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 .
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 1,3,6-8,13-14,17 are rejected under 35 U.S.C. 102(a)(1) or 102(a)(2) as anticipated by or, in the alternative, under 35 U.S.C. 103 as obvious over Lee et al. 20230408904
Lee et al. 20230408904 teaches the coating of carbon nanotubes with silicon nitride using atomic layer deposition (ALD) to form a protective coating. This coating can be 50 or 80 cycles thick and the At% of silicon can be 11-14% and the nitrogen 12-15 At% in 50 cycles and the silicon can be 18-21 At% and the nitrogen 20-23 at% in 80 cycles. Oxidation cannot be avoided in some cases. [0054-0080]. The attachment of the protected pellicle to an EUV photomask via a frame is illustrated in figure 12. Figure 13A illustrates forming a semiconductor device which is further described in the associated text [0015].
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The position of the examiner is that the embodiment disclosed at [0080] where 80 cycles of SiN is coated on the CNTs initially has an Si/N ratio of ~ 13.9/12.5 (1.112) and near the surface is more nitrogen rich having a ratio of 24.1/19.3 (1.248), which anticipates the claimed invention. The layers include some oxygen. The concentration gradually changes through the thickness to include an intermediate (sub) layer which meets the interdiffusion layer limitation.
If the anticipation rejection is not upheld, the examiner holds that it would have bene obvious to form the SiN layer to a thickness of 80- cycles where the SiN layer has a Si/N ratio of ~ 13.9/12.5 (1.112) and the Si/N ration near the surface of the layer is more nitrogen rich having a ratio of 24.1/19.3 (1.248) based upon the discussion at [0080]. The layers include some oxygen. The concentration gradually changes through the thickness to include an intermediate (sub) layer which meets the interdiffusion layer limitation.
Claims 1,3,6-8,12-14,17-18 and 20 are rejected under 35 U.S.C. 103 as being unpatentable over Lee et al. 20230408904.
Lee et al. 20230408904 does not exemplify the use of the CNT pellicle with 80 cycles of SiN in an exposure process.
It would have been obvious to use the pellicle with 80 cycles of SiN together with an EUV photomask as illustrated in figure 12 to expose a photoresist in the process described in figure 13A and [0015] with a reasonable expectation of forming a useful photoresist pattern.
Claims 1,3,6-14, 16-18 and 20 are rejected under 35 U.S.C. 103 as being unpatentable over Hsu et al. 20240094626
Hsu et al. 20240094626 teaches a first coating (130) over a carbon nanotube which is a silicide of Zr, Ti, Mn, Fe, Ru, Ni, Pd, Co, Mo, Nb, Ir or Rh and can be a nitrided silicide MSiN of Zr, Ti, Mn, Fe, Ru, Ni, Pd, Co, Mo, Nb, Ir or Rh. This is followed by a second coating (140) which prevents oxidation and can be AlN, TiN or SiC [0054-0059]. The formation of a silicon or silicon nitride layer, followed by a metal or metal nitride layer and the annealing of these is to form a graded layer disclosed [0060].
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Figure 13B illustrates the CNTs membrane with a ZrSiN coating. Figure 19A illustrates a carbon fiber with nanoparticles (150), a first coating layer (130) and a second coating (140) [0084]
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The formation of a third cover layer is disclosed. In some embodiments, a third cover layer 540 includes at least one layer of an oxide, such as HfO.sub.2, Al.sub.2O.sub.3, ZrO.sub.2, Y.sub.2O.sub.3, or La.sub.2O.sub.3. In some embodiments, the third cover layer 540 includes at least one layer of non-oxide compounds, such as B.sub.4C, YN, Si.sub.3N.sub.4, BN, NbN, RuNb, YF.sub.3, TiN, or ZrN. In some embodiments, the third cover layer 540 includes at least one metal layer made of, for example, Ru, Nb, Y, Sc, Ni, Mo, W, Pt, or Bi [0100]. The patterning of a semiconductor devices is disclosed with respect to figure 23A
Hsu et al. 20240094626 does not exemplify a composition including a nitrided silicide of Zr, Ti or Mo, overcoated with a nitride of Ti, the annealed composite or the use of either of these in forming semiconductor devices.
With respect to claims 1,3 and 9-10, it would have been obvious to one skilled in the art to modify the teachings at [0053-0059] by forming a ZrSiN, TiSiN or MoSiN layer as the first coating layer, followed by a TiN second layer with a reasonable expectation of forming a pellicle protected against hydrogen plasma damage.
With respect to claims 1,3 and 9-10, it would have been obvious to one skilled in the art to modify the teachings by forming nanoparticles on the surface of MoC, MoN, Ru or RuO2 as taught at [0084] followed by forming a ZrSiN, TiSiN or MoSiN layer as the first coating layer, followed by a TiN second layer as taught at [0053-0059] with a reasonable expectation of forming a pellicle protected against hydrogen plasma damage.
Alternatively with respect to claims 1,3,6-10,13,14 and 16-,17, it would have been obvious to one skilled in the art to modify the teachings at [0053-0060] by forming a ZrSiN, TiSiN or MoSiN layer as the first coating layer, followed by a TiN second layer and annealing these to form a graded layer with a reasonable expectation of forming a pellicle protected against hydrogen plasma damage.
Further with respect to claims 11-12, it would have been obvious to coat the resulting (ZrSiN, TiSiN or MoSiN)/ TiN bilayer with a third cover layer of HfO.sub.2, Al.sub.2O.sub.3, ZrO.sub.2, Y.sub.2O.sub.3, or La.sub.2O.sub., B.sub.4C, YN, Si.sub.3N.sub.4, BN, NbN, RuNb, YF.sub.3, TiN, or ZrN as taught at [0100] with a reasonable expectation of forming a pellicle protected against hydrogen plasma damage.
Further with respect to claims 17 and 19, it would have been obvious to attach the resulting pellicles to an EUV masks as taught at [0011] and using the composite in an EUV exposure process as disclosed in figures 23A-E [0027,0102] with a reasonable expectation of forming s useful patterned resist.
Claims 1-3,6-8 and 13-20 are rejected under 35 U.S.C. 103 as being unpatentable over
Lee et al. 20240036459 illustrates in figure 4C a carbon nanotube membrane which is formed and mounted to a frame (15) [0049]. The formation of a seed layer on the carbon nanotubes , followed by cover layers is taught with respect to figures 11, 12A, 13A,14A,15A. In some embodiments, the seed layer includes one or more of C, Al, B, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Jr, Pt, Au, or Rf, and compounds thereof. The compounds include oxides, nitrides, silicides or carbides. These can then be coated with cover layers [0068-0075]. the cover layer includes at least one layer made of a composition selected from the group consisting of C, Al.sub.2O.sub.3, AN, Al, B, BN, B.sub.4C, B.sub.2O.sub.3, B.sub.6Si, SiN, Si.sub.3N.sub.4, SiN.sub.2, SiC, SiZr, SiC, SiCN, NbSiN, Nb.sub.2O.sub.5, NbTiN, NbSe.sub.3, NbC, Nb.sub.5Si.sub.3, ZrN, ZrO.sub.2, ZrYO, ZrF.sub.4, ZrB.sub.2, ZnSe.sub.2, YN, Y.sub.2O.sub.3, YF.sub.3, Mo.sub.2N, Mo.sub.5Si.sub.3, Mo.sub.3Si, MoSiB, MoSi, MoC.sub.2, Mo.sub.2B.sub.4, MoC, Mo.sub.2C, MoSe.sub.2, MoS.sub.2, MoN, MoP, TiN, TiCN, TiS.sub.2, HfO.sub.2, HfN, HfF.sub.4, VN, WS.sub.2, WSe.sub.2, RuO.sub.2, RuIrO, Ru.sub.2Ni.sub.2, RuCu, RuPt, RuIr, RuP, ZrO.sub.2, IrO.sub.2, CoP, CoSe.sub.2, CoS.sub.2, NiMo, Fe.sub.3C, Fe.sub.2O.sub.3, and FePO. In one or more of the foregoing and following embodiments, the cover layer includes a single layer or multiple layers of a two-dimensional material. In one or more of the foregoing and following embodiments, the cover layer includes a nano-grain structure, a nano-island structure or a nano-particle structure. In one or more of the foregoing and following embodiments, a thickness of the cover layer is in a range from 0.5 nm to 10 nm [0083]. Figure 16 illustrates the CNT with a seed layer (410), a first cover layer (520) and a second cover layer (530) [0074]. FIG. 17A, the target layer is patterned utilizing the patterned photo resist layer as an etching mask, as shown in FIG. 17D. In some embodiments, the patterning the target layer includes applying an etching process to the target layer using the patterned photo resist layer as an etch mask. The portions of the target layer exposed within the openings of the patterned photo resist layer are etched while the remaining portions are protected from etching. Further, the patterned photo resist layer may be removed by wet stripping or plasma ashing, as shown in FIG. 17E [0079]. A pellicle is a thin transparent film stretched over a frame that is glued over one side of a photo mask to protect the photo mask from damage, dust and/or moisture. In extreme ultraviolet (EUV) lithography, a pellicle having a high transparency in the EUV wavelength region, a high mechanical strength and a low or no contamination is generally required. An EUV transmitting membrane is also used in an EUV lithography apparatus instead of a pellicle [0002].
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Lee et al. 20240036459 does not exemplify a pellicle with a nitride coating or its use in an EUV exposure process.
With respect to claims 1-3 and 6, it would have been obvious to one skilled in the art form a pellicle with a Ti, Cr, Zn, Y, Zr, Mo, or Hf seed layer as taught at [0073] and a cover layer of SiN, Si.sub.3N.sub.4, SiN.sub.2, SiC, SiZr, SiCN, NbSiN, NbTiN, Nb.sub.5Si.sub.3, ZrN, YN, Mo.sub.2N, MoN, TiN, TiCN or HfN as taught at [0042] with a reasonable expectation of forming a useful pellicle.
With respect to claims 1,3 and 6-16, it would have been obvious to one skilled in the art form a pellicle with a Al, Ti, Cr, Fe, Co, Zr, Nb, Mo, Ru, W or Pt as the seed layer (serving as hydrogen reduction layer) as taught at [0073] and a first cover layer of SiN (stress control layer), a second cover layer of Si.sub.3N.sub.4, SiN.sub.2, SiC, SiZr, SiCN, NbSiN, NbTiN, Nb.sub.5Si.sub.3, ZrN, YN, Mo.sub.2N, MoN, TiN, TiCN or HfN, (hydrogen permeation barrier layer) and a third cover layer of Y2O3, HfO2, Al2O3 (diffusion inhibitor) as taught at [0042] with a reasonable expectation of forming a useful pellicle.
With respect to claims 1-3,6-8 and 13-16, it would have been obvious to one skilled in the art form a pellicle with a Ti, Cr, Zn, Y, Zr, Mo, or Hf seed layer as taught at [0073] and a first cover layer of SiN, and a second cover layer of Si.sub.3N.sub.4, SiN.sub.2, SiC, SiZr, SiCN, NbSiN, NbTiN, Nb.sub.5Si.sub.3, ZrN, YN, Mo.sub.2N, MoN, TiN, TiCN or HfN as taught at [0042] with a reasonable expectation of forming a useful pellicle.
Further with respect to claims 17-20 , it would have been obvious to attach the resulting pellicles to an EUV photomask as taught at [0083] and use the composite to expose a resist as taught at [0077-0078].
Claims 1-3,9-10 and 17-20 are rejected under 35 U.S.C. 103 as being unpatentable over Timmermans et al. 20210191255
Timmermans et al. 20210191255 teaches with respect to figure 6b, MWCNTs which are coated with Zr and then coated with ZrO2 using 22 cycles of atonic layer deposition (ALD) [0078]. The pre-coating of a seed material allows functionalization of the surface without causing significant structural damage to the carbon nanotubes (CNTs [0014]. The CNT membrane may be a free-standing CNT membrane. The CNTs may be single-walled (SWCNT) or multi-walled (MWCNT). The term MWCNT as used herein is intended to encompass also double-walled CNTs (DWCNTs) [0015]. The sed material layer can be continuous or discontinuous and may have a thickness of 0.5 to 4 nm [0017]. An outer coating can be deposited upon the seed layer to provide reliable protection from damage by the hydrogen plasma environment [0018]. The seed material may be selected from the group of: C, Zr, ZrN, Hf, HfN, B, B.sub.4C, BN, Y, YN, La, LaN, SiC, SiN, Ti, TiN, W, Be, Au, Ru, Al, Mo, MoN, Sr, Nb, Sc, Ca, Ni, Ni—P, Ni—B, Cu, Ag. [0020,0062]. These materials may provide a seeding function for a broad class of materials which may be deposited by ALD and which may form an outer coating with sufficient reliability and EUV transmission [0020]. The coating material may be selected from the group of Zr, Al, B, C, Hf, La, Nb, Mo, Ru, Si, Ti or Y; or carbides, nitrides or oxides thereof [0021,0067]. The attachment of the pellicle membrane (10) to a frame (12) adding protective layers (14a, 14b) and attaching this to a photomask (22) is illustrated in figure 1
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A considerable major challenge remaining for realizing a CNT-based pellicle however is to make it withstand the hydrogen plasma environment of the EUV scanner during a large number of exposures, e.g. on the order of tens of thousands or more [0003].
Timmermans et al. 20210191255 does not exemplify a pellicle with a nitride coating or its use in an EUV exposure process.
With respect to claims 1-3 and 9, it would have been obvious to modify the embodiment where the CNT pellicle is coated with a Zr seed layer and a ZrO2 coating layer, by replacing the ZrO2 layer with a ZrN or ZrON coating layer based upon the teaches that the coating material may be selected from the group of Zr, Al, B, C, Hf, La, Nb, Mo, Ru, Si, Ti or Y; or carbides, nitrides or oxides thereof at [0021,0067], so the layer in contact with the CNT has a higher Zr, Ti, Hf, Y or Mo content and the top portion of the layer has a higher nitride content (lower Zr, Ti, Y, Hf or Mo content). This is considered a graded layer near the surface with a higher Zr, Ti, Y, Hf or Mo content at the CNT surface.
With respect to claims 1-3 and 9-10, it would have been obvious to form an embodiment where the CNT pellicle is coated with a Zr, Hf, Y, Ti or Mo seed layer as taught at [0020], followed by a ZrN, HfN, YN, TiN, MoN, ZrON, HfON, YON, TiON, or MoON coating layer based upon the teaches that the coating material may be selected from the group of Zr, Al, B, C, Hf, La, Nb, Mo, Ru, Si, Ti or Y; or carbides, nitrides or oxides thereof at [0021,0067], so the layer in contact with the CNT has a higher Zr, Ti, Hf, Y or Mo content and the top portion of the layer has a higher nitride content (lower Zr, Ti, Y, Hf or Mo content). This is considered a graded layer near the surface with a higher Zr, Ti, Y, Hf or Mo content at the CNT surface.
With respect to claims 1,3 and 9-10, it would have been obvious to form an embodiment where the CNT pellicle is coated with a SiN seed layer as taught at [0020], followed by a SiON coating layer based upon the teaches that the coating material may be selected from the group of Zr, Al, B, C, Hf, La, Nb, Mo, Ru, Si, Ti or Y; or carbides, nitrides or oxides thereof at [0021,0067], so the layer in contact with the CNT has a higher Zr, Ti, Hf, Y or Mo content and the top portion of the layer has a higher nitride content (lower Zr, Ti, Y, Hf or Mo content). This is considered a graded layer near the surface with a higher Zr, Ti, Y, Hf or Mo content at the CNT surface. Stoichiometric SiN has the formula Si3N4 (~43% Si) and SiON will have a lower silicon content as stoichiometric SiO is SiO2 (~33% silicon) .
Further with respect to claims 17-20 , it would have been obvious to attach the resulting pellicles to an EUV photomask and use the composite to expose a resist
Claims 1-10 and 13-20 are rejected under 35 U.S.C. 103 as being unpatentable over Lee et al. 20230408904, in view of Yeon et al. WO 2022010214, Timmermans et al. 20210191255 and Lee et al. 20240036459.
Yeon et al. WO 2022010214 (machine translation attached) describes the use of ALD to form a TiN coating by introducing TiCl4 vapor for 1 second, purging with argon for 2 seconds, introducing ammonia as a nitrogen source for 3 seconds and then purging with argon for 3 seconds, the (undisclosed) substrate is then heated to 460 degrees C. This was repeated 200 times to form a TiN film [135-137]. Example 5 is similar but forms a SiN film on the substrate by supplying Si2Cl6 for 1 second, purging with argon for 2 seconds, introducing ammonia for 3 seconds, treating with plasma and purging with argon for 3 seconds [142-145]. Example 7 was Application/Control Number: 17/843,723 Art Unit: 1737 Page 4 similar to example 1, but the substrate was changed to a carbon nanotube (CNT) pellicle [149 151]. Example 10 forms a SiO2 coating on the CNT pellicle using 1,1,3,3-tetramethyldisiloxane and ozone as the reactant gasses/vapors and is demonstrated to have increased resistance to hydrogen plasma [152-154,219,224] as shown in figure 10 for Application/Control Number: 17/843,723 Art Unit: 1737 [5. In addition, the mask of the present invention preferably includes a mask and a pellicle covering the mask surface, wherein the pellicle is made of CNT, fullerene, or a mixture thereof, and the surface of the pellicle is coated with a protective thin film, characterized in that , in this case, there is an advantage of greatly improving the lifespan of a mask employing the same by preventing corrosion or deterioration without reducing the transmittance of the pellicle [122]. The silicon nitride film precursor is, for example, SiH .sub.4, SiCl .sub.4, SiF .sub.4 SiCl .sub.2 H .sub.2, Si .sub.2 Cl .sub.6, TEOS, DIPAS, BTBAS, (NH .sub.2 )Si(NHMe) .sub.3, (NH .sub.2 )Si(NHEt) .sub.3 (NH .sub.2 )Si(NH .sup.n Pr) .sub.3, (NH .sub.2 )Si(NH .sup.i Pr) .sub.3, (NH .sub.2 )Si(NH .sup.n Bu) .sub.3, (NH .sub.2 )Si(NH .sup.i Bu) .sub.3, (NH .sub.2 )Si(NH .sup.t Bu) .sub.3, (NMe .sub.2 )Si(NHMe) .sub.3, , (NMe .sub.2 )Si(NHEt) .sub.3, (NMe .sub.2 )Si(NH .sup.n Pr) .sub.3, (NMe .sub.2 )Si( NH .sup.i Pr) .sub.3, (NMe .sub.2 )Si(NH .sup.n Bu) .sub.3, (NMe .sub.2 )Si(NH .sup.i Bu) .sub.3, (NMe .sub.2 )Si(NH .sup.t Bu) .sub.3 (NEt .sub.2 )Si(NHMe) .sub.3, (NEt .sub.2 )Si(NHEt) .sub.3, (NEt .sub.2 )Si(NH .sup.n Pr) .sub.3, (NEt .sub.2 )Si(NH .sup.i Pr) .sub.3 (NEt .sub.2 )Si(NH .sup.n Bu) .sub.3, (NEt .sub.2 )Si(NH .sup.i Bu) .sub.3, (NEt .sub.2 )Si(NH .sup.t Bu) .sub.3, (N .sup.n Pr .sub.2 )Si(NHMe) .sub.3, (N .sup.n Pr .sub.2 )Si(NHEt) .sub.3, (N .sup.n Pr .sub.2 )Si(NH .sup.n Pr) .sub.3, (N Application/Control Number: 17/843,723 Art Unit: 1737 Page 6 .sup.n Pr .sub.2 )Si(NH .sup.i Pr) .sub.3, (N .sup.n Pr .sub.2 )Si(NH .sup.n Bu) .sub.3, (N .sup.n Pr .sub.2 )Si(NH .sup.i Bu) .sub.3, (N .sup.n Pr .sub.2 )Si(NH .sup.t Bu) .sub.3, (N .sup.i Pr .sub.2 )Si(NHMe) .sub.3, (N .sup.i Pr .sub.2 )Si(NHEt) .sub.3, (N .sup.i Pr .sub.2 )Si(NH .sup.n Pr) .sub.3, (N .sup.i Pr .sub.2 )Si(NH .sup.i Pr) .sub.3, (N .sup.i Pr .sub.2 )Si(NH .sup.n Bu) .sub.3, (N .sup.i Pr .sub.2 )Si(NH .sup.i Bu) .sub.3, (N .sup.i Pr 2) .sub.2 )Si(NH .sup.t Bu) .sub.3, (N .sup.n Bu .sub.2 )Si(NHMc) .sub.3, (N .sup.n Bu .sub.2 )Si(NHEt) .sub.3, (N .sup.n Bu .sub.2 )Si(NH .sup.n Pr) .sub.3, (N .sup.n Bu .sub.2 )Si(NH .sup.i Pr) .sub.3, (N .sup.n Bu .sub.2 )Si(NH .sup.n Bu) .sub.3, (N .sup.n Bu .sub.2 )Si(NH .sup.i Bu) .sub.3, (N .sup.n Bu .sub.2 )Si(NH .sup.t Bu) .sub.3, (N .sup.i Bu .sub.2 )Si(NHMe) .sub.3, (N .sup.i Bu .sub.2 )Si(NHEt) .sub.3, (N .sup.i Bu .sub.2 )Si(NH .sup.n Pr) .sub.3, (N .sup.i Bu .sub.2 )Si(NH .sup.i Pr) .sub.3, (N .sup.i Bu .sub.2 )Si(NH .sup.n Bu) .sub.3, (N .sup.i Bu .sub.2 )Si(NH .sup.i Bu) .sub.3, (N .sup.i Bu .sub.2 )Si(NH .sup.t Bu) .sub.3, (N .sup.t Bu .sub.2 )Si(NHMe) .sub.3, (N .sup.t Bu .sub.2 )Si(NHEt) .sub.3, (N .sup.t Bu .sub.2 )Si(NH .sup.n Pr) .sub.3, (N .sup.t Bu .sub.2 )Si (NH .sup.i Pr) .sub.3, (N .sup.t Bu .sub.2 )Si(NH .sup.n Bu) .sub.3, (N .sup.t Bu .sub.2 )Si(NH .sup.i Bu) .sub.3, (N .sup.t Bu .sub.2 )Si(NH .sup.t Bu) .sub.3, (NH .sub.2) .sub.2 Si(NHMe) .sub.2, (NH .sub.2) .sub.2 Si(NHEt) .sub.2, (NH .sub.2) .sub.2 Si(NH .sup.n Pr) .sub.2, (NH .sub.2) .sub.2 Si(NH .sup.i Pr) .sub.2, (NH .sub.2) ) .sub.2 Si(NH .sup.n Bu) .sub.2, (NH .sub.2) .sub.2 Si(NH .sup.i Bu) .sub.2, (NH .sub.2) .sub.2 Si(NH .sup.t Bu) .sub.2 , (NMe .sub.2) .sub.2 Si(NHMe) .sub.2, (NMe .sub.2) .sub.2 Si(NHEt) .sub.2, (NMe .sub.2) .sub.2 Si(NH .sup.n Pr) .sub.2, (NMe .sub.2) .sub.2 Si(NH .sup.i Pr) .sub.2, (NMe .sub.2) .sub.2 Si(NH .sup.n Bu) .sub.2, (NMe .sub.2) ) .sub.2 Si(NH .sup.i Bu) .sub.2, (NMe .sub.2) .sub.2 Si(NH .sup.t Bu) .sub.2, (NEt .sub.2) .sub.2 Si(NHMe) .sub.2, (NEt .sub.2) .sub.2 Si(NHEt) .sub.2, (NEt .sub.2) .sub.2 Si(NH .sup.n Pr) .sub.2, (NEt .sub.2) .sub.2 Si(NH .sup.i Application/Control Number: 17/843,723 Art Unit: 1737 Page 7 Pr) .sub.2, (NEt .sub.2) .sub.2 Si(NH .sup.n Bu) .sub.2, (NEt .sub.2) .sub.2 Si(NH .sup.i Bu) .sub.2, (NEt .sub.2) .sub.2 Si(NH .sup.t Bu) .sub.2, (N .sup.n Pr .sub.2) .sub.2 Si(NHMe) .sub.2, (N .sup.n Pr .sub.2) .sub.2 Si(NHEt) .sub.2, (N .sup.n Pr .sub.2) .sub.2 Si(NH .sup.n Pr ) .sub.2, (N .sup.n Pr .sub.2) .sub.2 Si(NH .sup.i Pr) .sub.2, (N .sup.n Pr .sub.2) .sub.2 Si(NH .sup.n Bu) .sub.2, (N .sup.n Pr .sub.2) .sub.2 Si(NH .sup.i Bu) .sub.2, (N .sup.n Pr .sub.2) .sub.2 Si(NH .sup.t Bu) .sub.2, (N .sup.i Pr .sub.2) .sub.2 Si(NHMc) .sub.2, (N .sup.i Pr .sub.2 ) .sub.2 Si(NHEt) .sub.2, , (N .sup.i Pr .sub.2) .sub.2 Si(NH .sup.n Pr) .sub.2, (N .sup.i Pr .sub.2 ) .sub.2 Si(NH .sup.i Pr) .sub.2, (N .sup.i Pr .sub.2) .sub.2 Si(NH .sup.n Bu) .sub.2, (N .sup.i Pr .sub.2) .sub.2 Si(NH .sup.i Bu) .sub.2, (N .sup.i Pr .sub.2) .sub.2 Si(NH .sup.t Bu) .sub.2, , (N .sup.n Bu .sub.2) .sub.2 Si(NHMe) .sub.2, (N .sup.n Bu .sub.2) .sub.2 Si(NHEt) .sub.2, (N .sup.n Bu .sub.2) .sub.2 Si(NH .sup.n Pr) .sub.2, (N .sup.n Bu .sub.2) .sub.2 Si(NH .sup.i Pr) .sub.2, (N .sup.n Bu .sub.2) .sub.2 Si(NH .sup.n Bu) .sub.2, (N .sup.n Bu .sub.2) .sub.2 Si(NH .sup.i Bu) .sub.2, (N .sup.n Bu .sub.2) .sub.2 Si(NH .sup.t Bu) .sub.2, (N .sup.i Bu .sub.2) .sub.2 Si(NHMe) .sub.2, (N .sup.i Bu .sub.2) .sub.2 Si(NHEt) .sub.2, (N .sup.i Bu .sub.2) .sub.2 Si( NH .sup.n Pr) .sub.2, (N .sup.i Bu .sub.2) .sub.2 Si(NH .sup.i Pr) .sub.2, (N .sup.i Bu .sub.2) .sub.2 Si(NH .sup.n Bu) .sub.2, (N .sup.i Bu .sub.2) .sub.2 Si(NH .sup.i Bu) .sub.2, (N .sup.i Bu .sub.2) .sub.2 Si(NH .sup.t Bu) .sub.2, (N .sup.t Bu .sub.2) .sub.2 Si(NHMc) .sub.2, (N .sup.t Bu .sub.2) .sub.2 Si(NHEt) .sub.2, (N .sup.t Bu .sub.2) .sub.2 Si (NH .sup.n Pr) .sub.2 (N .sup.t Bu .sub.2) .sub.2 Si(NH .sup.i Pr) .sub.2, (N .sup.t Bu .sub.2) .sub.2 Si(NH .sup.n Bu) .sub.2, (N .sup.t Bu .sub.2) .sub.2 Si(NH .sup.i Bu) .sub.2, (N .sup.t Bu .sub.2) .sub.2 Si(NH .sup.t Bu) .sub.2, Si(HNCH .sub.2 CH .sub.2 NH) .sub.2, Si(MeNCH .sub.2 CH .sub.2 NMe) .sub.2 ,.sub. Si(EtNCH .sub.2 CH .sub.2 NEt) .sub.2, Si( .sup.n PrNCH .sub.2 CH .sub.2 N .sup.n Pr) .sub.2, Si( .sup.i PrNCH .sub.2 CH .sub.2 N .sup.i Pr) .sub.2, Si( .sup.n Application/Control Number: 17/843,723 Art Unit: 1737 Page 8 BuNCH .sub.2 CH .sub.2 N .sup.n Bu) .sub.2,Si ( .sup.i BuNCH .sub.2 CH .sub.2 N .sup.i Bu) .sub.2, Si( .sup.t BuNCH .sub.2 CH .sub.2 N .sup.t Bu) .sub.2, Si(HNCHCHNH) .sub.2, Si(MeNCHCHNMe) .sub.2, Si(EINCHCHNEI) .sub.2, Si( .sup.n PrNCHCHN .sup.n Pr) .sub.2 Si( .sup.i PrNCHCHN .sup.i Pr) .sub.2 Si( .sup.n BuNCHCHN .sup.n Bu) .sub.2, Si( .sup.i BuNCHCHN .sup.i Bu) .sub.2 Si( .sup.t BuNCHCHN .sup.t Bu) .sub.2, (HNCHCHNH)Si(HNCH.sub.2 CH .sub.2 NH), (McNCHCHNMc)Si(McNCH .sub.2 CH .sub.2 NMe), (EtNCHCHNEt)Si(EtNCH .sub.2 CH .sub.2 NEt), ( .sup.n PrNCHCHN .sup.n Pr)Si( .sup.n PrNCH .sub.2 CH .sub.2 N .sup.n Pr), (.sup.i PrNCHCHN .sup.i Pr)Si( .sup.i PrNCH .sub.2 CH .sub.2 N .sup.i Pr), ( .sup.n BuNCHCHN .sup.n Bu)Si( .sup.n BuNCH .sub.2 CH .sub.2 N .sup.n Bu), (.sup.i BuNCHCHN .sup.i Bu)Si( .sup.i BuNCH .sub.2 CH .sub.2 N .sup.i Bu), ( .sup.t BuNCHCHN .sup.t Bu)Si( .sup.t BuNCH .sub.2 CH .sub.2 N .sup.t Bu), (NH .sup.t Bu) .sub.2 Si(HNCH .sub.2 CH .sub.2 NH), (NH .sup.t Bu) .sub.2 Si(MeNCH .sub.2 CH .sub.2 NMe), (NH .sup.t Bu) .sub.2 Si(EtNCH .sub.2 CH .sub.2 NEt), (NH .sup.t Bu) .sub.2 Si( .sup.n PrNCH .sub.2 CH .sub.2 N .sup.n Pr), (NH .sup.t Bu) .sub.2 Si( .sup.i PrNCH .sub.2 CH .sub.2 N .sup.i Pr), (NH .sup.t Bu) .sub.2 Si( .sup.n BuNCH .sub.2 CH .sub.2 N .sup.n Bu), (NH .sup.t Bu) .sub.2 Si( .sup.i BuNCH .sub.2 CH .sub.2 N .sup.i Bu), (NH .sup.t Bu) .sub.2 Si( .sup.t BuNCH .sub.2 CH .sub.2 N .sup.t Bu), (NH .sup.t Bu) .sub.2 Si(HNCHCHNH), (NH .sup.t Bu) .sub.2 Si(MeNCHCHNMe) .sub., (NH .sup.t Bu) .sub.2 Si(EtNCHCHNEt), (NH .sup.t Bu) .sub.2 Si( .sup.n PrNCHCHN .sup.n Pr), (NH .sup.t Bu) .sub.2 Si( .sup.i PrNCHCHN .sup.i Pr), (NH .sup.t Bu) .sub.2 Si( .sup.n BuNCHCHN .sup.n Bu), (NH .sup.t Bu) .sub.2 Si( .sup.i BuNCHCHN .sup.i Bu), (NH .sup.t Bu) .sub.2 Si( .sup.t BuNCHCHN .sup.t Bu), ( .sup.i PrNCH .sub.2 CH .sub.2 N .sup.i Pr)Si(NHMe) .sub.2, ( .sup.i PrNCH .sub.2 CH .sub.2 N .sup.i Pr)Si(NHEt) .sub.2, ( .sup.i PrNCH .sub.2 CH .sub.2 N .sup.i Pr)Si(NH .sup.n Pr) .sub.2 ( Application/Control Number: 17/843,723 Art Unit: 1737 Page 9 .sup.i PrNCH .sub.2 CH .sub.2 N .sup.i Pr)Si(NH .sup.i Pr) .sub.2, ( .sup.i PrNCH .sub.2 CH .sub.2 N .sup.i Pr)Si(NH .sup.n Bu) .sub.2, ( .sup.i PrNCH .sub.2 CH .sub.2 N .sup.i Pr)Si(NH .sup.i Bu) .sub.2 (.sup.i PrNCH .sub.2 CH .sub.2 N .sup.i Pr)Si(NH .sup.t Bu) .sub.2 (.sup.i PrNCHCHN .sup.i Pr)Si(NHMe) .sub.2 (.sup.i PrNCHCHN .sup.i Pr)Si(NHEt) .sub.2 (.sup.i PrNCHCHN .sup.i Pr)Si (NH .sup.n Pr) .sub.2 ((.sup.i PrNCHCHN .sup.i Pr)Si(NH .sup.i Pr) .sub.2, (.sup.i PrNCHCHN .sup.i Pr)Si(NH .sup.n Bu) .sub.2, ( .sup.i PrNCHCHN .sup.i Pr)Si(NH .sup.i Bu) .sub.2 and ( .sup.i PrNCHCHN .sup.i Pr)Si(NH .sup.t Bu) .sub.2 It may be at least one selected from the group consisting of, but is not limited thereto. Wherein n Pr means n propyl, .sup.i Pr means iso-propyl, .sup.n Bu means n-butyl, .sup.i Bu means iso-butyl, .sup.t Bu means tert-butyl [70-71]. In addition, photolithography is used when patterning a wafer or a substrate for liquid crystal on a semiconductor device or a liquid crystal display panel or the like. In the photolithography, a mask is used as the original plate of patterning, and the pattern on the mask is transferred to a wafer or a substrate for liquid crystal. This is damaged, and eventually the yield and performance of semiconductor devices, liquid crystal panels, and the like are lowered. Accordingly, a method of coating a pellicle on the mask surface has been proposed to prevent impurities from adhering to the mask surface. Therefore, there is an urgent need to develop a pellicle that can greatly improve the lifespan of a mask without corrosion or deterioration without reducing transmittance [8-9]. The EUV transmittance of 13.5 nm wavelength of the pellicle (membrane) prepared in Examples 7,9 to 10 and Comparative Example 6 was measured using a transmittance analyzer, and the results are shown in Table 7 below [218]. Application/Control Number: 17/843,723 Art Unit: 1737 Page 10 Preferably, the reducing agent may be ammonia gas (NHn) or hydrogen gas (Hn ), the nitriding agent may be nitrogen gas (Nn), and the oxidizing agent may be HnO, H2O2 On, On or N2O [114]. At this time, as a transport gas or diluent gas for moving the inhibitor for forming the pellicle protective thin film and the pellicle protective thin film precursor compound on the pellicle, one or a mixture of two or more selected from .sub.argon (Ar), nitrogen (Nn), and helium (Hc) A gas may be used, but is not limited thereto. In the present description, as the purge gas, an inert gas may be used as an example, and preferably, the transport gas or the diluent gas may be used [110-111]
Lee et al. 20230408904 does not exemplify embodiments where the initial layer is silicon and multiple cover layers are formed.
With respect to claims 1-4,6-8 and 13-16, it would have been obvious to one skilled in the art to modify the embodiments of Lee et al. 20230408904 by coating the silicon first in forming the silicon nitride as is known in the art in example 5 of Yeon et al. WO 2022010214 and varying the composition of the silicon nitride layer based upon the teachings of Lee et al. 20230408904 at [0080], Lee et al. 20240036459 disclosing SiN, Si.sub.3N.sub.4, SiN.sub.2 at [0083] and the disclosure of SiN as the seed layer and cover layer in Timmermans et al. 20210191255 at [0020-0021,0062,0067] with a reasonable expectation of forming a pellicle resistant to hydrogen plasma damage.
With respect to claims 1-3,5-8 and 13-16, it would have been obvious to one skilled in the art to modify the embodiments of Lee et al. 20230408904 by coating the silicon first in forming the silicon oxynitride in a manner similar to examples 5 and 10 of Yeon et al. WO 2022010214 and varying the composition of the silicon oxynitride layer based upon the teachings of Lee et al. 20240036459 disclosing SiN, Si.sub.3N.sub.4, SiN.sub.2 at [0083] and the disclosure of SiN as the seed layer and silicon oxides and carbides as the cover layer in Timmermans et al. 20210191255 at [0020-0021,0062,0067] with a reasonable expectation of forming a pellicle resistant to hydrogen plasma damage.
With respect to claims 1-4,6-8 and 13-16, it would have been obvious to one skilled in the art to modify the embodiments of Lee et al. 20230408904 by coating seed layer of Zr, Hf, Y, Ti or Mo seed layer as taught at [0020] of Timmermans et al. 20210191255 and then coating the silicon first in forming the silicon nitride as is known in the art in example 5 of Yeon et al. WO 2022010214 and varying the composition of the silicon nitride layer based upon the teachings of Lee et al. 20230408904 at [0080], Lee et al. 20240036459 disclosing SiN, Si.sub.3N.sub.4, SiN.sub.2 at [0083] and the disclosure of SiN as the seed layer and cover layer in Timmermans et al. 20210191255 at [0020-0021,0062,0067] with a reasonable expectation of forming a pellicle resistant to hydrogen plasma damage.
With respect to claims 1-3,5-8 and 13-16, it would have been obvious to one skilled in the art to modify the embodiments of Lee et al. 20230408904 by coating seed layer of Zr, Hf, Y, Ti or Mo seed layer as taught at [0020] of Timmermans et al. 20210191255 and then coating the silicon first in forming the silicon oxynitride in a manner similar to examples 5 and 10 of Yeon et al. WO 2022010214 and varying the composition of the silicon oxynitride layer based upon the teachings of Lee et al. 20240036459 disclosing SiN, Si.sub.3N.sub.4, SiN.sub.2 at [0083] and the disclosure of SiN as the seed layer and silicon oxides and carbides as the cover layer in Timmermans et al. 20210191255 at [0020-0021,0062,0067] with a reasonable expectation of forming a pellicle resistant to hydrogen plasma damage.
With respect to claims 1-4,6-10 and 13-16, it would have been obvious to one skilled in the art to modify the embodiments of Lee et al. 20230408904 by coating seed layer of Zr, Ti, W, Ru, Al, Mo, Nb (hydrogen reduction) .seed layer as taught at [0020] of Timmermans et al. 20210191255 and then coating the silicon first in forming the silicon nitride as is known in the art in example 5 of Yeon et al. WO 2022010214 and varying the composition of the silicon nitride layer based upon the teachings of Lee et al. 20230408904 at [0080], Lee et al. 20240036459 disclosing SiN, Si.sub.3N.sub.4, SiN.sub.2 at [0083] and the disclosure of SiN as the seed layer and cover layer in Timmermans et al. 20210191255 at [0020-0021,0062,0067] with a reasonable expectation of forming a pellicle resistant to hydrogen plasma damage.
With respect to claims 1-3,5-10 and 13-16, it would have been obvious to one skilled in the art to modify the embodiments of Lee et al. 20230408904 by coating seed layer of Zr, Ti, W, Ru, Al, Mo, Nb.(hydrogen reduction seed layer as taught at [0020] of Timmermans et al. 20210191255 and then coating the silicon first in forming the silicon oxynitride in a manner similar to examples 5 and 10 of Yeon et al. WO 2022010214 and varying the composition of the silicon oxynitride layer based upon the teachings of Lee et al. 20240036459 disclosing SiN, Si.sub.3N.sub.4, SiN.sub.2 at [0083] and the disclosure of SiN as the seed layer and silicon oxides and carbides as the cover layer in Timmermans et al. 20210191255 at [0020-0021,0062,0067] with a reasonable expectation of forming a pellicle resistant to hydrogen plasma damage.
With respect to claims 1-4,6-10 and 13-16, it would have been obvious to one skilled in the art to modify the embodiments of Lee et al. 20230408904 by coating seed layer of Zr, Ti, W, Ru, Al, Mo, Nb (hydrogen reduction) .seed layer as taught at [0020] of Timmermans et al. 20210191255 and then coating the silicon first in forming the silicon nitride as is known in the art in example 5 of Yeon et al. WO 2022010214 and varying the composition of the silicon nitride layer based upon the teachings of Lee et al. 20230408904 at [0080], Lee et al. 20240036459 disclosing SiN, Si.sub.3N.sub.4, SiN.sub.2 at [0083] and the disclosure of SiN as the seed layer and cover layer in Timmermans et al. 20210191255 at [0020-0021,0062,0067] with a reasonable expectation of forming a pellicle resistant to hydrogen plasma damage.
With respect to claims 1-3,5-10 and 13-16, it would have been obvious to one skilled in the art to modify the embodiments of Lee et al. 20230408904 by coating seed layer of Zr, Ti, W, Ru, Al, Mo, Nb.(hydrogen reduction seed layer as taught at [0020] of Timmermans et al. 20210191255 and then coating the silicon first in forming the silicon oxynitride in a manner similar to examples 5 and 10 of Yeon et al. WO 2022010214 and varying the composition of the silicon oxynitride layer based upon the teachings of Lee et al. 20240036459 disclosing SiN, Si.sub.3N.sub.4, SiN.sub.2 at [0083] and the disclosure of SiN as the seed layer and silicon oxides and carbides as the cover layer in Timmermans et al. 20210191255 at [0020-0021,0062,0067] with a reasonable expectation of forming a pellicle resistant to hydrogen plasma damage.
Further with respect to claims 17-20 , it would have been obvious to attach the resulting pellicles to an EUV photomask and use the composite to expose a resist
Claims 1-20 are rejected under 35 U.S.C. 103 as being unpatentable over Lee et al. 20230408904, in view of Yeon et al. WO 2022010214, Timmermans et al. 20210191255 and Lee et al. 20240036459, further in view of Hsu et al. 20240094626.
In addition to the basis above, it would have been obvious to one skilled in the art to modify the pellicles rendered obvious by the combination of over Lee et al. 20230408904,Yeon et al. WO 2022010214, Timmermans et al. 20210191255 and Lee et al. 20240036459 and processes of using them by forming an outer coating of Y2O3, HfO2, Al2O3 (diffusion inhibitor) as taught at [0042] of Hsu et al. 20240094626 with a reasonable expectation of forming a useful pellicle.
Claims 1,3,6-8,13-14,17,18 and 20 provisionally rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1,4,5,8-18,20-25 of copending Application No. 18/133945 (20240094626)). Although the claims at issue are not identical, they are not patentably distinct from each other.
Application 18/133945 claims:
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220
635
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134
645
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137
638
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635
655
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138
639
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330
656
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295
646
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The position of the examiner is that the pellicle with the CNTs coated with transition metal silicide of Mo, Ti, Zr as recited in claim 4 and nitrided as recited in claim 5 and then a TiN coating (claim 1) meet the claims. The position of the examiner is that the pellicle with the CNTs coated with transition metal silicide of Mo, Ti, Zr as recited in claim 12 and nitrided as recited in claim 12 and then a TiN coating (claim 14) meet the claims. The same is true for the embodiments of claim 18 render the process of use obvious.
This is a provisional nonstatutory double patenting rejection because the patentably indistinct claims have not in fact been patented.
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure.
Tsai et al. 20250237941 teaches pellicle with multiple capping layers. The core can be CNT, ZrSiON, Nb, Si nanowire or other silicides [0038].
Hsu et al. 20250216770 has similar teachings but uses oxide capping layers.
Lin et al. 20220413378 teaches CNTs with various coatings.
Hsu et al. 20240345471 teaches CNTs which are functionalized, coated with MoO2 particles, followed by Ru nano-particles, annealed , overcoated with SiN and densified (see figure 12A-F and associated text)
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, Ching-Yu (Coris) Fung can be reached at 571-270-5713. 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 August 21, 2026
Prosecution Insights