh also teaches using reactive gases such as C3H6, where the reactive gas can include a mixture of reactive gases and compounds of formula X (pg. 13).
Storey teaches using vinyl compounds represented by the formula R1R2C=CR3R4, where each R individually can be hydrogen, halogen, an organic group, such as a hydrocarbon group or a substituted hydrocarbon group (0046). They teach that the organic groups can comprise linear or branched (saturated or unsaturated) hydrocarbon chains generally with 1-20 carbons atoms, 1-8 carbon atoms, or 2-6 carbon atoms (0046).
They do not teach using a compound having the general formula XII as the second polymer precursor.
Weikert teaches a dielectric coating having a hydrophobic surface formed by PECVD of organosilane, organosiloxane, organosilazane, organometallic, and/or hydrocarbon precursors (abstract). They teach that the hydrocarbon compound is preferably methane, acetylene, ethane, ethylene, styrene, or mixtures thereof (0121). They teach that the term “hydrocarbon compound” means a chemical compound comprising only carbon and hydrogen atoms, where examples include methane, ethane, ethylene, acetylene, benzene, toluene, propane, cyclooctadiene, cyclohexene, styrene, limonene, and the like (0210).
Lang teaches a method for depositing a low dielectric constant film by plasma assisted copolymerization of p-xylylene and a comonomer having carbon-carbon double bonds (abstract). They teach that commercially available comonomers include 1,4-cyclohexadiene, 1,4-cycloheptadiene, 1,5-cyclooctadiene, p-divinylbenzene, etc. (Col. 3, lines 58-67).
From the teachings of Storey, Weikert, and Lang, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have selected hydrocarbon compounds such as 1,4-cyclohexadiene, 1,4-cycloheptadiene, and/or 1,5-cyclooctadiene to be included in the second precursor composition because Singh teaches using p-divinyl benzene and styrene derivatives along with reactive gases, Storey teaches the vinyl compounds are desirable reactive gases in plasma deposition of a polymer, Weikert teaches using cyclooctadiene, benzene, styrene, etc. as monomers in plasma deposition of a hydrophobic film, and Lang teaches that 1,4-cyclohexadiene, 1,4-cycloheptadiene, 1,5-cyclooctadiene are desirable comonomers for plasma deposition which are commercially available such that it will be expected to provide desirable comonomers for forming a hydrophobic film because they are alternatives to the compounds used by Singh, include vinyl groups which is indicated as being desirable by Storey, Weikert indicates that cyclooctadiene is desirable for a hydrophobic film, and Lang teaches that various cyclic dienes are desirable comonomers that have similar structures to cyclooctadiene and similar structures to the formula X as taught by Singh (cyclic compounds having vinyl groups). Therefore, the second precursor will include compounds having the general formula XII.
Response to Arguments
Applicant's arguments filed 6/12/2025 have been fully considered.
In light of the amendments to claims 1 and 25, the previous claim objections are withdrawn.
In response to applicant's argument that the examiner's conclusion of obviousness is based upon improper hindsight reasoning, it must be recognized that any judgment on obviousness is in a sense necessarily a reconstruction based upon hindsight reasoning. But so long as it takes into account only knowledge which was within the level of ordinary skill at the time the claimed invention was made, and does not include knowledge gleaned only from the applicant's disclosure, such a reconstruction is proper. See In re McLaughlin, 443 F.2d 1392, 170 USPQ 209 (CCPA 1971). In the current case, Singh provides the suggestion of depositing a layer of SiOxCyHz followed by a CmHn layer using plasma vapor deposition, where the boundary between the layers is graded, and where the first layer is deposited at a higher pressure than the second layer. Storey provides the suggestion to plasma clean the surface of the substrate prior to deposition so as to remove contaminants. Edelstein teaches that plasma can be maintained during a pretreatment, first deposition, and second deposition step, where Storey teaches that it is more efficient to maintain plasma between cycles or steps in a deposition process. Rogers teaches a plasma deposition process where the pressure, power, and gas compositions are changed without pumping down to a base pressure and without extinguishing the plasma, where they teach that performing the coating process in the same vacuum cycle eliminates the added cost of additional pump down cycles and improves the quality of the interface between the coatings. Hall has also been added to indicate that when forming a graded film, the pressure, power, and gas flows can be changed. Therefore, the prior art provides the suggestion to perform the claimed deposition process while maintaining the plasma and without pumping down to the base pressure so as to provide the benefits of improving efficiency, eliminating the cost of additional pump down cycles, and improving the interface quality. Further, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have not pumped down to the base pressure when providing a graded interface because it will remove the precursor gases needed for forming the interface. Specifically, since Singh teaches forming the graded interface by gradually changing the gas mixture during plasma deposition, this suggests that the changes occur without pumping down because it is done during the deposition step. While Rogers does not teach using the claimed precursors, they teach using hydrocarbon, silane, and organosilane precursors for the Si-DLC layer and hydrocarbon precursors for the DLC layer (abstract and 0044). Therefore, they teach similar precursors to those of Singh and the claimed second precursors (in that they are hydrocarbons), where the benefits described by Rogers would be expected to also be provided in forming the layered films by plasma deposition. Further, Rogers is in the field of plasma deposition so as to be relevant to the claimed process.
In light of the amendments to the claims, the previous rejection over Zong is withdrawn, however, Zong has been combined with Singh in view of Storey, Edelstein, and Rogers for the suggestion of using 1,4-pentadiene as discussed above.
Conclusion
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/CHRISTINA D MCCLURE/ Examiner, Art Unit 1718