Rinsing agent for removing edge protection layer and residual metal hard mask components and method of using the same

Abstract

The present invention relates to a rinse agent for removing edge protection layer and residual hard mask components (e.g., metal) from the edge and at least one near surface of a wafer / substrate and a method of using the same, wherein the rinse agent comprises (i) acetic acid and / or a halogenated acetic acid of structure (A): wherein R1 and R2 are independently hydrogen or halogen and R3 is halogen, and (ii) a compound of structure (B): wherein R a , R b , R c , R d , R e , R f , R g and R h Each of may independently be hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted halogenated alkyl, substituted or unsubstituted alkylcarbonyl, halogen, and hydroxy.

Description

[0001] background

[0002] field

[0003] The disclosed subject matter relates to a rinse agent for removing edge protection layers in a photolithography patterning process and its use. The novel rinse agent is formulated to remove both edge protection layers and residual hard mask components (eg, metal) from wafer / substrate surfaces.

[0004] Related technologies

[0005] Multiple anti-reflective layers and hard masks are used for advanced photolithography patterning processes. For example, in the case where the photoresist does not provide enough dry etching resistance, it is preferred to act as a hard mask and have a bottom layer and / or anti-reflective coating of a photoresist with high etching resistance during substrate etching. One method is to incorporate silicon, titanium, zirconium, aluminum or other metal materials into the layer below the organic photoresist layer. In addition, another high carbon content anti-reflective or masking layer can be placed below the metal-containing anti-reflective layer to form a three-layer of high carbon film / hard mask film / photoresist. Such a layer can be used to improve the lithography performance of the imaging process. However, metal contamination in photolithography and etching tools and cross contamination between wafers during manufacturing can be problems that should be avoided.

[0006] A process and apparatus for reducing metal contamination during the manufacture of integrated circuit components is described in U.S. Pat. No. 8,791,030 ("Iwao"), which is hereby incorporated herein in its entirety. According to Iwao, a masking agent is supplied to the edge of a wafer / substrate and baked to form a masking film (also known as an edge protection layer ("EPL") or edge masking layer) at the edge of the wafer / substrate. A hard mask composition is then coated on the wafer / substrate and the EPL. An edge bead remover ("EBR") is used to remove the portion of the hard mask composition covering the edge protection layer and the hard mask composition is baked to form a hard mask. The EPL is then removed with an EPL removal solution. The result is that the hard mask is spaced apart from the edge of the wafer / substrate, thereby reducing contamination.

[0007] Masking agents for forming the EPL are described in patent application PCT / EP2018 / 056322 (published as WO / 2018 / 167112) entitled "Photolithographic Compositions and Methods of Use Thereof," which is incorporated herein by reference in its entirety. The compositions disclosed therein prevent metal contamination at the edges of substrates / wafers during the manufacture of electronic devices. As explained in PCT / EP2018 / 056322, it is desirable that the applied EPL be capable of being easily removed at a rate that achieves and / or maintains commercially acceptable process times without negative or damaging effects on the hard mask (such as may occur by wet etching).

[0008] PCT / EP2018 / 056322 further describes Figure 2a-f A general process for applying a masking agent to form an EPL in a method for manufacturing an electronic device described in . In this process, a metal hard mask composition or a metal oxide photoresist composition (collectively referred to as a "hard mask" or "hard mask composition") is applied to a substrate and an EPL (see FIG. 2c ). The EPL and the hard mask composition are then rinsed with an EBR and / or a backside rinse ("BR") material to remove at least a portion of the hard mask composition in contact with the EPL (see FIG. 2d ). Nevertheless, even after rinsing with the EBR or BR, one or more portions of the hard mask composition in contact with the EPL may remain. For example, the hard mask composition may partially penetrate the EPL or undercut the edge of the EPL. Thus, a certain amount of the hard mask and / or the components of the hard mask in contact with the EPL may not be removed during the EBR rinse. To date, no composition or process / method has been identified that provides for simultaneous removal of both the remaining residual components (e.g., metal) of the EPL and the hard mask. Instead, the step of removing the EPL must be followed by a subsequent processing step (e.g., rinsing with an additional EBR) in which any remaining residual components of the hard mask are removed from the edge and near surface of the wafer / substrate. This additional step is costly and time consuming, and is therefore inconsistent with achieving and / or maintaining commercially acceptable process times when utilizing EPL.

[0009] Therefore, there is a continuing need for materials that can remove EPL and any remaining residual components of hardmask at a faster rate than known EPL rinses while avoiding negative or damaging effects on the hardmask. As discussed below, the disclosed subject matter addresses the shortcomings known in the art regarding the removal of any remaining residual components of EPL and hardmask. The disclosed subject matter provides compositions and manufacturing methods and processes for quickly and efficiently removing applied EPL and remaining hardmask components and residues from the edge and near surface of a wafer / substrate.

[0010] Overview

[0011] In one aspect, the disclosed subject matter relates to a rinse agent for removing EPL and residual hard mask components (e.g., metals such as tin or titanium) from the edge of a wafer / substrate surface in a photolithography process, wherein the rinse agent comprises (i) between about 15 wt % and about 35 wt % acetic acid and (ii) between about 85 wt % and about 65 wt % of a compound having structure B:

[0012]

[0013] Where R a , R b , R c , R d, R e , R f , R g and R h Each of the above may independently be hydrogen, substituted or unsubstituted alkyl (preferably C 1-6 alkyl), substituted or unsubstituted halogenated alkyl (preferably halogenated C 1-6 alkyl), substituted or unsubstituted alkylcarbonyl (preferably C 1-6 In another aspect, the compound having structure B is anisole (i.e., wherein R a , R b , R c , R d , R e , R f , R g and R h each of which is hydrogen).

[0014] In another aspect, the disclosed subject matter relates to a rinse agent for removing EPL and residual hard mask components (e.g., metals such as tin or titanium) from the edge of a wafer / substrate surface in a photolithography process, wherein the rinse agent comprises:

[0015] (i) between about 1% and about 10% by weight of an acetic acid halide of structure A:

[0016]

[0017] wherein R1 and R2 are independently hydrogen or halogen and R3 is halogen; and

[0018] (ii) between about 99% and about 90% by weight of a compound having structure B:

[0019]

[0020] Where R a , R b , R c , R d , R e , R f , R g and R h Each of the above is independently hydrogen, substituted or unsubstituted alkyl (preferably C 1-6 alkyl), substituted or unsubstituted halogenated alkyl (preferably halogenated C 1-6 alkyl), substituted or unsubstituted alkylcarbonyl (preferably C 1-6In another aspect, the compound having structure A is trifluoroacetic acid (i.e., wherein each of R1, R2, and R3 in structure A is fluorine) or difluoroacetic acid (i.e., wherein R3 and one of R1 and R2 is fluorine, and the other of R1 and R2 is hydrogen). In yet another aspect, the compound having structure B is anisole (i.e., wherein R1 in structure B is fluorine). a , R b , R c , R d , R e , R f , R g and R h each of which is hydrogen).

[0021] In another aspect, the rinse agent is particularly effective in removing EPL and residual hard mask components (e.g., metals such as tin or titanium) formed by masking agents described and / or claimed in PCT / EP2018 / 056322 from the edge and near the surface of the wafer / substrate in a photolithography process. In another aspect, the rinse agent solution is particularly effective for removing EPL formed by masking agents described and / or claimed in PCT / EP2018 / 056322. In yet another aspect, the masking agent is a masking agent described and / or claimed in PCT / EP2018 / 056322, wherein the masking agent comprises polymer units having one or more of the following formulas:

[0022] a.

[0023] b.

[0024] c. and

[0025] d.

[0026] In another aspect, the flushing agent comprises (i) between about 15% and about 35% by weight acetic acid and (ii) between about 85% and about 65% by weight anisole and / or a compound having structure B. In another aspect, the flushing agent comprises (i) about 15% by weight acetic acid and (ii) preferably about 85% by weight anisole and / or a compound having structure B.

[0027] In another aspect, the flushing agent comprises (i) about 20 wt % acetic acid and (ii) preferably about 80 wt % anisole and / or a compound having structure B. In another aspect, the flushing agent comprises (i) about 25 wt % acetic acid and (ii) preferably about 75 wt % anisole and / or a compound having structure B.

[0028] In another aspect, the flushing agent comprises (i) about 30 wt % acetic acid and (ii) preferably about 70 wt % anisole and / or a compound having structure B.

[0029] In another aspect, the flushing agent comprises (i) about 35 wt % acetic acid and (ii) preferably about 65 wt % anisole and / or a compound having structure B.

[0030] In another aspect, the flushing agent comprises (i) between about 1 wt % and about 10 wt % trifluoroacetic acid and / or difluoroacetic acid and (ii) between about 99 wt % and about 90 wt % anisole and / or a compound having structure B.

[0031] In another aspect, the flushing agent comprises (i) about 1 wt % of a halogenated acetic acid of structure A and (ii) preferably about 99 wt % of anisole and / or a compound having structure B. In another aspect, the halogenated acetic acid of structure A is at least one of trifluoroacetic acid and difluoroacetic acid.

[0032] In another aspect, the flushing agent comprises (i) about 2 wt % of a halogenated acetic acid of structure A and (ii) preferably about 98 wt % of anisole and / or a compound having structure B. In another aspect, the halogenated acetic acid of structure A is at least one of trifluoroacetic acid and difluoroacetic acid.

[0033] In another aspect, the flushing agent comprises (i) about 3 wt % of a halogenated acetic acid of structure A and (ii) about 97 wt % of anisole and / or a compound having structure B. In another aspect, the halogenated acetic acid of structure A is at least one of trifluoroacetic acid and difluoroacetic acid.

[0034] In another aspect, the flushing agent comprises (i) about 4 wt % of a halogenated acetic acid of structure A and (ii) preferably about 96 wt % of anisole and / or a compound having structure B. In another aspect, the halogenated acetic acid of structure A is at least one of trifluoroacetic acid and difluoroacetic acid.

[0035] In another aspect, the flushing agent comprises (i) about 5 wt % of a halogenated acetic acid of structure A and (ii) about 95 wt % of anisole and / or a compound having structure B. In another aspect, the halogenated acetic acid of structure A is at least one of trifluoroacetic acid and difluoroacetic acid.

[0036] In another aspect, the flushing agent comprises (i) about 6 wt % of a halogenated acetic acid of structure A and (ii) about 94 wt % of anisole and / or a compound having structure B. In another aspect, the halogenated acetic acid of structure A is at least one of trifluoroacetic acid and difluoroacetic acid.

[0037] In another aspect, the flushing agent comprises (i) about 7 wt % of a halogenated acetic acid of structure A and (ii) preferably about 93 wt % of anisole and / or a compound having structure B. In another aspect, the halogenated acetic acid of structure A is at least one of trifluoroacetic acid and difluoroacetic acid.

[0038] In another aspect, the flushing agent comprises (i) about 8 wt % of a halogenated acetic acid of structure A and (ii) about 92 wt % of anisole and / or a compound having structure B. In another aspect, the halogenated acetic acid of structure A is at least one of trifluoroacetic acid and difluoroacetic acid.

[0039] In another aspect, the flushing agent comprises (i) about 9 wt % of a halogenated acetic acid of structure A and (ii) about 91 wt % of anisole and / or a compound having structure B. In another aspect, the halogenated acetic acid of structure A is at least one of trifluoroacetic acid and difluoroacetic acid.

[0040] In another aspect, the flushing agent comprises (i) about 10 wt % of a halogenated acetic acid of structure A and (ii) preferably about 90 wt % of anisole and / or a compound having structure B. In another aspect, the halogenated acetic acid of structure A is at least one of trifluoroacetic acid and difluoroacetic acid.

[0041] In another aspect, the disclosed subject matter relates to a method and process of using the rinse agent to remove EPL and residual hard mask components (e.g., metals such as tin or titanium) from the edge and near surface of a wafer / substrate in a lithography process, including in the manufacture of electronic devices.

[0042] In one aspect, the method and process include a step of removing the EPL and residual hard mask components (e.g., metals such as tin or titanium) by washing the wafer / substrate with the rinse agent. Therefore, the method and process can be referred to as a method for cleaning a wafer or substrate, comprising cleaning a wafer or substrate with a rinse agent. In another aspect, the method and process include a step of treating the edge and near surface of a wafer / substrate with a masking agent to form an EPL. In another aspect, the masking agent is a masking agent described and / or claimed in PCT / EP2018 / 056322. In another aspect, the masking agent is a masking agent described and / or claimed in PCT / EP2018 / 056322, wherein the masking agent includes a polymer unit having one or more of the following formulas:

[0043] a.

[0044] b.

[0045] c. and

[0046] d.

[0047] In another aspect, the method and process include one or more additional steps selected from the group consisting of: (a) heating the masking agent to form the EPL; (b) applying a hard mask composition to the substrate and the EPL; (c) removing at least a portion of the hard mask composition in contact with the EPL by rinsing the hard mask composition and the EPL with an EBR and / or BR material; (d) heating the hard mask composition to form a hard mask; and (e) performing at least one post-coating bake.

[0048] In another aspect, the method and process include performing the following steps in sequence without an intervening step: (i) treating the wafer / substrate edge and near surface with a masking agent; (ii) heating the applied masking agent to form an EPL; (iii) applying a hard mask composition to the substrate and the EPL; (iv) removing at least a portion of the hard mask composition in contact with the EPL by rinsing the hard mask composition and EPL with an EBR and / or BR material; (v) heating the hard mask composition to form a hard mask; (vi) removing the EPL and residual hard mask components by washing the wafer / substrate with the rinse agent; and (vii) optionally performing at least one post-coating bake. Those skilled in the art will recognize that performing the aforementioned steps in sequence does not exclude performing steps (e.g., supplying a wafer / substrate) before or after the steps performed in sequence. In another aspect, the masking agent is a masking agent described and / or claimed in PCT / EP2018 / 056322. In a further aspect, the masking agent is a masking agent described and / or claimed in PCT / EP2018 / 056322, wherein the masking agent comprises polymer units having one or more of the following formulae:

[0049] a.

[0050] b.

[0051] c. and

[0052] d.

[0053] In another aspect, the disclosed subject matter relates to methods and processes for coating and removing edge protection layers and residual hard mask components (e.g., metals such as tin or titanium) from a wafer / substrate, the methods and processes comprising the following steps: (a) applying a masking agent to the edge and near surface of the wafer / substrate; (b) heating the masking agent to form the EPL at the edge and near surface of the wafer / substrate; (c) applying a hard mask composition to the wafer / substrate and the EPL; (d) removing at least a portion of the hard mask composition in contact with the EPL by rinsing the hard mask composition with at least one EBR and / or BR material; (e) heating the hard mask composition to form a hard mask; (f) washing the wafer / substrate with a rinse agent comprising: (i) between about 15 wt % and about 35 wt % acetic acid and (ii) between about 85 wt % and about 65 wt % anisole and / or a compound having structure B; and (g) optionally performing at least one post-coating bake step. In another aspect, the masking agent is a masking agent described and / or claimed in PCT / EP2018 / 056322. In yet another aspect, the masking agent is a masking agent described and / or claimed in PCT / EP2018 / 056322, wherein the masking agent comprises a polymer unit having one or more of the following formulas:

[0054] a.

[0055] b.

[0056] c. and

[0057] d.

[0058] In another aspect, the disclosed subject matter relates to methods and processes for coating and removing edge protection layers and residual hard mask components (e.g., metals such as tin or titanium) from a wafer / substrate, the methods and processes comprising the following steps: (a) applying a masking agent to the edge and near surface of the wafer / substrate; (b) heating the masking agent to form the EPL at the edge and near surface of the wafer / substrate; (c) applying a hard mask composition to the wafer / substrate and the EPL; (d) removing at least a portion of the hard mask composition in contact with the EPL by rinsing the hard mask composition with at least one EBR and / or BR material; (e) heating the hard mask composition to form a hard mask; (f) washing the wafer / substrate with a rinse agent comprising: (i) between about 1 wt % and about 10 wt % of a halogenated acetic acid of structure A and (ii) between about 99 wt % and about 90 wt % of anisole and / or a compound having structure B; and (g) optionally performing at least one post-coating bake step. In another aspect, the masking agent is a masking agent described and / or claimed in PCT / EP2018 / 056322. In yet another aspect, the masking agent is a masking agent described and / or claimed in PCT / EP2018 / 056322, wherein the masking agent comprises a polymer unit having one or more of the following formulas:

[0059] a.

[0060] b.

[0061] c. and

[0062] d.

[0063] In another aspect, the halogenated acetic acid of structure A is at least one of trifluoroacetic acid and difluoroacetic acid. BRIEF DESCRIPTION OF THE DRAWINGS

[0065] The accompanying drawings are included to provide a further understanding of the disclosed subject matter and are incorporated in and constitute a part of this specification, and illustrate embodiments of the disclosed subject matter and together with the description serve to explain the principles of the disclosed subject matter. In the drawings:

[0066] Figure 1 A wafer / substrate having an EPL coated thereon is described;

[0067] Figure 2a-fSchematic representations of one embodiment of the methods and processes for using rinse solutions disclosed herein are illustrated. In FIG2a, a masking agent is applied to the edge of a substrate. In FIG2b, the masking agent is heated to form an EPL. In FIG2c, a hard mask composition is applied to the substrate and the EPL. In FIG2d, the hard mask composition and the EPL are rinsed with an EBR to remove at least a portion of the hard mask composition in contact with the EPL. In FIG2e, the hard mask composition is heated to form a hard mask. In FIG2f, the EPL and residual hard mask components (e.g., metals such as tin or titanium) are removed from the edge of the wafer / substrate with a rinse agent;

[0068] Figure 3 a graph illustrating the amount of residual metal (i.e., titanium) present on a wafer / substrate surface after EPL is removed from the edge of the wafer / substrate surface using different formulations of the disclosed rinse agent including acetic acid and anisole; and

[0069] Figure 4 Graph illustrating the residual metal (ie, titanium) content present on a wafer / substrate surface after removal of EPL from the edge of the wafer / substrate surface using different formulations of the disclosed rinse agent including trifluoroacetic acid and anisole.

[0070] definition

[0071] For this application, unless otherwise stated, the following terms used in the specification and claims shall have the following meanings.

[0072] In this application, unless otherwise specifically stated, the use of the singular includes the plural, and the words "a / an" and "the" mean "at least one". In addition, the use of the term "including" and other forms (such as "includes" and "included") is not limiting. Similarly, unless otherwise specifically stated, terms such as "element" or "component" encompass both elements or components that include one unit and elements or components that include more than one unit. As used herein, unless otherwise indicated, the conjunction "and" is intended to be inclusive and the conjunction "or" is not intended to be exclusive. For example, the phrase "or alternatively" is intended to be exclusive. As used herein, the term "and / or" refers to any combination of the aforementioned elements, including the use of a single element.

[0073] When used in conjunction with a measurable numerical variable, the term "about" or "approximately" refers to the indicated value of the variable and all values ​​of the variable that are within the experimental error of the indicated value (e.g., within 95% confidence limits of the mean) or within a percentage of the indicated value (e.g., ±10%, ±5%), whichever is greater.

[0074] As used herein, “C x-y " indicates the number of carbon atoms in the chain. For example, C 1-6 Alkyl refers to an alkyl chain having a chain of 1 to 6 carbons (eg, methyl, ethyl, propyl, butyl, pentyl, and hexyl). Unless otherwise specifically stated, the chain may be straight or branched.

[0075] Unless otherwise indicated, "alkyl" refers to a hydrocarbon group that can be linear, branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, etc.), cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, etc.), or polycyclic (e.g., norbornyl, adamantyl, etc.). These alkyl moieties may be substituted or unsubstituted.

[0076] "Halogenated alkyl" refers to a straight chain, cyclic or branched saturated alkyl group as defined above, in which one or more hydrogens have been replaced by halogens (e.g., F, Cl, Br and I). Thus, for example, a fluorinated alkyl group (also referred to as a "fluoroalkyl group") refers to a straight chain, cyclic or branched saturated alkyl group as defined above, in which one or more hydrogens have been replaced by fluorine (e.g., trifluoromethyl, perfluoroethyl, 2,2,2-trifluoroethyl, perfluoroisopropyl, perfluorocyclohexyl, etc.). Such a haloalkyl moiety (e.g., a fluoroalkyl moiety) may be unsubstituted or further substituted if it is not perhalogenated / polyhalogenated.

[0077] "Alkoxy" (also known as "alkyloxy") refers to an alkyl group as defined above attached through an oxy (-O-) moiety (e.g., methoxy, ethoxy, propoxy, butoxy, 1,2-isopropoxy, cyclopentyloxy, cyclohexyloxy, etc.). These alkoxy moieties may be substituted or unsubstituted.

[0078] "Alkylcarbonyl" refers to an alkyl group as defined above attached through a carbonyl (-C(=O-)) moiety (eg, methylcarbonyl, ethylcarbonyl, propylcarbonyl, butylcarbonyl, cyclopentylcarbonyl, etc.) These alkylcarbonyl moieties may be substituted or unsubstituted.

[0079] "Halo" or "halide" refers to a halogen (eg, F, Cl, Br, and I).

[0080] "Hydroxy" (also known as "hydroxyl") refers to an -OH group.

[0081] Unless otherwise indicated, when referring to alkyl, alkoxy, fluorinated alkyl, etc., the term "substituted" refers to one of these moieties that also contains one or more substituents, including but not limited to the following substituents: alkyl, substituted alkyl, unsubstituted aryl, substituted aryl, alkyloxy, alkylaryl, haloalkyl, halo, hydroxy, amino, and aminoalkyl. Similarly, the term "unsubstituted" refers to these same moieties in which no substituents are present except hydrogen.

[0082] The section headings used herein are for organizational purposes and should not be construed as limiting the subject matter described. All documents or portions of documents cited in this application (including but not limited to patents, patent applications, articles, books, and papers) are expressly incorporated herein by reference in their entirety for any purpose. In the event that any of the incorporated documents and similar materials defines a term in a manner inconsistent with the definition of the term in this application, the present application shall prevail.

[0083] Detailed description

[0084] It should be understood that the foregoing general description and the following detailed description are illustrative and explanatory and do not limit the subject matter as claimed. The objects, features, advantages and concepts of the disclosed subject matter will be apparent to those skilled in the art from the description provided in this specification, and those skilled in the art will be able to easily practice the disclosed subject matter based on the description presented herein. The description of any "preferred embodiments" and / or examples showing preferred modes for practicing the disclosed subject matter are included for explanation purposes, and the "preferred embodiments" and / or examples are not intended to limit the scope of the claims.

[0085] It will also be apparent to those skilled in the art that various modifications may be made in how to practice the disclosed subject matter based on the aspects described in this specification without departing from the spirit and scope of the subject matter disclosed herein.

[0086] As described above, the disclosed subject matter relates to a rinse agent comprising (i) acetic acid and / or a halogenated acetic acid of structure A and (ii) anisole and / or a derivative of anisole (i.e., a compound other than anisole within the scope of structure B), which can be used to remove EPL and residual hard mask components (e.g., metals such as tin or titanium) from the edge and near-surface of a wafer / substrate surface during a photolithography process.

[0087] Rinse agent components

[0088] The flushing agent includes (i) acetic acid (CAS 64-19-7) or a halogenated acetic acid of structure A and (ii) anisole (CAS 100-66-3; also known as methoxybenzene or methylphenyl ether) and / or anisole derivatives in varying concentrations. The flushing agent includes, for example, between about 15% to about 35% by weight acetic acid and between about 85% and about 65% by weight anisole and / or anisole derivatives. The flushing agent may alternatively include between about 1% and about 10% by weight halogenated acetic acid of structure A and between about 99% and about 90% by weight anisole and / or a compound having structure B.

[0089] Those skilled in the art will recognize that amounts exceeding about 35 wt % acetic acid or amounts exceeding about 10 wt % of halogenated acetic acid of Structure A will generally have an adverse effect on the wafer / substrate and / or other features imprinted thereon, even though such compositions are effective in removing EPL and residual hardmask components. However, to the extent that the wafer / substrate can withstand exposure to higher weight percentages of acetic acid or halogenated acetic acid of Structure A, the disclosed rinse agents may include amounts exceeding about 35 wt % acetic acid or amounts exceeding about 10 wt % of halogenated acetic acid of Structure A.

[0090] Those skilled in the art will also readily recognize that the amounts of acetic acid and / or halogenated acetic acid of structure A and anisole and / or derivatives of anisole can be adjusted within these ranges, and that all such combinations thereof are within the scope of the disclosed subject matter, and that the relative amounts of the combination of acetic acid and / or halogenated acetic acid of structure A and anisole and / or derivatives of anisole do not necessarily need to equal 100 weight percent. In one embodiment, for example, the rinse agent includes about 20 weight percent acetic acid and about 75 weight percent anisole and / or derivatives of anisole. In another embodiment, the rinse agent includes about 30 weight percent acetic acid and about 70 weight percent anisole and / or derivatives of anisole. In yet another embodiment, the rinse agent may include about 32.5 weight percent acetic acid and about 67 weight percent anisole and / or derivatives of anisole. In yet another embodiment, the rinse agent may include about 18.5 weight percent acetic acid and about 75 weight percent anisole and / or derivatives of anisole. In other embodiments, the rinse agent may include about 2% by weight of the halogenated acetic acid of structure A and about 98% by weight of anisole and / or anisole derivatives. In other embodiments, the rinse agent may include about 4% by weight of the halogenated acetic acid of structure A and about 96% by weight of anisole and / or anisole derivatives. In other embodiments, the rinse agent may include about 10% by weight of the halogenated acetic acid of structure A and about 90% by weight of anisole and / or anisole derivatives.

[0091] Those skilled in the art will further recognize that a flushing agent comprising between "about 15% and about 35% by weight" of acetic acid or between "about 1% and about 10% by weight" of a halogenated acetic acid of structure A is not a strictly defined range and may include amounts of acetic acid and / or halogenated acetic acid of structure A that are slightly outside of those ranges. In one embodiment, for example, a flushing agent comprising between "about 15% and about 35% by weight" of acetic acid and / or between "about 1% and about 10% by weight" of a halogenated acetic acid of structure A may include ±10% weight percentage of acetic acid and / or halogenated acetic acid of structure A. Thus, an embodiment of a flushing agent comprising "about 15% by weight" of acetic acid may include between 13.5% and 16.5% by weight of acetic acid. An embodiment of a flushing agent comprising "about 20% by weight" of acetic acid may include between 18% and 22% by weight of acetic acid. An embodiment of a flushing agent comprising "about 30% by weight" of acetic acid may include between 27% and 33% by weight of acetic acid. Similarly, embodiments of flushing agents including "about 2 wt %" of halogenated acetic acid of Structure A may include between 1.8 wt % and 2.2 wt % of halogenated acetic acid of Structure A. Embodiments of flushing agents including "about 4 wt %" of halogenated acetic acid of Structure A may include between 3.6 wt % and 4.4 wt % of halogenated acetic acid of Structure A. Embodiments of flushing agents including "about 10 wt %" of halogenated acetic acid of Structure A may include between 9 wt % and 11 wt % of halogenated acetic acid of Structure A.

[0092] In one embodiment, for example, a flushing agent including between "about 15% and about 35% by weight" of acetic acid and / or between "about 1% and about 10% by weight" of a halogenated acetic acid of structure A may include ±5% weight percentage of acetic acid and / or halogenated acetic acid of structure A. Thus, embodiments of flushing agents including "about 15% by weight" of acetic acid may include between 14.25% and 15.75% by weight of acetic acid. Embodiments of flushing agents including "about 20% by weight" of acetic acid may include between 19% and 21% by weight of acetic acid. Embodiments of flushing agents including "about 30% by weight" of acetic acid may include between 28.5% and 31.5% by weight of acetic acid. Similarly, embodiments of flushing agents including "about 2% by weight" of a halogenated acetic acid of structure A may include between 1.9% and 2.1% by weight of a halogenated acetic acid of structure A. Embodiments of flushing agents including "about 4 wt %" of halogenated acetic acid may include between 3.8 wt % and 4.2 wt % of halogenated acetic acid of structure A. Embodiments of flushing agents including "about 10 wt %" of halogenated acetic acid of structure A may include between 9.5 wt % and 10.5 wt % of halogenated acetic acid of structure A.

[0093] Those skilled in the art will further recognize that flushing agents including between "about 85% and about 65% by weight" or between "about 99% and about 90% by weight" of anisole and / or derivatives of anisole are not strictly defined ranges and may include amounts of anisole and / or derivatives of anisole slightly outside of those ranges. In one embodiment, for example, flushing agents including between "about 85% and about 65% by weight" of anisole and / or derivatives of anisole may include ±10% weight percentage of anisole and / or derivatives of anisole. Thus, embodiments of flushing agents including "about 85% by weight" of anisole and / or derivatives of anisole may include between 93.5% and 76.5% by weight of anisole and / or derivatives of anisole. Embodiments of flushing agents including "about 80% by weight" of anisole and / or derivatives of anisole may include between 88% and 72% by weight of anisole and / or derivatives of anisole. Embodiments of the irrigant comprising "about 70% by weight" of anisole and / or derivatives of anisole may comprise between 77% and 63% by weight of anisole and / or derivatives of anisole.

[0094] In another embodiment, for example, an irrigant including between "about 85% and about 65% by weight" of anisole and / or derivatives of anisole may include ±5% by weight percentage of anisole and / or derivatives of anisole. Thus, embodiments of irrigants including "about 85% by weight" of anisole and / or derivatives of anisole may include between 89.25% and 80.75% by weight of anisole and / or derivatives of anisole. Embodiments of irrigants including "about 80% by weight" of anisole and / or derivatives of anisole may include between 84% and 76% by weight of anisole and / or derivatives of anisole. Embodiments of irrigants including "about 70% by weight" of anisole and / or derivatives of anisole may include between 76.5% and 73.5% by weight of anisole and / or derivatives of anisole.

[0095] In another embodiment, the flushing agent consists essentially of: (i) acetic acid and / or halogenated acetic acid of structure A and (ii) anisole and / or derivatives of anisole in different concentrations. In such an embodiment, the combined amount of acetic acid and / or halogenated acetic acid of structure A and anisole and / or derivatives of anisole is not equal to 100% by weight, and may include other ingredients that do not substantially change the effectiveness of the flushing agent (e.g., one or more additional solvents including water, common additives and / or impurities). Therefore, in other embodiments, the flushing agent may include acetic acid and / or halogenated acetic acid of structure A with different amounts of water. In one such embodiment, the flushing agent may include acetic acid and / or halogenated acetic acid of structure A with more than 1% by weight of water. In another such embodiment, the flushing agent may include anhydrous acetic acid (also known as glacial acetic acid) (i.e., acetic acid with less than 1% by weight of water). For example, such an embodiment may also include different technical grades of acetic acid, anhydrous / glacial acetic acid and / or halogenated acetic acid of structure A with different amounts of impurities (e.g., reagent grade, trace grade, ultra-trace grade, electronic grade, HPLC grade, etc.).

[0096] In another embodiment, the flushing agent consists of (i) acetic acid and / or a halogenated acetic acid of structure A and (ii) anisole and / or a derivative of anisole in varying concentrations. In such an embodiment, the combined amount of acetic acid and / or a halogenated acetic acid of structure A and anisole and / or a derivative of anisole is equal to about 100% by weight, but may also include other minor and / or trace amounts of impurities, which are present in such minor amounts that do not substantially change the effectiveness of the flushing agent. For example, in one such embodiment, the flushing agent may contain 2% by weight or less of total impurities and / or other ingredients (e.g., one or more additional solvents including water). In another embodiment, the flushing agent may contain 1% by weight or less of total impurities and / or other ingredients (e.g., one or more additional solvents including water). In another embodiment, the flushing agent may contain 0.05% by weight or less of total impurities and / or other ingredients (e.g., one or more additional solvents including water). For example, such an embodiment may include anhydrous / glacial acetic acid. For example, such embodiments may also include different technical grades (e.g., reagent grade, trace grade, ultra-trace grade, electronic grade, HPLC grade, etc.) of acetic acid, anhydrous / glacial acetic acid, and / or halogenated acetic acid of Structure A having different amounts of impurities. For example, such embodiments may also include trace amounts of metallic impurities present in amounts far below 0.05 wt % (e.g., at ppb levels).

[0097] Those skilled in the art will further recognize that the halogenated acetic acids of structure A that can be used in the disclosed flushing agents include (i) those halogenated acetic acid compounds of structure A, wherein R1 and R2 are each hydrogen and R3 is a halogen selected from fluorine, bromine, iodine and chlorine, (ii) those halogenated acetic acid compounds of structure A, wherein two or more of R1, R2 and R3 are the same halogen selected from fluorine, bromine, iodine and chlorine, and (iii) those halogenated acetic acid compounds of structure A, wherein two or more of R1, R2 and R3 are different halogens selected from fluorine, bromine, iodine and chlorine. Examples of such compounds include, but are not limited to, fluoroacetic acid, iodoacetic acid, bromoacetic acid, chloroacetic acid, difluoroacetic acid, trifluoroacetic acid, diiodoacetic acid, triiodoacetic acid, dibromoacetic acid, tribromoacetic acid, dichloroacetic acid, trichloroacetic acid, and halogenated acetic acids comprising two or more different halogens (e.g., wherein two or more of R1, R2 and R3 in structure A are each different halogens). The flushing agent may further include a mixture of two or more halogenated acetic acids of structure A.

[0098] Those skilled in the art will further recognize that derivatives of anisole, including variously substituted anisole compounds, can also be used in the disclosed flushing agents. In this regard, the disclosed flushing agents include a mixture of acetic acid or a halogenated acetic acid of structure A and anisole and / or anisole derivative of the following structure B:

[0099]

[0100] Structure B

[0101] As described above, R a , R b , R c , R d , R e , R f , R g and R h Each of can be independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted halogenated alkyl, substituted or unsubstituted alkylcarbonyl, halogen and hydroxy. Examples of specific derivatives of anisole suitable for use in the described and / or claimed rinse agents include, but are not limited to, halogenated anisole compounds (e.g., wherein R a , R b , R c , R d and R e One or more of which are independently fluorine, iodine, bromine or chlorine).

[0102] EPL Masking Agent

[0103] The disclosed rinse agent is suitable for removing EPL formed on the edge and near surface of the wafer / substrate. In one embodiment, the disclosed rinse agent is suitable for removing EPL formed by the masking agent described and / or claimed in PCT / EP2018 / 056322, including those masking agents having the following components:

[0104] a. A polymer comprising a unit having structure (I):

[0105]

[0106] in

[0107] X is selected from the group consisting of -SO2-, -C(=O)- and -O-;

[0108] A is a direct bond or A is selected from the group of structure (II):

[0109]

[0110] R1, R2, R3, R4 and R5 are each independently selected from the following group: H, halogen, (C 1-3 ) alkyl, (C 1-3 ) fluorinated alkyl, hydroxyl, (C 1-3 ) alkoxy and (C 1-3 )alkylcarbonyl; and

[0111] q, r, s and t are each independently selected from the group consisting of: 0, 1, 2, 3 and 4; and

[0112] b. Organic solvents,

[0113] The average molecular weight of the polymer is less than 50,000.

[0114] In another embodiment where the EPL is formed from a composition disclosed and / or claimed in PCT / EP2018 / 056322, the flushing agent is particularly effective when the polymer unit having structure (I) shown above is one of the following, and preferably one of the following:

[0115] a.

[0116] b.

[0117] c. and

[0118] d.

[0119] When applied, the EPL may be applied, for example, at a width of at least about 0.5 mm. Alternatively, the EPL may be applied at a width of at least about 0.75 mm. Furthermore, the EPL may be applied at a width of no more than about 2.0 mm. Alternatively, the EPL may be applied at a width of no more than about 1.0 mm.

[0120] refer to Figure 1 , when applying the EPL to the wafer / substrate 1, the EPL is applied to the edge 2 of the wafer / substrate and to one or more surfaces of the wafer / substrate adjacent to the edge of the wafer / substrate (i.e., the top surface 3 and / or the bottom surface 4). Thus, the EPL may be positioned to cover the edge of the substrate and extend over the front and / or back side of the substrate. For example, the EPL may be applied to the near surface of the edge and extend to a width of about 0.5 mm to about 2.0 mm on the top surface of the wafer / substrate, and to a width of about 2.5 mm on the edge and then on the back side of the wafer / substrate edge.

[0121] Hard Mask

[0122] As noted above, the disclosed rinse agents advantageously provide for simultaneous removal of applied EPL and residual hard mask components from the edge and near surface of the wafer / substrate (e.g., where the hard mask has penetrated or undercut the EPL). Examples of residual hard mask components that can be removed with the disclosed rinse agents include components of both metal hard mask compositions and metal oxide photoresist compositions used in photolithography processes. Suitable metal hardmask and metal oxide photoresist compositions include, but are not limited to, those described in U.S. Pat. Nos. 9,315,636, 8,568,958, 9,201,305, 9,296,922, 9,409,793, and 9,499,698 and U.S. Patent Application Nos. 62 / 437,449 (filed on Dec. 21, 2016) and 14 / 978,232 (filed on Dec. 22, 2015), which are hereby incorporated by reference in their entirety. Hardmask components that are removed or can be removed by the disclosed rinse agents include various metals, including tin, titanium, zirconium, tantalum, lead, antimony, thallium, indium, ytterbium, gallium, hafnium, aluminum, magnesium, molybdenum, germanium, iron, cobalt, nickel, copper, zinc, gold, silver, cadmium, tungsten, and platinum.

[0123] Regardless of the method used to apply the hard mask, the rinse agent can be effective for removing residual hard mask components. In this regard, in the disclosed method / process, the hard mask composition can be applied to the wafer / substrate surface to form a hard mask using any of a variety of techniques. Suitable techniques include, but are not limited to, spin-on coating, chemical vapor deposition (CVD), and atomic layer deposition (ALD). When spin coating is utilized, it is preferred to use at least one casting solvent, wherein the solvent used should not adversely affect the EPL. Therefore, suitable casting solvents for the hard mask composition include, but are not limited to, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), ethyl lactate, methoxyethanol, ethoxypropanol, ethoxyethanol, 1-pentanol, 4-methyl-2-pentanol, and mixtures thereof.

[0124] In the disclosed method / process, any of a variety of techniques may be used to remove the portion of the hard mask composition in contact with the EPL. It will be appreciated by those skilled in the art that removal of the portion of the hard mask composition in contact with the EPL should not have an adverse effect on the portion of the hard mask composition that is not in contact with the EPL. Suitable techniques include, but are not limited to, chemical mechanical polishing (CMP), plasma etching, and wet etching. When wet etching is utilized, any of a variety of solvents (such as EBR) may be used, with the proviso that the solvent does not have an adverse effect on the EPL or the hard mask. Suitable EBRs include, but are not limited to, PGMEA, PGME, ethyl lactate, methoxyethanol, ethoxypropanol, ethoxyethanol, 1-pentanol, 4-methyl-2-pentanol, and mixtures thereof.

[0125] In the disclosed methods / processes, the hardmask composition can be treated by various techniques to form a hardmask. For example, the hardmask composition can be treated by heating at a temperature between about 150° C. and about 450° C. for a time between about 60 seconds and about 120 seconds.

[0126] Typical electronic devices that may be fabricated using the compositions and methods of the disclosed subject matter include, but are not limited to, computer chips, integrated circuits, and semiconductor devices. Example

[0127] Reference will now be made to more specific embodiments of the invention and to experimental results providing support for such embodiments.The following examples are given to more fully illustrate the disclosed subject matter and should not be construed as limiting the disclosed subject matter in any way.

[0128] It will be apparent to those skilled in the art that various modifications and variations may be made in the disclosed subject matter and specific embodiments provided herein without departing from the spirit or scope of the disclosed subject matter. Therefore, it is intended that the disclosed subject matter (including the description provided by the following embodiments) covers modifications and variations of the disclosed subject matter that appear within the scope of any claims and their equivalents.

[0129] Materials and Methods

[0130] MHM 082 is a titanium-containing metal hard mask composition available from EMD Performance Materials.

[0131] EPL 003 is a polysulfone in anisole solution available from EMD Performance Materials.

[0132] U98 polymer is a high carbon-containing polymer available from EMD Performance Materials.

[0133] The ArF diluent was a 70 / 30 (by weight) mixture of PGMEA / PGME available from EMD Performance Materials.

[0134] Metal content was determined by ICP-MS on an Elan DRC II using the following operating parameters:

[0135]

[0136]

[0137] Metal Hard Mask ("MHM") Formulation: To evaluate the effectiveness of removing any remaining components of the hard mask, an MHM formulation containing a masking agent for coating onto a wafer / substrate ("MHM Formulation") was prepared by combining MHM 082 (2514.285 g), triethanolamine (314.285 g), and U-98 polymer (78.57 g) and dissolving in ArF diluent (12,092.857 g) and filtering through a 0.2 micron filter.

[0138] Example 1: The MHM formulation was spin coated (7500 rpm) on a wafer without any baking, and the wafer was immersed in 100% anisole on a laboratory hot plate until all the film was removed. The wafer was then washed for 6 minutes with an acid solution of HCl and hydrogen peroxide, which was prepared by adding about 30.4 g of water to a flask to which 35.7 g of hydrogen peroxide (30%) and 33.9 g of HCl (37%) were added under stirring (about 1 hour). The titanium content of the extracted solution was determined by ICP-MS to be 89.14 ppb as described above.

[0139] Example 2: The MHM formulation was spin coated (7500 rpm) on a wafer without any baking and the wafer was immersed in a mixture of 5% (by weight) acetic acid and 95% (by weight) anisole on a laboratory hot plate until all the film was removed. The wafer was then washed for 6 minutes with an acid solution of HCl and hydrogen peroxide, which was prepared by adding about 30.4 g of water to a flask to which 35.7 g of hydrogen peroxide (30%) and 33.9 g of HCl (37%) were added under stirring (about 1 hour). The titanium content of the extracted solution was determined by ICP-MS to be 89.14 ppb as described above.

[0140] Example 3: The MHM formulation was spin coated (7500 rpm) on a wafer without any baking and the wafer was immersed in a mixture of 10% (by weight) acetic acid and 90% (by weight) anisole on a laboratory hot plate until all the film was removed. The wafer was then washed for 6 minutes with an acid solution of HCl and hydrogen peroxide, which was prepared by adding about 30.4 g of water to a flask to which 35.7 g of hydrogen peroxide (30%) and 33.9 g of HCl (37%) were added under stirring (about 1 hour). The titanium content of the extracted solution was determined by ICP-MS to be 90.33 ppb as described above.

[0141] Example 4: The MHM formulation was spin coated (7500 rpm) on a wafer without any baking and the wafer was immersed in a mixture of 20% (by weight) acetic acid and 80% (by weight) anisole on a laboratory hot plate until all the film was removed. The wafer was then washed for 6 minutes with an acid solution of HCl and hydrogen peroxide, which was prepared by adding about 30.4 g of water to a flask to which 35.7 g of hydrogen peroxide (30%) and 33.9 g of HCl (37%) were added under stirring (about 1 hour). The titanium content of the extracted solution was determined by ICP-MS to be 58.73 ppb as described above.

[0142] Example 5: The MHM formulation was spin coated (7500 rpm) on a wafer without any baking and the wafer was immersed in a mixture of 30% (by weight) acetic acid and 70% (by weight) anisole on a laboratory hot plate until all the film was removed. The wafer was then washed for 6 minutes with an acid solution of HCl and hydrogen peroxide, which was prepared by adding about 30.4 g of water to a flask to which 35.7 g of hydrogen peroxide (30%) and 33.9 g of HCl (37%) were added under stirring (about 1 hour). The titanium content of the extracted solution was determined by ICP-MS to be 58.84 ppb as described above.

[0143] Example 6: The MHM formulation was spin coated (7500 rpm) on a wafer without any baking and the wafer was immersed in a mixture of 2% (by weight) trifluoroacetic acid and 98% (by weight) anisole on a laboratory hot plate until all the film was removed. The wafer was then washed for 6 minutes with an acid solution of HCl and hydrogen peroxide, which was prepared by adding about 30.4 g of water to a flask to which 35.7 g of hydrogen peroxide (30%) and 33.9 g of HCl (37%) were added under stirring (about 1 hour). The titanium content of the extracted solution was determined by ICP-MS to be 49.2 ppb as described above.

[0144] Example 7: The MHM formulation was spin coated (7500 rpm) on a wafer without any baking and the wafer was immersed in a mixture of 4% (by weight) trifluoroacetic acid and 96% (by weight) anisole on a laboratory hot plate until all the film was removed. The wafer was then washed for 6 minutes with an acid solution of HCl and hydrogen peroxide, which was prepared by adding about 30.4 g of water to a flask to which 35.7 g of hydrogen peroxide (30%) and 33.9 g of HCl (37%) were added under stirring (about 1 hour). The titanium content of the extracted solution was determined by ICP-MS to be 50.89 ppb as described above.

[0145] Example 8: The MHM formulation was spin coated (7500 rpm) on a wafer without any baking and the wafer was immersed in a mixture of 10% (by weight) trifluoroacetic acid and 90% (by weight) anisole on a laboratory hot plate until all the film was removed. The wafer was then washed for 6 minutes with an acid solution of HCl and hydrogen peroxide, which was prepared by adding about 30.4 g of water to a flask to which 35.7 g of hydrogen peroxide (30%) and 33.9 g of HCl (37%) were added under stirring (about 1 hour). The titanium content of the extracted solution was determined by ICP-MS to be 49.13 ppb as described above.

[0146] result

[0147] As shown in Table 1 below, for rinse agents including between about 15 wt % and 35 wt % acetic acid and between about 85 wt % and 65 wt % anisole, a significant and unexpected decrease in the residue amount (ie, the amount of metal residue) of the coated hardmask was observed.

[0148]

[0149]

[0150] Table 1

[0151] As shown in Table 1 below, for example, a flushing agent including between about 20 and 30 wt % acetic acid and between about 80 and 70 wt % anisole unexpectedly reduced residual metal content by 35% compared to other mixtures of acetic acid and anisole.

[0152] As shown in Table 2 below, the use of trifluoroacetic acid (i.e., the halogenated acetic acid compound of Structure A) also demonstrated a significant and unexpected reduction in the residual amount (i.e., the amount of metal residue) of the coated hard mask. In particular, when a rinse agent including between about 1 wt % and 10 wt % trifluoroacetic acid and between about 99 wt % and 90 wt % anisole was used, a reduction in the residual amount of titanium was observed.

[0153]

[0154] Table 2

[0155] As shown in Table 2, for example, rinses including between about 2 wt % and 10 wt % trifluoroacetic acid and between about 98 wt % and 90 wt % anisole were surprisingly slightly more effective in removing residual metal content compared to the acetic acid formulation in Table 1. In particular, the average remaining metal residue value for the most effective acetic acid / anisole rinses (58.76 ppb) (i.e., 20 / 80 and 30 / 70) based on Table 1 was compared to the average remaining metal residue value for the trifluoroacetic acid / anisole rinse of Table 2 (49.74 ppb), demonstrating that the trifluoroacetic acid-containing rinse was about 15% more effective in removing residual amounts of the applied hardmask.

[0156] Although the disclosed and claimed subject matter has been described and illustrated with a certain degree of particularity, it is to be understood that the present disclosure is disclosed by way of example only and that those skilled in the art may resort to various changes in conditions and order of steps without departing from the spirit and scope of the disclosed and claimed subject matter.

Claims

1. A flushing agent comprising (i) between 15% and 35% by weight of acetic acid and (ii) between 85% and 65% by weight of a compound having structure B: Where R a , R b , R c , R d , R e , R f , R g and R h Each of which may independently be hydrogen, substituted or unsubstituted C 1-6 Alkyl, substituted or unsubstituted C 1-6 Alkylcarbonyl, halogen or hydroxy.

2. The flushing agent according to claim 1, wherein R a , R b , R c , R d , R e , R f , R g and R h Each of which may independently be a substituted or unsubstituted halogenated C 1-6 alkyl.

3. The flushing agent according to claim 1 or 2, wherein R in structure B a , R b , R c , R d , R e , R f , R g and R h Each of is hydrogen.

4. The flushing agent according to claim 1 or 2, wherein the flushing agent contains 15% by weight of acetic acid.

5. The flushing agent according to claim 1 or 2, wherein the flushing agent contains 20% by weight of acetic acid.

6. The flushing agent according to claim 1 or 2, wherein the flushing agent contains 25% by weight of acetic acid.

7. The flushing agent according to claim 1 or 2, wherein the flushing agent contains 30% by weight of acetic acid.

8. The flushing agent according to claim 1 or 2, wherein the flushing agent contains 35% by weight of acetic acid.

9. A method for cleaning a wafer or substrate, comprising: The wafer or substrate is washed with a rinse agent according to claim 1 or 2 .

10. The method according to claim 9, wherein R in structure B a , R b , R c , R d , R e , R f , R g and R h Each of is hydrogen.

11. The method according to claim 9, wherein the flushing agent contains 15 wt % acetic acid, and wherein R a , R b , R c , R d , R e , R f , R g and R h Each of is hydrogen.

12. The method according to claim 9, wherein the flushing agent contains 20 wt % acetic acid, and wherein R a , R b , R c , R d , R e , R f , R g and R h Each of is hydrogen.

13. The method according to claim 9, wherein the flushing agent contains 25 wt % acetic acid, and wherein R a , R b , R c , R d , R e , R f , R g and R h Each of is hydrogen.

14. The method according to claim 9, wherein the flushing agent contains 30 wt % acetic acid, and wherein R a , R b , R c , R d , R e , R f , R g and R h Each of is hydrogen.

15. The method according to claim 9, wherein the flushing agent contains 35 wt % acetic acid, and wherein R a , R b , R c , R d , R e , R f , R g and R h Each of is hydrogen.

16. The method according to claim 9, further comprising one or more steps selected from the group consisting of: (a) applying a masking agent to the edge and at least one near surface of the wafer or substrate; (b) heating the applied masking agent to form an edge protection layer on the edge and at least one near surface of the wafer or substrate; (c) applying a hard mask composition to the wafer or substrate and the edge protection layer; (d) removing at least a portion of the coated hardmask composition in contact with the edge protection layer, wherein the removing comprises rinsing the hardmask composition with at least one edge bead remover material; (e) heating the applied hard mask composition to form a hard mask; and (f) performing at least one post-coating bake.

17. A flushing agent comprising (i) between 1% and 10% by weight of a halogenated acetic acid of structure A: wherein R1 and R2 are independently hydrogen or halogen and R3 is halogen; and (ii) between 99% and 90% by weight of a compound having structure B: Where R a , R b , R c , R d , R e , R f , R g and R h Each of which may independently be hydrogen, substituted or unsubstituted C 1-6 Alkyl, substituted or unsubstituted C 1-6 Alkylcarbonyl, halogen or hydroxy.

18. The flushing agent according to claim 17, wherein R a , R b , R c , R d , R e , R f , R g and R h Each of which may independently be a substituted or unsubstituted halogenated C 1-6 alkyl.

19. The flushing agent according to claim 17 or 18, wherein R in structure B a , R b , R c , R d , R e , R f , R g and R h Each of is hydrogen.

20. The flushing agent according to claim 17 or 18, wherein in the halogenated acetic acid of structure A, R1 and R2 are each hydrogen and R3 is a halogen selected from fluorine, bromine, iodine and chlorine.

21. The flushing agent according to claim 17 or 18, wherein in the halogenated acetic acid of structure A, two or more of R1, R2 and R3 are halogens selected from fluorine, bromine, iodine and chlorine.

22. The flushing agent according to claim 17 or 18, wherein the halogenated acetic acid of structure A is difluoroacetic acid, and wherein R a , R b , R c , R d , R e , R f , R g and R h Each of is hydrogen.

23. The flushing agent according to claim 17 or 18, wherein the halogenated acetic acid of structure A is trifluoroacetic acid, and wherein R a , R b , R c , R d , R e , R f , R g and R h Each of is hydrogen.

24. A method for cleaning a wafer or substrate, comprising: The wafer or substrate is washed with a rinse agent according to claim 17 or 18 .

25. The method according to claim 24, further comprising one or more steps selected from the group consisting of: (a) applying a masking agent to the edge and at least one near surface of the wafer or substrate; (b) heating the applied masking agent to form an edge protection layer on the edge and at least one near surface of the wafer or substrate; (c) applying a hard mask composition to the wafer or substrate and the edge protection layer; (d) removing at least a portion of the coated hardmask composition in contact with the edge protection layer, wherein the removing comprises rinsing the hardmask composition with at least one edge bead remover material; (e) heating the applied hard mask composition to form a hard mask; and (f) performing at least one post-coating bake.

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