Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
The response of the applicant has been read and given careful consideration. Rejection(s) of the previous action not repeated blow are withdrawn. Responses to the arguments of the applicant are presented after the first rejection they are directed to.
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claims 6,7,14 and 15 are rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
The resists are not positive or negative tone, but rather the polarity of the resist image is determined by the developer used. (see Meyers et al. 20160116839, cited below). The examiner suggests modifying claims 6 and 14 to recite that the developing of the metal-oxide photoresist yields a positive tone image and claims 7 and 15 to recited that the developing of the metal-oxide photoresist yields a positive tone image.
This would overcome the 112 rejection and is congruent with the fact that the claims are method claims. The examiner notes that the applicant did not argue this rejection in the response of 6/1/2026.
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 16-19 are rejected under 35 U.S.C. 103 as being unpatentable over Jiang et al. 20200326627.
Jiang et al. 20200326627 in example 1, teaches tin oxide resists, which are coated on a silicon substrate, dried at 100 degrees C for 2 minutes on a hotplate, exposed using EUV, post baked at 160 degrees C for 2 minutes, developed in a solvent to yield a negative tone image and then baked on a hotplate in air for 5 minutes at 150 degrees C [0070-0072]. Example 2-12 are similar. A soft bake, or a post-apply bake (PAB) is typically performed prior to radiation exposure to hydrolyze the hydrolysable bonds in the precursor compositions, and/or further drive off solvent, and promote densification of the coating material. In some embodiments, the PAB can be performed at temperatures from about 25° C. to about 250° C., in additional embodiments from about 50° C. to about 200° C. and in further embodiments from about 80° C. to about 150° C. The post exposure heating can generally be performed for at least about 0.1 minute, in further embodiments from about 0.5 minutes to about 30 minutes and in additional embodiments from about 0.75 minutes to about 10 minutes. A person of ordinary skill in the art will recognize that additional ranges of PEB temperatures and times within the explicit ranges above are contemplated and are within the present disclosure. The coated material generally comprises a polymeric metal oxo-hydroxo network based on the binding oxo-hydroxo ligands to the metals in which the metals also have some alkyl ligands, or a molecular solid comprised of polynuclear metal oxo-hydroxo species with alkyl ligands[0042]. Following exposure to radiation and the formation of a latent image, a subsequent post-exposure bake (PEB) is typically performed. In some embodiments, the PEB can be performed at temperatures from about 45° C. to about 250° C., in additional embodiments from about 50° C. to about 190° C. and in further embodiments from about 60° C. to about 175° C. The post exposure heating can generally be performed for at least about 0.1 minute, in further embodiments from about 0.5 minutes to about 30 minutes and in additional embodiments from about 0.75 minutes to about 10 minutes. A person of ordinary skill in the art will recognize that additional ranges of PEB temperatures and times within the explicit ranges above are contemplated and are within the present disclosure. The PEB can be designed to further consolidate the exposed regions without decomposing the un-exposed regions into a metal oxide [0047]. After completion of the development step including any optional rinses, the coating materials can be heat treated to further condense the material and to further dehydrate, densify, or remove residual developer from the material. This heat treatment can be particularly desirable for embodiments in which the oxide coating material is incorporated into the ultimate device, although it may be desirable to perform the heat treatment for some embodiments in which the coating material is used as a resist and ultimately removed if the stabilization of the coating material is desirable to facilitate further patterning. In particular, the bake of the patterned coating material can be performed under conditions in which the patterned coating material exhibits desired levels of etch selectivity. In some embodiments, the patterned coating material can be heated to a temperature from about 100° C. to about 600° C., in further embodiments from about 175° C. to about 500° C. and in additional embodiments from about 200° C. to about 400° C. The heating can be performed for at least about 1 minute, in other embodiment for about 2 minutes to about 1 hour, in further embodiments from about 2.5 minutes to about 25 minutes. The heating may be performed in air, vacuum, or an inert gas ambient, such as Ar or N.sub.2. A person of ordinary skill in the art will recognize that additional ranges of temperatures and time for the heat treatment within the explicit ranges above are contemplated and are within the present disclosure. Likewise, non-thermal treatments, including blanket UV exposure, or exposure to an oxidizing plasma such as O.sub.2 may also be employed for similar purposes [0059]. After patterning, the patterned material can be used for further processing such as deposition of material into gaps in the patterned material, and/or etching to remove substrate material between gaps in the patterned material. hen, the patterned resist material can be removed following further processing with a suitable etchant composition, such as a dilute base or BCl.sub.3 plasma. The processing is frequently repeated to form stacks of patterned layers to form functional components [0068].
Jiang et al. 20200326627 does exemplify a process where the patterned resist is treated with radical species.
In the processes of the examples, the temperatures and duration of the baking steps after coating (PAB), after exposure (PEB) and after development (drying) are within the temperature and duration ranges recited in claim 19 and as no special conditions are described, the examiner holds that atmospheric conditions (760 torr in the presence of air which includes oxygen (20.9%), nitrogen (78%), argon (0.9%), hydrogen (0.55ppm), ammonia (trace) and helium (5.24 ppm)), and it would have been obvious to modify the process by either exposing the patterned photoresist to an oxygen plasma as described at [0059] and/or removing/stripping the resist after processing the underlying materials/substrate using a BCl.sub.3 plasma as taught at [0068] with a reasonable expectation of forming a useful patterned device/substrate.
In response to the arguments of 6/1/2026, the thermal treatments are at atmospheric pressure and take place after coating, after exposure, but before development and as a drying step to remove the developer/solvent , while the plasma treatments occur after these. While the steps are recited in a specific order, they are open occurring at any point after deposition of the metal-oxide resist.
Claims 16-20 are rejected under 35 U.S.C. 103 as being unpatentable over De Schepper et al. WO 20230239628
De Schepper et al. WO 20230239628 teaches that a organotin photoresist may be wet developed to form either positive or negative tone images, but try development yields a negative tone pattern (page 7/lines 14-26). After deposition, the coating can be heated at 50-200 degrees C,. for 10 seconds to 10 minutes (page 10/line 29-33). After exposure, the resist can be heated at 45-250 degrees C for 0.5 to 30 minutes at pressures of at least 200 Torr and in inert gas, oxygen, air or modified air (11/line 23-page 12/line 31). Development is disclosed at pages 13-18. The plasma descumming of the patterned tin photoresist is disclosed using pressures of 50 mTorr- 1 Torr, processing tines of 0.1 to 10 seconds and inert gasses such as N2, He, Ar, Ne, Kr and/or Xe using an ICP or the like (18/22-19/30)
De Schiepper et al. WO 20230239528 does not exemplify the process including the heating and plasma treatment steps.
It would have been obvious to one skilled in the art to heat the resist after deposition at 50-200 degrees C,. for 10 seconds to 10 minutes (page 10/line 29-33). Exposing the resist using EUV, heating at 45-250 degrees C for 0.5 to 30 minutes at pressures of at least 200 Torr and in inert gas, oxygen, air or modified air (11/line 23-page 12/line 31), developing the resist to form either a positive or negative tone pattern as taught at (page 7/lines 14-26) and plasma descumming of the patterned tin photoresist is disclosed using pressures of 50 mTorr- 1 Torr, processing tines of 10 seconds and inert gasses such as N2, He, Ar, Ne, Kr and/or Xe using an ICP or the like (18/22-19/30) with a reasonable expectation of forming a useful patterned resist.
Claims 16-19 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Wu et al. 20210013034
Wu et al. 20210013034 in example 2 teaches depositing a tin based resist by reacting isopropyl tri(dimethylamino)Tin and water and allowing then to form on a carbon film coated silicon substrate held at 70 degrees C at 2Torr pressure to form a coating 20 nm thick. This is then exposed using EUV, post baked as 180 degrees C for 2 minutes and developed in 2-heptanone, rinsed with water and then used to etch the substrate using a Helium/oxygen plasms [0053-0055]. After deposition, a remote hydrogen plasma may be used the replace the Sn-L bonds with Sn-H which increases the reactivity of the tin resist to EUV [0028]. Plasma processes include transformer coupled plasma (TCP), inductively coupled plasma (ICP) or capacitively coupled plasma (CCP), employing equipment and techniques among those known in the art. For example, a process may be conducted at a pressure of >5 mT (e.g., >15 mT), at a power level of <1000 W (e.g., <500 W). Temperatures may be from 0 to 300° C. (e.g., 30 to 120° C.), at flow rate of 100 to 1000 standard cubic centimeters per minute (sccm), e.g., about 500 sccm, for from 1 to 3000 seconds (e.g., 10-600 seconds) [0043]. To transfer the pattern into the underlying layers, a plasma etch process may be used. For example, for a Sn-based CVD resist film, a H.sub.2 or H.sub.2/CH.sub.4 plasma may be used to remove the unexposed resist material [0047]. In a wet development process, the chemical changes in the exposed areas result in the formation of more cross-linked materials with larger molecular weight and significant decrease in solubility in selective organic solvents. Non-cross-linked regions may be removed by use of suitable organic solvents, such as isopropyl alcohol, n-butyl acetate, or 2-heptanone. An unexpected benefit of the dry deposition of the films is that the films are completely soluble. Without limiting the mechanism, function or utility of present technology, this benefit may be related to the vapor-phase polymerization/condensation that occurs during deposition, possibly forming cyclic oligomers that are readily soluble in select solvents [0039]. With further reference to FIG. 2, the patterning 4 may follow an optional post-deposition baking 3 of the fil [0035].
With respect to claims 16-19, in the processes of the example 2, the temperatures and duration of the baking step after exposure (PEB) is within the temperature and duration ranges recited in claim 19 and as no special conditions are described, the examiner holds that atmospheric conditions (760 torr in the presence of air which includes oxygen (20.9%), nitrogen (78%), argon (0.9%), hydrogen (0.55ppm), ammonia (trace) and helium (5.24 ppm)) and the plasma etching of the underlying carbon film occurs after these the claims are anticipated
In response to the arguments of 6/1/2026, the thermal treatments are at atmospheric pressure and take place after coating, after exposure, but before development and as a drying step to remove the developer/solvent , while the plasma treatments occur after these. While the steps are recited in a specific order, they are open occurring at any point after deposition of the metal-oxide resist.
Claims 1,4-7 and 16-20 are rejected under 35 U.S.C. 103 as being unpatentable over Wu et al. 20210013034
Wu et al. 20210013034 does not exemplify a process where the resist is treated by radicals after deposition and before exposure.
With respect to claims 1,5-7 and 16-20, It would have been obvious to one of ordinary skill in the art to modify the process of example 2 by adding a treatment with a remote hydrogen plasma to replace the Sn-L bonds with Sn-H which increases the reactivity of the tin resist to EUV [0028] with a reasonable expectation of forming a useful patterned substrate and the resist having a higher sensitivity to the EUV exposure. Further, it would have been obvious to use and ICP or remote plasma operating at temperatures of 0 to 300° C, pressures of 2Torr, for 10-3000 seconds based upon the disclosure at [0043,0053-0055] with a reasonable expectation of forming a useful EUV resist and patterned substrate.
The examiner relies upon the response above as no further arguments were advanced.
Claims 1, 4-8 and 13-19 are rejected under 35 U.S.C. 103 as obvious over Yu et al. WO 2021158433
Yu et al. WO 2021158433 includes a disclosure which relates generally to the field of semiconductor processing. In particular aspects, the disclosure is directed to methods and apparatus for processing of EUV photoresists (e.g., EUV-sensitive metal and/or metal oxide-containing resist films) in the context of EUV patterning and EUV patterned film development to form a patterning mask [0002]. The reference describes either or both of the post-application and past-exposure treatments may involve a remote plasma process, together with or instead of thermal processing, to generate radicals to react with the metal-containing photoresist to thereby modify its material properties. With reference to Fig. 2, in some embodiments the remote plasma treatment process occurs after the photoresist 202a is deposited and before it is exposed to EUV radiation. In this case, the treatment may be referred to as a post-application plasma treatment. With reference to Fig. 3, in some embodiments the remote plasma treatment process occurs after the photoresist 302a is deposited and exposed to EUV radiation to form exposed portions 302c and unexposed portions 302b. In this case, the treatment may be referred to as a post exposure plasma treatment [0048]. In various embodiments, the photoresist has been applied to the substrate layer but not yet exposed to patterning radiation. In some such embodiments, the treatment may be a post-application bake (PAB). In these or other embodiments, the treatment may be a post application remote plasma treatment. In various embodiments, the treatment may increase an exposure radiation sensitivity of the photoresist to thereby achieve a lower dose to size while the substrate is exposed to the patterning radiation, and to achieve a lower line edge roughness after the substrate is exposed to the patterning radiation, as compared to a higher dose to size and a higher line edge roughness that would be achieved without the treatment. In these or other embodiments, the treatment may be conducted at a temperature between about 90 to 250°C or 90 to 190°C [0006]. In various embodiments herein, a temperature of the substrate may be ramped while performing the treatment on the photoresist. In these or other embodiments, the pressure during the treatment may be controlled at atmospheric pressure and below. For instance, the pressure during treatment may be controlled between about 0.1-760 Torr, or between about 0.1-10 Torr. In these or other embodiments, the treatment may involve exposing the photoresist to a remote plasma that generates radicals that react with the photoresist to modify one or more material properties of the photoresist. In some such cases, the radicals may be generated from a gas species selected from the group consisting of water, hydrogen (H), oxygen (O2), ozone, hydrogen peroxide, carbon monoxide, carbon dioxide, carbonyl sulfide, sulfur dioxide, chlorine (CI2), ammonia, nitrous oxide, nitric oxide, methane, an alcohol, acetyl acetone, formic acid, oxalyl chloride, pyridine, a carboxylic acid, an amine, and combinations thereof. [0009] In certain embodiments, the treatment may be a thermal treatment performed using a first set of processing conditions and a second set of processing conditions, where the first and second sets of processing conditions vary with respect to at least one of ambient gases or mixtures, temperatures, and/or pressures to thereby modulate material properties of the photoresist and to tune etch selectivity of the photoresist [0009]. According to various aspects of this disclosure, one or more post treatments to metal and/or metal oxide-based photoresists after deposition (e.g., post-application bake (PAB)) and/or exposure (e.g., post-exposure bake (PEB)) are capable of increasing material property differences between exposed and unexposed photoresist (PR) and therefore decreasing dose to size (DtS), improving PR profile, and improving line edge roughness and line width roughness (LER/LWR) after subsequent dry development. Such processing can involve a thermal process with the control of one or more of temperature, gas ambient, and moisture, resulting in improved dry development performance in processing to follow. In some instances, a remote plasma might be used. In the case of post-application processing (e.g., PAB), a thermal process with control of one or more of temperature, gas ambient (e.g., using one or more of the gases described herein), pressure, and moisture can be used after deposition and before exposure to change the composition of unexposed metal and/or metal oxide-containing photoresist. The change can increase the EUV sensitivity of the material and thus lower dose to size and line edge roughness can be achieved after exposure and dry development. In the case of post-exposure processing (e.g., PEB), a thermal process with the control of one or more of temperature, gas atmosphere (e.g., using one or more of the gases described herein), pressure, and moisture can be used to change the composition of both unexposed and exposed photoresist. In some cases, the treatment may preferentially alter the composition and/or material properties of the exposed photoresist compared to the unexposed photoresist, such that the change in composition and/or material property is greater in the exposed photoresist than in the unexposed photoresist. In some other cases, the treatment may preferentially alter the composition/material properties of the unexposed photoresist compared to the exposed photoresist, such that the change in composition and/or material property is greater in the unexposed photoresist than in the exposed photoresist. These preferential interactions may arise due to chemical changes that occur during EUV exposure, for example the loss of alkyl groups within the photoresist. The changes that occur during the treatment can increase the difference in composition/material properties between the unexposed and exposed photoresist, thereby enhancing the difference in etch rate between the unexposed and exposed photoresist. A higher etch selectivity (e.g., during dry development of the pattern in the photoresist) can thereby be achieved. Due to the improved selectivity, a squarer PR profile can be obtained with improved surface roughness, and/or less photoresist residual/scum. In either case, in alternative implementations, the thermal process could be replaced by or supplemented with a remote plasma process. The remote plasma process may act to increase reactive species, thereby lowering the energy barrier for a desired reaction and increasing productivity. Remote plasma can generate more reactive radicals and therefore lower the reaction temperature/time for the treatment (e.g., as compared to treatments that rely solely on thermal energy), leading to increased productivity [0030-0033]. For example, the treatment temperature may range from about 90 to 250.sup.°C, such as 90 to 190°C, for a PAB, and from about 170 to 250°C or more for a PEB [0036]. In some embodiments, the treatment may involve a thermal process with control of temperature, gas ambient, and/or moisture. The gas ambient may include a reactive gas species such as air, water (H2O), hydrogen (Fk), oxygen (Ck), ozone (O3), hydrogen peroxide (H2O2), carbon monoxide (CO), carbon dioxide (CO2), carbonyl sulfide (COS), sulfur dioxide (SO2), chlorine (Ck), ammonia (NFb), nitrous oxide (N2O), nitric oxide (NO), methane (CFk), methylamine (CH3NH2), dimethylamine ((CFk^NFl), trimethylamine (N(CFb)3), ethylamine (CH3CH2NH2), diethylamine ((CFFCFL^NFl), triethylamine (N(CH2CH3)3), pyridine (C5H5N), alcohols (CnFkn+iOFl, including but not limited to methanol, ethanol, propanol, and butanol), acetyl acetone (CFFCOCFbCOCFF), formic acid (HCOOH), oxalyl chloride ((COCl)2), carboxylic acids (C Tkn+iCOOH), and other small molecule amines (NR'R.sup.2R\ where each of R.sup.1, R.sup.2, and R.sup.3 is independently selected from hydrogen, hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combinations thereol), etc. Substituted forms of any of these reactive gases may also be used. In some cases, the substrate may be exposed to two or more reactive gases during a treatment operation [0041]. In various embodiments, the gas ambient may include an inert gas such as N2, Ar, He, Ne, Kr, Xe, etc. In some cases, the inert gas may be provided together with one or more of the reactive gases listed above. In other cases, the gas ambient may be inert or substantially inert. For instance, the gas ambient may be free or substantially free of reactive gases. As used herein, a gas atmosphere may be considered substantially free of reactive gases if such gases are only present at trace amounts. In various cases where an inert atmosphere is used, the inert atmosphere may increase the contrast in composition and/or material properties by reducing over oxidation in relevant areas of the photoresist. For instance, in some cases where the photoresist is treated thermally in an inert atmosphere after exposing the photoresist to patterning radiation, the inert atmosphere promotes an increase in material contrast (e.g., composition and/or material properties) by reducing over oxidation present on unexposed areas of the photoresist. [0044] Any of the embodiments described herein may include a reduction step, which may operate to reduce oxidized or overoxidized areas of the photoresist. Such a reduction step may be particularly useful after a step that oxidizes the photoresist (or portions thereof). In various embodiments, the reduction step may involve exposing the substrate to a reducing atmosphere or an inert atmosphere. In some cases, the reduction step may involve heating the substrate and/or exposing the substrate to plasma. The plasma may be generated from inert gas and/or reducing gas [0043]. Fig. 4B schematically shows a cross-sectional view of an inductively coupled plasma apparatus 400 appropriate for implementing certain embodiments or aspects of embodiments such as vapor (dry) deposition, thermal treatment as described herein, plasma treatment as described herein, dry development and/or etch, an example of which is a Kiyo® reactor, produced by Lam Research Corp. of Fremont, CA. In other embodiments, other tools or tool types having the functionality to conduct one or more operations of the dry deposition, treatment (thermal or remote plasma), development and/or etch processes described herein may be used for implementation [0054]. EUVL patterning may be conducted using any suitable tool, often referred to as a scanner, for example the TWINSCAN NXE: 3300B® platform supplied by ASML of Veldhoven, NL). The EUVL patterning tool may be a standalone device from which the substrate is moved into and out of for deposition and etching as described herein. Or, as described below, the EUVL patterning tool may be a module on a larger multi-component tool. Fig. 5 depicts a semiconductor process cluster tool architecture with vacuum-integrated deposition, EUV patterning and dry development/etch modules that interface with a vacuum transfer module, suitable for implementation of the processes described herein. While the processes may be conducted without such vacuum integrated apparatus, such apparatus may be advantageous in some implementations [0072]. For example, the treatment temperature may range from about 90 to 250.sup.°C, such as 90 to 190°C, for a PAB, and from about 170 to 250°C or more for a PEB. Decreased etch rate and greater etch selectivity have been found to occur with higher treatment temperatures in the noted ranges [0036]. In particular embodiments, the PAB and/or PEB treatments may be conducted with gas ambient flow in the range of 100-10,000 seem. In these or other embodiments, the moisture content in the ambient environment may be controlled between about a few percent up to 100% (e.g., in some cases between about 20%-50%). In these or other embodiments, a pressure during treatment may be controlled, for example at or below atmospheric pressure (e.g., using a vacuum to achieve sub-atmospheric pressures). In some cases, the pressure during treatment may be between about 0.1-760 Torr, for example between about 0.1-10 Torr, or between about 0.1-1 Torr in some cases. In these or other embodiments, a duration of the treatment may be controlled between about 1 to 15 minutes, for example between about 2-5 minutes, or about 2 minutes. These findings can be used to tune the treatment conditions to tailor or optimize processing for particular materials and circumstances. For example, the selectivity achieved for a given EUV dose with a 220.sup.° C to 250°C PEB thermal treatment in air at about 20% humidity for about 2 minutes can be made similar to that for about a 30% higher EUV dose with no such thermal treatment. So, depending on the selectivity requirements/constraints of the semiconductor processing operation, a thermal treatment such as described herein can be used to lower the EUV dose needed. Or, if higher selectivity is required and higher dose can be tolerated, much higher selectivity (e.g., a dry etch selectivity of up to 100 in exposed vs. unexposed regions of the photoresist) can be obtained than would be possible in a wet development context. Remote plasma-based treatments may result in the same or similar benefits [0038-0039]. Resists have been developed using a wet (solvent) approach, which requires the wafer to move to a track, where it is exposed to developing solvent, dried and baked [0028]
With respect to claims 1, 4-8 and 13-20, the examiner holds that it would have been obvious to one of ordinary skill in the art to modify the process of coating of coating the metal oxide photoresists, exposing them to EUV and developing them discussed at [0002] by heating the resist as a PAB at 90 to 250.sup.°C and/or from about 170 to 250°C or more for a PEB in air at 0.1-760 Torr as taught at [0036,0038-0039] together with a remote plasma treatment (which inherently produced radicals) as either a post application treatment or a post exposure treatment as discussed at [0041,0044] with a reasonable expectation of forming a resist pattern with improved etch selectivity as taught at [0038-0039]. Further, it would have been obvious to use a remote plasma based upon the disclosure of these.
With respect to claims 1, 4-8 and 13-20, the examiner holds that it would have been obvious to one of ordinary skill in the art to modify the process of coating of coating the metal oxide photoresists, exposing them to EUV and developing them discussed at [0002] by heating the resist as a PAB at 90 to 250.sup.°C and/or from about 170 to 250°C or more for a PEB in air at 0.1-760 Torr for 1-15 minutes as taught at [0036,0038-0039] together with a remote plasma treatment (which inherently produced radicals) as either a post application treatment or a post exposure treatment as discussed at [0041,0044] with a reasonable expectation of forming a resist pattern with improved etch selectivity as taught at [0038-0039]. ]. Further, it would have been obvious to use a remote plasma based upon the disclosure of these.
Claims 1,4-8 and 11-19 are rejected under 35 U.S.C. 103 as being unpatentable over
Jiang et al. 20200326627, in view of Tan et al. WO 2023009336
Tan et al. WO 2023009336 teaches the treatment of the resist in an inert or reducing atmosphere to reduce the oxidized or over-oxidized area The inert gasses can be N2, He, Ar, Ne, Kr This may use a heating and/or plasma exposure. Gasses include ammonia (NH3). The treatment may be after application/deposition as in figure 2 (PAB) or after exposure and before development (post exposure bake). These plasmas may be remote plasmas used. The operations may be performed in a different order [0041-0053,0110]. The use of ICPs and microwave plasmas is disclosed [0080].
Jiang et al. 20200326627 does not teaches plasma treatment after application or exposure.
In addition to the basis above, it would have been obvious to modify the teachings of Jiang et al. 20200326627 by plasma treating resist after deposition or exposure to reduce the oxidation as taught by Tan et al. WO 2023009336.
Claims 1,4-8 and 11-20 are rejected under 35 U.S.C. 103 as being unpatentable over Jiang et al. 20200326627 and Tan et al. WO 2023009336 in view of Peter et al. 20230314954.
Peter et al. 20230314954 teaches that process conditions may be optimized for the photoresist rework. In some embodiments, higher temperature, higher pressure, and/or higher reactant flow may lead to increased etch rate. Suitable process conditions for a photoresist rework may be: reactant flow of 100-500 sccm (e.g., 500 sccm HCl, HBr, HI, BCl.sub.3 or H.sub.2 and Cl.sub.2 or Br.sub.2), temperature of 20° C. to 140° C. (e.g., 80° C.), pressure of 20-1000 mTorr (e.g., 300 mTorr) or pressure of 50-765 Torr (e.g., 760 Torr), plasma power of 0 W to 800 W (e.g., 500 W) at high frequency (e.g., 13.56 MHz), wafer bias of 0 to 200 V.sub.b (a higher bias may be used with harder underlying substrate materials) and for a time of about 20 seconds to 3 minutes, sufficient to completely remove the EUV photoresist, dependent on the photoresist film and composition and properties. In some embodiments, photoresist rework can be performed without application of plasma. The photoresist rework can be performed thermally with a halide-containing gas such as a hydrogen halide (e.g., HBr) at elevated temperatures (e.g., between 80° C. to 120° C.). It should be understood that while these conditions are suitable for some processing reactors, e.g., a Kiyo etch tool available from Lam Research Corporation, Fremont, CA, a wider range of process conditions may be used according to the capabilities of the processing reactor [0056]. The inductively coupled plasma apparatus 800 includes an overall process chamber 824 structurally defined by chamber walls 801 and a window 811. The chamber walls 801 may be fabricated from stainless steel, aluminum, or plastic. The window 811 may be fabricated from quartz or other dielectric material. An optional internal plasma grid 850 divides the overall process chamber into an upper sub-chamber 802 and a lower sub chamber 803. In most embodiments, plasma grid 850 may be removed, thereby utilizing a chamber space made of sub chambers 802 and 803. A chuck 817 is positioned within the lower sub-chamber 803 near the bottom inner surface. The chuck 817 is configured to receive and hold a semiconductor wafer 819 upon which the etching and deposition processes are performed. The chuck 817 can be an electrostatic chuck for supporting the wafer 819 when present. In some embodiments, an edge ring (not shown) surrounds chuck 817, and has an upper surface that is approximately planar with a top surface of the wafer 819, when present over chuck 817. The chuck 817 also includes electrostatic electrodes for chucking and dechucking the wafer 819. A filter and DC clamp power supply (not shown) may be provided for this purpose. Other control systems for lifting the wafer 819 off the chuck 817 can also be provided. The chuck 817 can be electrically charged using an RF power supply 823. The RF power supply 823 is connected to matching circuitry 821 through a connection 827. The matching circuitry 821 is connected to the chuck 817 through a connection 825. In this manner, the RF power supply 823 is connected to the chuck 817. In various embodiments, a bias power of the electrostatic chuck may be set at about 50V or may be set at a different bias power depending on the process performed in accordance with disclosed embodiments. For example, the bias power may be between about 20 V.sub.b and about 100 V, or between about 30 V and about 150 V [0129].
Neither of Jiang et al. 20200326627 and Tan et al. WO 2023009336 describe the use of specific plasmas to treat resists
It would have been obvious to one skilled in the art to modify the processes rendered obvious by the combination of Jiang et al. 20200326627 and Tan et al. WO 2023009336 by using the plasma conditions disclosed at [0056] of Peter et al. 20230314954 with a reasonable expectation of processing the resist.
Claims 1-8 and 11-20 are rejected under 35 U.S.C. 103 as being unpatentable over Jiang et al. 20200326627 and Tan et al. WO 2023009336, in view of Kenane et al. WO 2023114730 and Liu et al. 20230154750
Kenane et al. WO 2023114730 in example 1 describes in example 2, an organotin resist coated to a thickness of 100 nm, baked at 200 degrees C for 3 minutes in air or nitrogen, exposed using an e-beam, developed and [0318]. post-application bake (PAB) or another post-application treatment can be performed. Such treatment can improve etch resistance of unexposed material to aqueous or non-aqueous solution. In one instance, such treatment can enhance the hydrophobicity difference (or contrast) between unexposed and exposed regions, thus the PAB operation is conducted. In another instance, such treatment can reduce the hydrophobicity difference (or contrast) between unexposed and exposed regions, thus the PAB operation is not conducted. In yet another instance, use of PAB removes residual moisture from the layer to form a hardened resist film. The PAB can involve some combination of thermal treatment, chemical exposure, and/or moisture to increase the EUV sensitivity of the film, thereby reducing the EUV dose to develop a pattern in the film. In particular embodiments, the PAB step is conducted at a temperature greater than about 100° C. or at a temperature of from about 100° C. to about 200° C. or from about 100° C. to about 250° C. In other embodiments, the PAB step is conducted at a temperature from about 190° C. to about 350° C. in the absence of an O-containing gas. In another instance, post-application treatment includes exposing the film to an inert gas or CO.sub.2, which can optionally include cooling or heating. Use of an inert gas can provide metal-oxygen-metal species, and use of CO.sub.2 can provide metal carbonate species within the film [0094] In operation 304, the film is exposed to EUV radiation to develop a pattern. Generally, the EUV exposure causes a change in the chemical composition of the film, creating a contrast in etch selectivity that can be used to remove a portion of the film. Such a contrast can provide a positive tone resist, as described herein. EUV exposure can include, e.g., an exposure having a wavelength in the range of about 10 nm to about 20 nm in a vacuum ambient (e.g., about 13.5 nm in a vacuum ambient) [0095] Operation 305 is an optional post-exposure bake (PEB) of the exposed film, thereby further removing residual moisture, promoting chemical condensation within the film, or increasing contrast in etch selectivity of the exposed film; or post-treating the film in any useful manner. In one instance, such treatment can reduce the hydrophobicity difference (or contrast) between unexposed and exposed regions, thus the PEB operation is not conducted. In another instance, the exposed film can be thermally treated (e.g., at a low temperature and/or optionally in the presence of various chemical species) to promote reactivity within the EUV exposed or unexposed portions of the resist upon exposure to a stripping agent or a positive tone developer (e.g., a halide-based aqueous acid, such as HCl, HBr, HI, or combinations thereof). In another instance, the exposed film can be thermally treated (e.g., at a low temperature) to further crosslink ligands within the EUV unexposed portions of the resist, thereby providing EUV exposed portions that can be selectively removed upon exposure to a stripping agent (e.g., a positive tone developer). In yet another instance, PEB is omitted [0093]. the PR pattern can be developed by way of positive tone development or negative tone development. In operation 306, the PR pattern is developed by way of positive development in the presence of an aqueous acid. In various embodiments of development, the exposed regions are removed (to provide a pattern within a positive tone resist). These steps may be wet processes using one or more developers or developing solutions, followed by an optional rinse operation (e.g., with deionized water or another solvent) or an optional dry operation (e.g., with air or under inert conditions with optional heat). In particular embodiments, the development step is a wet process applied to a tin-based film [0094]. In any embodiment herein, the method can include (e.g., after development) rinsing, further hardening, and/or baking the patterned film, thereby providing a resist mask disposed on a top surface of the substrate. Hardening steps can include any useful process to further crosslink or react the EUV unexposed or exposed regions, such as steps of exposing to plasma (e.g., O.sub.2, O.sub.3, Ar, He, or CO.sub.2 plasma), exposing to ultraviolet radiation, annealing (e.g., at a temperature of about 180° C. to about 240° C.), thermal baking, or combinations thereof that can be useful for a post-development baking (PDB) step [0106]. The strategy of engineering a vertical composition gradient in a PR film is particularly applicable to dry deposition methods, such as CVD and ALD, and can be realized by tuning the flow ratios between different reactants during deposition. The type of composition gradients that can be engineered include: the ratios between different R or L ligands for the precursor, use of different precursors having more hydrophobic R ligands, the percentages of counter-reactants that contain carbon-containing elements, and combinations of the above. In addition, such compositional gradients can include a higher fraction of bulky, terminal substituents located at the top surface of the film. For example, in the case of Sn-based resists, the incorporation of tin precursors with two or more R groups is possible at the top surface, thereby presenting additional hydrophobic R groups at the top surface of the PR film [0140-0141] Such gradient films can be formed by using any precursors (e.g., tin or non-tin precursors) and/or counter-reactants described herein. Yet other films, methods, precursors, and other compounds are described in U.S. Provisional Pat. Appl. No. 62/909,430, filed Oct. 2, 2019, and International Appl No. PCT/US20/53856, filed Oct. 1, 2020, published as International Pub. No. WO 2021/067632, in which each is titled SUBSTRATE SURFACE MODIFICATION WITH HIGH EUV ABSORBERS FOR HIGH PERFORMANCE EUV PHOTORESISTS; and International Appl. No. PCT/US20/70172, filed Jun. 24, 2020, published as International Pub. No. WO 2020/264557, and titled PHOTORESIST WITH MULTIPLE PATTERNING RADIATION-ABSORBING ELEMENTS AND/OR VERTICAL COMPOSITION GRADIENT, the disclosures of which at least relating to the composition, deposition, and patterning of directly photopatternable metal oxide films to form EUV resist masks are incorporated by reference herein [0157]. Suitable vapor deposition processes include chemical vapor deposition (CVD), atomic layer deposition (ALD), plasma-enhanced chemical vapor deposition (PECVD), or plasma-enhanced atomic layer deposition (PEALD). In some embodiments, the deposition is ALD, in a cyclical process of depositing the Sn—X.sub.n and depositing the oxygen-containing counter-reactant. In some embodiments, the deposition is CVD, by simultaneously flowing the Sn—Xe and the oxygen-containing counter-reactant. Materials and processes among those useful herein for depositing SnO.sub.x layers are described in Nazarov et al., Atomic Layer Deposition of Tin Dioxide Nanofilms: A Review, 40 Rev. Adv. Mater. Sci. 262 (2015). A SnO.sub.x substrate may be deposited by a CVD or ALD process, as described herein.[0160]. The process conditions for the dry development may be reactant flow of 100 sccm to 500 sccm (e.g., 500 sccm HBr or HCl), temperature of −10° C. to 120° C. (e.g., −10° C.), pressure of 1 mTorr to 500 mTorr (e.g., 300 mTorr) with no plasma and for a time of about 10 sec to 1 min, dependent on the photoresist film and their composition and properties [0217]. Suitable process conditions for a dry bevel edge and backside clean may be a reactant flow of 100 sccm to 500 sccm (e.g., 500 sccm HCl, HBr, or H.sub.2 and Cl.sub.2 or Br.sub.2, BC.sub.3 or H.sub.2), temperature of −10° C. to 120° C. (e.g., 20° C.), pressure of 20 mTorr to 500 mTorr (e.g., 300 mTorr), plasma power of 0 to 500 W at high frequency (e.g., 13.56 MHz), and for a time of about 10 sec to 20 sec, dependent on the photoresist film and composition and properties. It should be understood that while these conditions are suitable for some processing reactors, e.g., a Kiyo etch tool available from Lam Research Corporation, Fremont, CA, a wider range of process conditions may be used according to the capabilities of the processing reactor [0221].Plasma processes include transformer coupled plasma (TCP), inductively coupled plasma (ICP) or capacitively coupled plasma (CCP), employing equipment and techniques among those known in the art. For example, a process may be conducted at a pressure of >0.5 mTorr (e.g., such as from 1 mTorr to 100 mTorr), at a power level of <1000 W (e.g., <500 W). Temperatures may be from 30° C. to 300° C. (e.g., 30° C. to 120° C.), at flow rate of 100 to 1000 standard cubic centimeters per minute (sccm), e.g., about 500 sccm, for from 1 to 3000 seconds (e.g., 10 seconds to 600 seconds) [0214]
Liu et al. 20230154750 teaches the deposition of organometallic resists using chemical vapor deposition (CVD) or atomic layer deposition) (ALD) at temperatures of 100 to 500 degrees C and pressures of 5 mTorr to 10 Torr and plasma powers of less than 1000 W [0020,0039]. There may be a post-deposition bakes at 70-150 degrees C at 100 Torr to 760 Torr for 20 seconds to 10 minutes [0023]. The post exposure bake can be more than 350 degrees C at ambient conditions [0028]. The use of EUV exposure is disclosed [0026]
It would have been obvious to one skilled in the art to modify the processes of Jiang et al. 20200326627 and Tan et al. WO 2023009336 by using the atomic layer deposition (ALD) processes as taught by Kenane et al. WO 2023114730 and Liu et al. 20230154750, where plasma treatments are performed during the ALD coating process as taught in Liu et al. 20230154750 and/or as hardening processes as taught in Kenane et al. WO 2023114730 using the treatment conditions of Liu et al. 20230154750 with a reasonable expectation of forming a useful resist pattern based upon all the references using tin based resists. Further, it would have been obvious to modify the processes rendered obvious by the combination of Jiang et al. 20200326627 and Tan et al. WO 2023009336 in combination with Kenane et al. WO 2023114730 and Liu et al. 20230154750 by using other temperatures disclosed by Jiang et al. 20200326627, Tan et al. WO 2023009336 or Kenane et al. WO 2023114730 in place of the temperatures used in the examples of Jiang et al. 20200326627 with a reasonable expectation of forming useful resists based upon the disclosed useful temperature ranges and to use positive or negative tone wet developments as taught by Kenane et al. WO 2023114730
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
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MARTIN J. ANGEBRANNDT
Primary Examiner
Art Unit 1737
/MARTIN J ANGEBRANNDT/Primary Examiner, Art Unit 1737 June 17, 2026
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