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 and 6-20 are rejected under 35 U.S.C. 103 as being unpatentable over Weidman et al. WO 2021202681 and Yu et al. WO 2021158433
Weidman et al. WO 2021202681 teaches with respect to figure 2 a process where a metal containing resist is coated, flood/blanket/uniformly exposed to UV, pattern-wise exposed to EUV, developed, (optionally cleaned) and optionally post development hardened. In figure 4, the resist pattern shown in figure 400b has been given a low blanket DUV dose and an patterned EUV dose of 34 mJ/cm2. Figure 400c was exposed using a high intensity DUV blanket exposure and a pattern-wise EUV exposure of 25 mJ/cm2 [0051]. In some embodiments, a blanket UV treatment technique as discussed herein may be combined with a thermal treatment. For example, the substrate may be baked before or after the patterned EUV exposure. Thermal processing of substrate prior to and/or following patterned EUV exposure is further discussed in U.S. Pat. App. No. 62/970,020, filed February 4, 2020 and titled POST APPLICATION/EXPOSURE TREATMENTS TO IMPROVE DRY DEVELOPMENT PERFORMANCE OF METAL- CONTAINING EUV RESIST, the disclosure of which at least in regards to thermally treating a25 substrate having a metal-containing EUV resist, is hereby incorporated by reference herein. [0037]. In some embodiments, the wavelengths used for a blanket UV treatment are less than about 300 nm. In some embodiments, the blanket UV treatment uses an emitter with a peak20 wavelength of about 250 nm (e.g., 248 nm). In some embodiments, the emitter has a wavelength of about 190 nm (e.g., 193 nm). In some embodiments a broadband emitter is used, with a peak wavelength of e.g., less than about 300 nm, about 250 nm, or about 190 nm. In some embodiments, the energy dose for a PAC blanket UV treatment may be between about 1 and 100 mJ/cm2 or between about 20 and 100 mJ/cm2. For example, in some embodiments the energy dose for a PAC 25 blanket UV treatment is between about 1–100, 2–80, or 3–60 mJ/cm2 with a 248nm emitter (KrF laser) . In some embodiments the duration of a blanket UV treatment is between about 1 second and 300 seconds [0045].
Yu et al. WO 2021158433 (priority document is 62/970020) teaches with respect to figure 3, a post exposure thermal treatment of the resist [0015]. In various embodiments, the photoresist has been patterned by partial exposure to patterning radiation resulting in exposed and unexposed portions of the photoresist. In some such embodiments, the treatment is a post-exposure bake (PEB). In these or other embodiments, the treatment may be a post-exposure remote plasma treatment. In various embodiments, the treatment may be conducted at a temperature between about 170 to 250.sup.°C or higher. In these or other embodiments, a composition of both the unexposed and exposed portions of the photoresist may be changed by the treatment to (i) increase an etch rate in a dry development etch gas, (ii) increase a difference in the composition between the unexposed and exposed portions of the photoresist, and/or (iii) increase a difference in one or more material properties between the unexposed and exposed portions of the photoresist [0007]. 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 [0030]. 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 [0032]. The treatment temperature may range from about 170 to 250°C or more for a PEB [0036]. FIGS. 6A-6D depict experimental results showing the improved material contrast and selectivity between unexposed and exposed portions of a photoresist layer that can be achieved by controlling temperature during a PEB. In each example, the substrate was exposed to a PEB in which the temperature of the substrate was controlled (e.g., by controlling the substrate support temperature). Afterwards, the photoresist layer on each substrate was developed using dry techniques to form a series of photoresist features on the substrate. In FIG. 6A, the temperature was controlled at about 235°C. In FIG. 6B, the temperature was controlled at about 220°C. In FIG. 6C, the temperature was controlled at about 205°C. In FIG. 6D, the temperature was controlled at about 190°C. At lower treatment temperatures, the photoresist profile showed significant tapering/rounded features. By contrast, at higher treatment temperatures, the photoresist profile is substantially improved, with the features being much less tapered/round, and much more square. The higher PEB temperatures provide greater material contrast between exposed and unexposed portions of the photoresist, thereby providing higher selectivity when the photoresist is developed. Further, the substrates treated with higher PEB temperatures show higher critical dimensions of the lines after development, which corresponds to a lower dose to size. In other words, the higher treatment temperatures can be used to achieve a desired critical dimension at a lower dose of EUV radiation than would be required to achieve the same critical dimension when the substrate is treated at lower temperatures (or not treated at all). As mentioned above, dry development techniques were used after the PEB treatments. In many cases, wet development techniques are not able to develop a photoresist layer that has been treated with a PEB at high temperatures, e.g., >180°C, for the reasons discussed above [0037]. For instance, in one example where the treatment is a thermal treatment, the treatment may be referred to as a post-exposure bake (PEB). The treatment may modify both the exposed portions 302c and the unexposed portions 302b of the EUV photoresist, thereby forming a modified version of the exposed portion 302e and a modified version of the unexposed portion 302d. The modifications produced by the treatment may increase the etch rate of the photoresist material in a dry development etch gas. Alternatively or in addition, the modifications produced by the treatment may increase the difference in the composition/material properties between the unexposed portions and exposed portions of the photoresist. In other words, the difference between the composition/material properties when comparing (1) the modified version of the unexposed portion 302d of the photoresist after the treatment and (2) the modified version of the exposed portion 302e of the photoresist after the treatment, is more substantial than the difference between the composition/material properties when comparing (1) the unexposed portions 302b of the photoresist prior to treatment and (2) the exposed portions 302c of the photoresist prior to treatment [0045].
Weidman et al. WO 2021202681 does not exemplify processing of the tin oxide resist including a post exposure bake.
With respect to claims 1-3,6,10-16 and 19-20, it would have been obvious to modify the processes described with respect to figures 400b or 400a of Weidman et al. WO 2021202681 [0051] by adding a post exposure bake such as the heating at 170-250 degrees C disclosed at [0036] of Yu et al. WO 2021158433 to 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 disclosed at [0032] of Yu et al. WO 2021158433 with a reasonable expectation of success in forming a useful patterned resist based upon the direction to the priority document corresponding to Yu et al. WO 2021158433 for its disclosed of thermal treatment at [0037] of Weidman et al. WO 2021202681
With respect to claims 1-3 and 6-20, it would have been obvious to modify the processes described with respect to figures 400b or 400a of Weidman et al. WO 2021202681 [0051] using intensities of 1–100 mJ/cm2 with a 248nm emitter (KrF laser) as the DUV source as taught at [0045] of Weidman et al. WO 2021202681 and adding a post exposure bake such as the heating at 170-250 degrees C disclosed at [0036] of Yu et al. WO 2021158433 to 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 photoresist profile can be obtained with improved surface roughness, and/or less photoresist residual/scum disclosed at [0032] of Yu et al. WO 2021158433 with a reasonable expectation of success in forming a useful patterned resist based upon the direction to the priority document corresponding to Yu et al. WO 2021158433 for its disclosed of thermal treatment at [0037] of Weidman et al. WO 2021202681
Yu et al. WO 2021158433 does not exemplify processing of the tin oxide resist including the DUV exposure before the pattern-wise EUV exposure.
With respect to claims 1-3,6, 11,12 and 14-16 , it would have been obvious to one skilled in the art to modify the process disclosed with respect to figures 3, which includes applying the resist (302), to the substrate (301), pattern-wise exposing the resist using EUV and post baking the resist which may increase the etch rate in a dry development process taught at [0046] of Yu et al. WO 2021158433, by adding a blanket DUV exposure as taught by Weidman et al. WO 2021202681 to reduce the amount of EUV exposure required as taught with respect to figures 400a, 400b and 400c of Weidman et al. WO 2021202681 with a reasonable expectation of success in forming a useful patterned resist noting the reference to the priority document corresponding to Yu et al. WO 2021158433 at [0037] of Weidman et al. WO 2021202681. The examiner holds that the absorption rates/coefficients are inherent to the resist and therefore the absorption at least one wavelength in the DUV is lower than at least one wavelength in the EUV.
With respect to claims 1-3,6, 11-16 and 20, it would have been obvious to one skilled in the art to modify the process disclosed with respect to figures 3, which includes applying the resist (302), to the substrate (301), pattern-wise exposing the resist using EUV and post baking (PEB) the resist which may increase the etch rate in a dry development process taught at [0046] of Yu et al. WO 2021158433, by preforming PEB heating at 170-250 degrees C as taught at [0036] of Yu et al. WO 2021158433 to 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 which leads to a squarer photoresist profile can be obtained with improved surface roughness, and/or less photoresist residual/scum disclosed at [0032] of Yu et al. WO 2021158433 and adding a blanket DUV exposure as taught by Weidman et al. WO 2021202681 to reduce the amount of EUV exposure required as taught with respect to figures 400a, 400b and 400c of Weidman et al. WO 2021202681 with a reasonable expectation of success in forming a useful patterned resist noting the reference to the priority document corresponding to Yu et al. WO 2021158433 at [0037] of Weidman et al. WO 2021202681.
With respect to claims 1-3 and 6-20, it would have been obvious to one skilled in the art to modify the process disclosed with respect to figures 3, which includes applying the resist (302), to the substrate (301), pattern-wise exposing the resist using EUV and post baking (PEB) the resist which may increase the etch rate in a dry development process taught at [0046] of Yu et al. WO 2021158433, by preforming PEB heating at 170-250 degrees C as taught at [0036] of Yu et al. WO 2021158433 to 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 which leads to a squarer photoresist profile can be obtained with improved surface roughness, and/or less photoresist residual/scum disclosed at [0032] of Yu et al. WO 2021158433 and adding a blanket DUV exposure using intensities of 1–100 mJ/cm2 with a 248nm emitter (KrF laser) as the DUV source as taught at [0045] of Weidman et al. WO 2021202681 to reduce the amount of EUV exposure required as taught with respect to figures 400a, 400b and 400c of Weidman et al. WO 2021202681 with a reasonable expectation of success in forming a useful patterned resist noting the reference to the priority document corresponding to Yu et al. WO 2021158433 at [0037] of Weidman et al. WO 2021202681.
Claims 1-20 are rejected under 35 U.S.C. 103 as being unpatentable over Weng et al. 20220365428, in view of Yu et al. WO 2021158433 and Weidman et al. WO 2021202681.
Weng et al. 20220365428 teaches with respect to figure 2B, a substrate (202), a layer (204), a antireflection coating (206) a tin or tin oxide based photoresist (208), which is subjected to a pre-exposure bake (2C) to remove solvent , pattern-wise exposed (2D) using EUV, e-beam or deep UV, post baked (2E) and then developed (2F). The pattern can then be used for masking etching, ion implantation or the like [0021-0035]. FIG. 3B illustrates an example photoresist material reaction 320. The example photoresist material reaction 320 may include a precipitation reaction to form a photoresist material including tin (Sn) clusters bearing two or more types of carboxylate ligands. As shown in FIG. 3B, the example photoresist material reaction 320 may include a compound 322 and a silver (Ag) salt 324 of a first carboxylic acid. The compound 322 may include one or more tin (Sn) clusters or tin oxide (SnO.sub.x) clusters, such as a 3-tin cluster, a 4-tin cluster, a 6-tin cluster, a 10-tin cluster, a 12-tin cluster, or another tin cluster. The compound 322 may also include chlorine (Cl), a second carboxylic acid including hydroxyl (—OH), and a substituent R1 including isopropyl or n-butyl, among other examples. The silver salt 324 may include a substituent R2, which may be different from the second carboxylic acid [0040].
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FIGS. 4A-4C are diagrams of example photoresist material reactions described herein. The example photoresist material reactions may be performed to form photoresist materials that may be used in various semiconductor processing operations described herein, such as the semiconductor processing operations described above in connection with FIGS. 2A-2F. In particular, the example photoresist material reactions described in connection with FIGS. 4A-4C may be performed to form photoresist materials that may be used to form the photoresist layer 208. The example photoresist material reactions described in connection with FIGS. 4A-4C may be performed to form photoresist materials that include a plurality of tin oxide (SnO.sub.x) clusters bearing inorganic carbonate (CO.sub.3) ligands. The carbonate ligands along with the tin oxide clusters may reduce, minimize, and/or prevent crystallization of the photoresist materials, which may increase the coating performance of the photoresist materials and may decrease the surface roughness of the photoresist layer 208. Moreover, the carbonate ligands may be unstable during exposure of the photoresist layer 208. The instability may enable the use of lower radiation exposure energy levels when pattering the photoresist layer 208 [0043].
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The tin cluster (or tin oxide (SnO.sub.x) cluster) 312 may include a collection of tin (or tin oxide) atoms ranging from 3-tin to 12-tin. For example, the tin cluster 312 may include a 3-tin cluster, a 4-tin cluster, a 6-tin cluster, a 10-tin cluster, a 12-tin cluster, or another tin cluster. Generally, the lower the cluster number, the smaller the cluster size. As an example, a 4-tin cluster may range from approximately 0.4 nanometers in size to approximately 1 nanometer in size, whereas a 6-tin cluster may range from approximately 0.6 nanometers in size to approximately 1 nanometer in size. The line width roughness (LWR) performance of the photoresist material 318 may increase the smaller the cluster size of the tin cluster 312. However, smaller cluster sizes may provide fewer cross-linking sites and fewer ligand sites, which may result in increased radiation exposure for patterning a photoresist layer formed using the photoresist material 318. In some implementations, a single tin cluster number is used to form the photoresist material 318. In some implementations, a plurality of different tin cluster numbers are used to form the photoresist material 318 [0038]
Weng et al. 20220365428 does not exemplify processing of the tin oxide resist including the DUV exposure before the pattern-wise EUV exposure and considers the PEB optional.
With respect to claims 1-3,5,6,11-16, and 20, it would have been obvious to practice the process disclosed with respect to figures 2A-F of Weng et al. 20220365428 using the tin oxide materials illustrated in figures 3B, 4A or 4B modified by adding a DUV blanket exposure taught by Weidman et al. WO 2021202681 to reduce the amount of EUV exposure required as taught in figures 400a to 400c and to preform the post exposure bake at 170-250 degrees C as taught at [0036] of Yu et al. WO 2021158433 to 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 which leads to a squarer photoresist profile can be obtained with improved surface roughness, and/or less photoresist residual/scum disclosed at [0032] of Yu et al. WO 2021158433 with a reasonable expectation of success in forming a useful patterned resist noting that the resists are disclosed as EUV and DUV sensitive at [0021-0035] of Weng et al. 20220365428
With respect to claims 1-3 and 5-20, it would have been obvious to practice the process disclosed with respect to figures 2A-F of Weng et al. 20220365428 using the tin oxide materials illustrated in figures 3B, 4A or 4B modified by adding a DUV blanket exposure using intensities of 1–100 mJ/cm2 with a 248nm emitter (KrF laser) as the DUV source as taught at [0045] of Weidman et al. WO 2021202681 to reduce the amount of EUV exposure required as taught in figures 400a to 400c and to perform the post exposure bake at 170-250 degrees C as taught at [0036] of Yu et al. WO 2021158433 to 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 which leads to a squarer photoresist profile can be obtained with improved surface roughness, and/or less photoresist residual/scum disclosed at [0032] of Yu et al. WO 2021158433 with a reasonable expectation of success in forming a useful patterned resist noting that the resists are disclosed as EUV and DUV sensitive at [0021-0035] of Weng et al. 20220365428
With respect to claims 1-20, it would have been obvious to practice the process disclosed with respect to figures 2A-F of Weng et al. 20220365428 using the tin oxide materials illustrated in figures 4B (which is partially hydrated/has hydroxyl groups which are circled) modified by adding a DUV blanket exposure using intensities of 1–100 mJ/cm2 with a 248nm emitter (KrF laser) as the DUV source as taught at [0045] of Weidman et al. WO 2021202681 to reduce the amount of EUV exposure required from the 150 mJ/cm2 disclosed at [0026] of Weng et al. 20220365428 as taught in figures 400a to 400c of Weidman et al. WO 2021202681 and to perform the post exposure bake at 170-250 degrees C as taught at [0036] of Yu et al. WO 2021158433 to 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 which leads to a squarer photoresist profile can be obtained with improved surface roughness, and/or less photoresist residual/scum disclosed at [0032] of Yu et al. WO 2021158433 with a reasonable expectation of success in forming a useful patterned resist noting that the resists are disclosed as EUV and DUV sensitive at [0021-0035] of Weng et al. 20220365428
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 July 1, 2026
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