Cleaning agents and their use for removing edge protection layers and residual metal hardmask components - Patents.com

Abstract

To provide a rinse and methods of use thereof for removing an edge protection layer and residual hardmask components (e.g., metals) from the edge and at least one proximate surface of a wafer / substrate.SOLUTION: A rinse includes (i) acetic acid and / or a halogenated acetic acid and (ii) a compound having the structure below (where, Ra-Rh independently may be hydrogen, a substituted / unsubstituted (C1-6) alkyl group, a substituted / unsubstituted halogenated (C1-6) alkyl group, a substituted / unsubstituted (C1-6) alkylcarbonyl group, a halogen or a hydroxy group).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The disclosed invention relates to a cleaning agent and its use for removing edge protection layers in lithographic patterning processes. The new cleaning agent is formulated to remove both edge protection layers and residual hard mask components (e.g., metals) from wafer / substrate surfaces. [Background technology]

[0002] Multiple antireflective layers and hard masks are used in advanced lithographic patterning processes. For example, when a photoresist does not provide sufficient dry etch resistance, an underlayer and / or antireflective coating for the photoresist is preferred, which acts as a hard mask and has high etch resistance during substrate etching. One approach has been to incorporate silicon, titanium, zirconium, aluminum, or other metallic materials into layers beneath an organic photoresist layer. Additionally, other high-carbon content antireflective or mask layers can be placed beneath the metal-containing antireflective layer to form a high-carbon film / hard mask film / photoresist trilayer. Such layers can be used to improve the lithographic performance of the imaging process. However, metal contamination in lithography and etching tools, as well as cross-contamination between wafers during manufacturing, can be problems to be avoided.

[0003] One method 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 incorporated herein by reference in its entirety. According to Iwao, a maskant is applied 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 over the wafer / substrate and EPL. The hard mask composition overlying the edge protection layer is removed using an edge bead remover ("EBR"), and the hard mask composition is baked to form a hard mask. The EPL is then removed using an EPL removal solution. The result is a hard mask that is separated from the edge of the wafer / substrate, thereby reducing contamination.

[0004] Masking agents that form EPLs are described in patent application PCT / EP2018 / 056322 (published as WO / 2018 / 167112) entitled "Lithographic Compositions and Methods of Use Thereof," which is incorporated herein by reference in its entirety. The compositions disclosed therein prevent metal contamination at the substrate / wafer edge during the manufacture of electronic devices. As explained in PCT / EP2018 / 056322, it is desirable that the applied EPL be easily removable at a rate that enables and / or maintains industrially acceptable process times without negative or damaging effects on the hard mask (such as can occur with wet etching).

[0005] PCT / EP2018 / 056322 further describes a general method for applying a maskant to form an EPL in a method for fabricating an electronic device, as shown in Figures 2a-f. In such a process, a metal hardmask composition or a metal oxide photoresist composition (collectively, a "hardmask" or "hardmask composition") is applied over the substrate and the EPL (see Figure 2c). The EPL and hardmask composition are then cleaned with an EBR and / or a backside clean ("BR") material to remove at least the portion of the hardmask composition in contact with the EPL (see Figure 2d). Nevertheless, the portion(s) of the hardmask composition in contact with the EPL may remain even after cleaning with an EBR or BR. The hardmask composition may, for example, partially penetrate into the EPL or remove the underside of its edge. As a result, it is possible that some amount of the hardmask and / or its components in contact with the EPL are not removed during the EBR clean. To date, no compositions or processes / methods have been identified that provide simultaneous removal of both EPL and remaining residual components of the hard mask (e.g., metal). Instead, the EPL removal step must be followed by a subsequent process step (e.g., an additional EBR cleaning step) in which remaining residual components of the hard mask are removed from the edge and adjacent surfaces of the wafer / substrate. This additional step is not only costly but also time consuming, and therefore contradicts enabling and / or maintaining industrially acceptable process times when EPL is utilized.

[0006] Therefore, there is a continuing need for materials that can remove EPL and remaining hardmask residual components at a faster rate than known EPL cleaning agents while avoiding negative or damaging effects on the hardmask. As described below, the disclosed invention addresses known shortcomings in the prior art associated with removing EPL and remaining hardmask residual components. The disclosed invention provides compositions and methods and processes for rapidly and efficiently removing applied EPL and remaining hardmask components and residue from the edge and adjacent surfaces of a wafer / substrate. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] US$8,791,030 [Patent Document 2] PCT / EP2018 / 056322(WO / 2018 / 167112) [Patent Document 3] US$9,315,636 [Patent Document 4] US$8,568,958 [Patent Document 5] US9,201,305 [Patent Document 6] US$9,296,922 [Patent Document 7] US$9,409,793 [Patent Document 8] US$9,499,698 [Patent Document 9] US62 / 437,449 [Patent Document 10] US14 / 978,232 Summary of the Invention

[0008] In one aspect, the disclosed invention relates to a cleaning 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 lithography process, the cleaning agent comprising: (i) between approximately 15% and approximately 35% by weight of acetic acid; and (ii) between approximately 85% and approximately 65% ​​by weight of a compound having structure B.

[0009] [ka] In the formula, R a , R b , R c , R d , R e , R f , R g and R h are each independently hydrogen, a substituted or unsubstituted alkyl group (which is preferably C 1~6 alkyl groups), substituted or unsubstituted halogenated alkyl groups (which are preferably halogenated C 1~6 alkyl group), a substituted or unsubstituted alkylcarbonyl group (which is preferably C 1~6 In yet another aspect, the compound having structure B is an anisole (i.e., R in structure B is an alkylcarbonyl group), a halogen, and a hydroxy group. a , R b , R c , R d , R e , R f , R g and R h are hydrogen).

[0010] In one other aspect, the disclosed invention is a cleaning 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 lithography process, comprising: (i) between approximately 1% and approximately 10% by weight of a halogenated acetic acid of structure A;

[0011] [ka] wherein R1 and R2 are independently hydrogen or halogen, and R3 is halogen. (ii) between approximately 99% and approximately 90% by weight of compounds having structure B;

[0012] [ka] (In the formula, R a , R b , R c , R d , R e , R f , R g and R h are each independently hydrogen, a substituted or unsubstituted alkyl group (which is preferably C 1~6 alkyl groups), substituted or unsubstituted halogenated alkyl groups (which are preferably halogenated C 1~6 alkyl group), a substituted or unsubstituted alkylcarbonyl group (which is preferably C 1~6 alkylcarbonyl groups), halogen and hydroxy groups In yet another aspect, the compound having structure A is trifluoroacetic acid (i.e., R1, R2, and R3 in structure A are each fluorine) or difluoroacetic acid (i.e., R3, one of R1, and R2 are fluorine, and the other of R1 and R2 is hydrogen). In yet another aspect, the compound having structure B is anisole (i.e., R1 in structure B is a , R b , R c , R d , R e , R f , R g and R h are hydrogen).

[0013] In another aspect, the cleaning solution is particularly effective for removing EPL formed from the masking agent described and / or claimed in PCT / EP2018 / 056322 and residual hard mask components (e.g., metals such as tin or titanium) from the edge and adjacent surfaces of a wafer / substrate surface during lithography processing. In yet another aspect, the cleaning solution is particularly effective for removing EPL formed from the 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 polymeric units having one or more of the following formulae:

[0014] [ka] In another aspect, the cleaning 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 the compound having structure B. In another aspect, the cleaning agent comprises (i) about 15% by weight acetic acid, and (ii) preferably about 85% by weight anisole and / or the compound having structure B.

[0015] In another aspect, the cleaning agent comprises (i) approximately 20% by weight acetic acid, and (ii) preferably approximately 80% by weight anisole and / or a compound having structure B. In another aspect, the cleaning agent comprises (i) approximately 25% by weight acetic acid, and (ii) preferably approximately 75% by weight anisole and / or a compound having structure B.

[0016] In another aspect, the cleaning agent comprises (i) approximately 30% by weight acetic acid, and (ii) preferably approximately 70% by weight anisole and / or a compound having structure B.

[0017] In another aspect, the cleaning agent comprises (i) approximately 35% by weight acetic acid, and (ii) preferably approximately 65% ​​by weight anisole and / or a compound having structure B.

[0018] In another aspect, the cleaning agent comprises (i) between about 1% and about 10% by weight of trifluoroacetic acid and / or difluoroacetic acid, and (ii) between about 99% and about 90% by weight of anisole and / or a compound having structure B.

[0019] In another aspect, the cleaning agent comprises (i) approximately 1% by weight of a halogenated acetic acid of structure A and (ii) preferably approximately 99% by weight of anisole and / or a compound having structure B. In yet another aspect, the halogenated acetic acid of structure A is at least one of trifluoroacetic acid and difluoroacetic acid.

[0020] In another aspect, the cleaning agent comprises (i) approximately 2% by weight of a halogenated acetic acid of structure A and (ii) preferably approximately 98% by weight of anisole and / or a compound having structure B. In yet another aspect, the halogenated acetic acid of structure A is at least one of trifluoroacetic acid and difluoroacetic acid.

[0021] In another aspect, the cleaning agent comprises (i) approximately 3% by weight of a halogenated acetic acid of structure A and (ii) approximately 97% by weight of anisole and / or a compound having structure B. In yet another aspect, the halogenated acetic acid of structure A is at least one of trifluoroacetic acid and difluoroacetic acid.

[0022] In another aspect, the cleaning agent comprises (i) approximately 4% by weight of a halogenated acetic acid of structure A and (ii) preferably approximately 96% by weight of anisole and / or a compound having structure B. In yet another aspect, the halogenated acetic acid of structure A is at least one of trifluoroacetic acid and difluoroacetic acid.

[0023] In another aspect, the cleaning agent comprises (i) approximately 5% by weight of a halogenated acetic acid of structure A and (ii) approximately 95% by weight of anisole and / or a compound having structure B. In yet another aspect, the halogenated acetic acid of structure A is at least one of trifluoroacetic acid and difluoroacetic acid.

[0024] In another aspect, the cleaning agent comprises (i) approximately 6% by weight of a halogenated acetic acid of structure A and (ii) approximately 94% by weight of anisole and / or a compound having structure B. In yet another aspect, the halogenated acetic acid of structure A is at least one of trifluoroacetic acid and difluoroacetic acid.

[0025] In another aspect, the cleaning agent comprises (i) approximately 7% by weight of a halogenated acetic acid of structure A and (ii) preferably approximately 93% by weight of anisole and / or a compound having structure B. In yet another aspect, the halogenated acetic acid of structure A is at least one of trifluoroacetic acid and difluoroacetic acid.

[0026] In another aspect, the cleaning agent comprises (i) approximately 8% by weight of a halogenated acetic acid of structure A and (ii) approximately 92% by weight of anisole and / or a compound having structure B. In yet another aspect, the halogenated acetic acid of structure A is at least one of trifluoroacetic acid and difluoroacetic acid.

[0027] In another aspect, the cleaning agent comprises (i) approximately 9% by weight of a halogenated acetic acid of structure A and (ii) approximately 91% by weight of anisole and / or a compound having structure B. In yet another aspect, the halogenated acetic acid of structure A is at least one of trifluoroacetic acid and difluoroacetic acid.

[0028] In another aspect, the cleaning agent comprises (i) approximately 10% by weight of a halogenated acetic acid of structure A and (ii) preferably approximately 90% by weight of anisole and / or a compound having structure B. In yet another aspect, the halogenated acetic acid of structure A is at least one of trifluoroacetic acid and difluoroacetic acid.

[0029] In another aspect, the disclosed invention relates to methods and processes for using the cleaning agents to remove EPL and residual hard mask components (e.g., metals such as tin or titanium) from the edge and adjacent surfaces of wafer / substrate surfaces in lithography processes, including the manufacture of electronic devices.

[0030] In one aspect, the method and process includes removing the EPL and residual hard mask components (e.g., metals such as tin or titanium) by cleaning the wafer / substrate with the cleaning agent. Therefore, the method and process can also be referred to as a wafer or substrate cleaning method, which includes cleaning the wafer or substrate with the cleaning agent. In yet another aspect, the method and process includes treating the wafer / substrate edge and adjacent surfaces with a masking agent to form an EPL. In yet another aspect, the masking agent is a masking agent described and / or claimed in PCT / EP2018 / 056322 (Patent Document 2). In yet another aspect, the masking agent is a masking agent described and / or claimed in PCT / EP2018 / 056322 (Patent Document 2), wherein the masking agent includes polymeric units having one or more of the following formulae:

[0031] [ka] In another aspect, the methods and processes include one or more additional steps selected from the group consisting of: (a) heating the maskant to form an EPL; (b) applying a hardmask composition to the substrate and the EPL; (c) removing at least a portion of the hardmask composition in contact with the EPL by rinsing the hardmask composition and the EPL with an EBR and / or BR material; (d) heating the hardmask composition to form a hardmask; and (e) performing at least one post-applied bake.

[0032] In another aspect, the method and process include sequentially, without intervening steps, performing the following steps: (i) treating the wafer / substrate edge and adjacent surfaces with a maskant; (ii) heating the applied maskant to form an EPL; (iii) applying a hardmask composition to the substrate and the EPL; (iv) cleaning the hardmask composition and the EPL with an EBR and / or BR material to remove at least a portion of the hardmask composition in contact with the EPL; (v) heating the hardmask composition to form a hardmask; (vi) cleaning the wafer / substrate with the cleaning agent to remove the EPL and residual hardmask components; and (vii) optionally performing at least one post-applied bake. It will be apparent to those skilled in the art that the sequential performance of the above steps does not exclude the performance of steps (e.g., providing a wafer / substrate) before or after the sequential steps. In yet 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 polymeric units having one or more of the following formulae:

[0033] [ka] In another aspect, the disclosed invention provides a method and process for applying and removing an edge protection layer and residual hard mask components (e.g., metals such as tin or titanium) from a wafer / substrate, comprising the steps of: (a) applying a maskant onto the edge and adjacent surfaces of the wafer / substrate; (b) heating the maskant to form an EPL on the edge and adjacent surfaces of the wafer / substrate; (c) applying a hard mask composition onto the wafer / substrate and the EPL; and (d) 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) cleaning the wafer / substrate with a cleaning agent, the cleaning agent comprising (i) between approximately 15% and approximately 35% by weight of acetic acid, and (ii) between approximately 85% and approximately 65% ​​by weight of anisole and / or a compound having structure B; and (g) optionally, performing at least one post-applied bake step. In yet 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 polymeric units having one or more of the following formulae:

[0034] [ka] In another aspect, the disclosed invention provides a method and process for applying and removing an edge protection layer and residual hard mask components (e.g., metals such as tin or titanium) from a wafer / substrate, comprising the steps of: (a) applying a maskant onto the edge and adjacent surfaces of the wafer / substrate; (b) heating the maskant to form an EPL on the edge and adjacent surfaces of the wafer / substrate; (c) applying a hard mask composition onto the wafer / substrate and the EPL; and (d) removing the hard mask composition by rinsing the hard mask composition with at least one EBR and / or BR material. (e) removing at least a portion of the hard mask composition that is in contact with the EPL; (e) heating the hard mask composition to form a hard mask; (f) cleaning the wafer / substrate with a cleaning agent, the cleaning agent comprising: (i) between approximately 1% and approximately 10% by weight of a halogenated acetic acid of Structure A, and (ii) between approximately 99% and approximately 90% by weight of anisole and / or a compound having Structure B; and (g) optionally, performing at least one post-applied bake step. In yet another aspect, the masking agent is a masking agent described and / or claimed in PCT / EP2018 / 056322 (Patent Document 2). In yet another aspect, the masking agent is a masking agent described and / or claimed in PCT / EP2018 / 056322 (Patent Document 2), wherein the masking agent comprises polymeric units having one or more of the following formulae:

[0035] [ka] In yet another aspect, the halogenated acetic acid of structure A is at least one of trifluoroacetic acid and difluoroacetic acid.

[0036] The accompanying drawings provide a further understanding of the disclosed invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosed invention, and together with the description, serve to explain the principles of the disclosed invention. [Brief explanation of the drawings]

[0037] [Figure 1] FIG. 1 shows a wafer / substrate with EPL applied. [Figure 2] 2a-f are schematic diagrams of one embodiment of a method and process for using the cleaning solutions disclosed herein. In FIG. 2a, a maskant is applied to the edge of a substrate. In FIG. 2b, the maskant is heated to form an EPL. In FIG. 2c, a hardmask composition is applied over the substrate and EPL. In FIG. 2d, the hardmask composition and EPL are cleaned with EBR to remove at least the portion of the hardmask composition in contact with the EPL. In FIG. 2e, the hardmask composition is heated to form a hardmask. In FIG. 2f, the EPL and residual hardmask components (e.g., metals such as tin or titanium) are removed from the edge of the wafer / substrate with a cleaner. [Figure 3] FIG. 3 is a graph showing the residual metal (i.e., titanium) present on the wafer / substrate surface after removing EPL from the edge of the wafer / substrate surface using different disclosed cleaning formulations containing acetic acid and anisole. [Figure 4] FIG. 4 is a graph showing the residual metal (i.e., titanium) present on a wafer / substrate surface after removing EPL from the edge of the wafer / substrate surface using different disclosed cleaning formulations containing trifluoroacetic acid and anisole.

[0038] definition Unless otherwise stated, the following terms used in the specification and claims have the following meanings in this application.

[0039] As used herein, the use of the singular includes the plural, and unless specifically stated otherwise, the singular means "at least one." Furthermore, the use of the term "comprises," as well as other verb forms such as "comprise," is not limiting. Also, the use of terms such as "element" or "component" includes elements or components containing one unit, as well as elements or components containing more than one unit, unless specifically stated otherwise. As used herein, the conjunction "and" is intended to be inclusive, and the conjunction "or" is not intended to be exclusive unless otherwise indicated. For example, the phrase "or instead" 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.

[0040] The term "about" or "approximately," when used in connection with a measurable variable, refers to the stated value of the variable, as well as all values ​​of the variable that are within experimental error of the stated value (e.g., within a 95% confidence limit of the mean) or within a percentage of the stated value (e.g., within ±10%, within ±5%), whichever is greater.

[0041] As used here, "C x-y " indicates the number of carbon atoms in the chain. For example, C 1-6 Alkyl refers to alkyl groups having a chain of between 1 and 6 carbons (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl). Unless otherwise specifically stated, the chain can be linear or branched.

[0042] Unless otherwise specified, alkyl refers to a hydrocarbon group that can be linear, branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, and the like), cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, and the like), or polycyclic (e.g., norbornyl, adamantyl, and the like). These alkyl portions can be substituted or unsubstituted.

[0043] "Halogenated alkyl" refers to a linear, cyclic, or branched saturated alkyl group, as defined above, in which one or more of the hydrogens have been replaced with a halogen (e.g., F, Cl, Br, and I). Thus, for example, a fluorinated alkyl (also known as a "fluoroalkyl") refers to a linear, cyclic, or branched saturated alkyl group, as defined above, in which one or more of the hydrogens have been replaced with a fluorine (e.g., trifluoromethyl, perfluoroethyl, 2,2,2-trifluoroethyl, perfluoroisopropyl, perfluorocyclohexyl, and the like). Such haloalkyl moieties (e.g., fluoroalkyl moieties), when not perhalogenated / multihalogenated, may be unsubstituted or further substituted.

[0044] "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, and the like). These alkoxy moieties may be substituted or unsubstituted. "Alkylcarbonyl" refers to an alkyl group, as defined above, attached through a carbonyl (-C(=O)-) moiety (e.g., methylcarbonyl, ethylcarbonyl, propylcarbonyl, butylcarbonyl, cyclopentylcarbonyl, and the like). These alkylcarbonyl moieties may be substituted or unsubstituted.

[0045] "Halo" or "halide" refers to halogen (e.g., F, Cl, Br, and I).

[0046] "Hydroxy" (also known as "hydroxyl") refers to the --OH group.

[0047] Unless otherwise indicated, the term "substituted," when referring to alkyl, alkoxy, fluorinated alkyl, and the like, refers to one of these moieties that also contain one or more substituents, including, but not limited to, alkyl, substituted alkyl, unsubstituted aryl, substituted aryl, alkyloxy, alkylaryl, haloalkyl, halide, hydroxy, amino, and aminoalkyl. Similarly, the term "unsubstituted" refers to these same moieties in which there are no substituents other than hydrogen.

[0048] The section headings used herein are for organizational purposes only and should not be construed as limiting the subject matter described. All references or portions thereof cited herein, including but not limited to patents, patent applications, papers, books, and treatises, are incorporated herein in their entirety for all purposes. In the event that the definitions of terms in any of the references and similar materials cited herein conflict with those herein, the definitions herein shall control. DETAILED DESCRIPTION OF THE INVENTION

[0049] It should be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not intended to be limiting with respect to the invention as claimed. The objects, features, advantages, and concepts of the disclosed invention will be apparent to those skilled in the art from the description set forth herein, and the disclosed invention can be readily implemented by those skilled in the art based on the description set forth herein. The description of "preferred embodiments" and / or examples indicating preferred modes for carrying out the disclosed invention are included for illustrative purposes and are not intended to limit the scope of the claims.

[0050] It will also be apparent to those skilled in the art that various modifications may be made in the practice of the disclosed invention based on the aspects described herein without departing from the spirit and scope of the invention disclosed herein.

[0051] As previously described, the disclosed invention relates to a cleaning agent that includes (i) acetic acid and / or halogenated acetic acids of structure A, and (ii) anisole and / or derivatives of anisole (i.e., compounds other than anisole that fall within structure B), and that can be utilized to remove EPL and residual hard mask components (e.g., metals such as tin or titanium) from the edge and adjacent surfaces of a wafer / substrate surface in a lithography process.

[0052] Cleaning agent ingredients The cleaning agent contains various concentrations of (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 a derivative of anisole. The cleaning agent may contain, for example, between approximately 15% and approximately 35% by weight of acetic acid, and between approximately 85% and approximately 65% ​​by weight of anisole and / or a derivative of anisole. Alternatively, the cleaning agent may contain between approximately 1% and approximately 10% by weight of a halogenated acetic acid of structure A, and between approximately 99% and approximately 90% by weight of anisole and / or a compound having structure B.

[0053] It will be apparent to those skilled in the art that amounts of acetic acid greater than approximately 35% by weight or amounts of halogenated acetic acid of Structure A greater than approximately 10% by weight will generally have a detrimental effect on the wafer / substrate and / or other features applied thereto, even though such compositions are effective in removing EPL and residual hard mask components. However, if the wafer / substrate is one that is suitable for exposure to higher weight % acetic acid or halogenated acetic acid of Structure A, the disclosed cleaning solutions can include amounts greater than approximately 35% by weight or greater than approximately 10% by weight of acetic acid.

[0054] It will also be apparent to those skilled in the art that the amounts of acetic acid and / or halogenated acetic acid of Structure A and anisole and / or anisole derivatives can be adjusted within these ranges, and that all such combinations are within the scope of the disclosed invention, and that the total relative amounts of acetic acid and / or halogenated acetic acid of Structure A and anisole and / or anisole derivatives do not necessarily have to equal 100% by weight. In one embodiment, for example, the cleaning agent contains approximately 20% by weight of acetic acid and approximately 75% by weight of anisole and / or anisole derivatives. In another embodiment, the cleaning agent contains approximately 30% by weight of acetic acid and approximately 70% by weight of anisole and / or anisole derivatives. In yet another embodiment, the cleaning agent can contain approximately 32.5% by weight of acetic acid and approximately 67% by weight of anisole and / or anisole derivatives. In yet another embodiment, the cleaning agent can contain approximately 18.5% by weight of acetic acid and approximately 75% by weight of anisole and / or anisole derivatives. In a further embodiment, the cleaning agent can comprise approximately 2% by weight of a halogenated acetic acid of structure A and approximately 98% by weight of anisole and / or anisole derivatives. In a further embodiment, the cleaning agent can comprise approximately 4% by weight of a halogenated acetic acid of structure A and approximately 96% by weight of anisole and / or anisole derivatives. In yet another embodiment, the cleaning agent can comprise approximately 10% by weight of a halogenated acetic acid of structure A and approximately 90% by weight of anisole and / or anisole derivatives.

[0055] Furthermore, it will be apparent to those skilled in the art that cleaning agents containing between "approximately 15% and approximately 35% by weight" acetic acid or between "approximately 1% and approximately 10% by weight" halogenated acetic acid of Structure A are not strict limits and may contain amounts of acetic acid and / or halogenated acetic acid of Structure A slightly outside these ranges. In one embodiment, for example, a cleaning agent containing between "approximately 15% and approximately 35% by weight" acetic acid and / or between "approximately 1% and approximately 10% by weight" halogenated acetic acid of Structure A may contain ±10% of the weight percentages. Thus, one embodiment of a cleaning agent containing "approximately 15% by weight" acetic acid may contain between 13.5% and 16.5% by weight acetic acid. One embodiment of a cleaning agent containing "approximately 20% by weight" acetic acid may contain between 18% and 22% by weight acetic acid. An embodiment of a cleaning agent containing "approximately 30% by weight" acetic acid can contain between 27% and 33% by weight acetic acid. Similarly, an embodiment of the cleaning agent containing "approximately 2% by weight" halogenated acetic acid of structure A can contain between 1.8% and 2.2% by weight of halogenated acetic acid of structure A. An embodiment of the cleaning agent containing "approximately 4% by weight" halogenated acetic acid of structure A can contain between 3.6% and 4.4% by weight of halogenated acetic acid of structure A. An embodiment of the cleaning agent containing "approximately 10% by weight" halogenated acetic acid of structure A can contain between 9% and 11% by weight of halogenated acetic acid of structure A.

[0056] In one embodiment, for example, a cleaning agent containing between "approximately 15% and approximately 35% by weight" acetic acid and / or between "approximately 1% and approximately 10% by weight" halogenated acetic acid of structure A can contain ±5% of said weight percentages of acetic acid and / or halogenated acetic acid of structure A. Thus, one embodiment of a cleaning agent containing "approximately 15% by weight" acetic acid can contain between 14.25% and 15.75% by weight acetic acid. One embodiment of the cleaning agent containing "approximately 20% by weight" acetic acid can contain between 19% and 21% by weight acetic acid. One embodiment of the cleaning agent containing "approximately 30% by weight" acetic acid can contain between 28.5% and 31.5% by weight acetic acid. Similarly, one embodiment of the cleaning agent containing "approximately 2% by weight" halogenated acetic acid of structure A can contain between 1.9% and 2.1% by weight of halogenated acetic acid of structure A. An embodiment of the cleaning agent containing "approximately 4% by weight" of a halogenated acetic acid can contain between 3.8% and 4.2% by weight of a halogenated acetic acid of structure A. An embodiment of the cleaning agent containing "approximately 10% by weight" of a halogenated acetic acid of structure A can contain between 9.5% and 10.5% by weight of a halogenated acetic acid of structure A.

[0057] Furthermore, it will be apparent to those skilled in the art that cleaning agents containing between "approximately 85% by weight and approximately 65% ​​by weight" or between "approximately 99% by weight and approximately 90% by weight" of anisole and / or anisole derivatives are not strict limits and may contain amounts of anisole and / or anisole derivatives slightly outside these ranges. In one embodiment, for example, anisole and / or anisole derivatives between "approximately 85% by weight and approximately 65% ​​by weight" may contain anisole and / or anisole derivatives at ±10% of the weight percentage. Thus, one embodiment of the cleaning agent containing "approximately 85% by weight" of anisole and / or anisole derivatives may contain between 93.5% by weight and 76.5% by weight of anisole and / or anisole derivatives. One embodiment of the cleaning agent containing "approximately 80% by weight" of anisole and / or anisole derivatives may contain between 88% by weight and 72% by weight of anisole and / or anisole derivatives. One embodiment of the cleaning agent containing "approximately 70% by weight" anisole and / or derivatives of anisole may contain between 77% and 63% by weight anisole and / or derivatives of anisole.

[0058] In another embodiment, for example, a cleaning agent containing between approximately 85% and approximately 65% ​​by weight of anisole and / or anisole derivatives can contain anisole and / or anisole derivatives by ±5% of that weight percentage. Thus, one embodiment of the cleaning agent containing approximately 85% by weight of anisole and / or anisole derivatives can contain between 89.25% and 80.75% by weight of anisole and / or anisole derivatives. One embodiment of the cleaning agent containing approximately 80% by weight of anisole and / or anisole derivatives can contain between 84% and 76% by weight of anisole and / or anisole derivatives. One embodiment of the cleaning agent containing approximately 70% by weight of anisole and / or anisole derivatives can contain between 76.5% and 73.5% by weight of anisole and / or anisole derivatives.

[0059] In a further embodiment, the cleaning agent consists essentially of (i) acetic acid and / or halogenated acetic acid of Structure A, and (ii) anisole and / or anisole derivatives, in varying concentrations. In such an embodiment, the total amount of acetic acid and / or halogenated acetic acid of Structure A and anisole and / or anisole derivatives is not 100% by weight, and other components (e.g., additional solvent(s), including water, common additives, and / or impurities) may be included as long as they do not substantially alter the effectiveness of the cleaning agent. Thus, in another embodiment, the cleaning agent may include acetic acid and / or halogenated acetic acid of Structure A containing varying amounts of water. In one such embodiment, the cleaning agent may include acetic acid and / or halogenated acetic acid of Structure A with water in an amount greater than 1% by weight. In another such embodiment, the cleaning agent may include acetic anhydride (also known as glacial acetic acid) (i.e., acetic acid with a water content of less than 1% by weight). Such embodiments can also include, for example, various technical grades (e.g., reagent grade, trace grade, ultra-trace grade, electronics grade, HPLC grade, etc.) of acetic acid, anhydrous / glacial acetic acid, and / or halogenated acetic acids of structure A, having various amounts of impurities.

[0060] In another embodiment, the cleaning agent comprises various concentrations of (i) acetic acid and / or halogenated acetic acid of Structure A, and (ii) anisole and / or anisole derivatives. In such an embodiment, the total amount of acetic acid and / or halogenated acetic acid of Structure A and anisole and / or anisole derivatives is approximately 100% by weight, but may contain minor and / or trace amounts of other impurities present in amounts so small that they do not substantially alter the effectiveness of the cleaning agent. For example, in one such embodiment, the cleaning agent may contain impurities and / or other components (e.g., additional solvent(s) including water) in a total amount of 2% by weight or less. In another embodiment, the cleaning agent may contain impurities and / or other components (e.g., additional solvent(s) including water) in a total amount of 1% by weight or less. In a further embodiment, the cleaning agent may contain impurities and / or other components (e.g., additional solvent(s) including water) in a total amount of 0.05% by weight or less. These embodiments may include, for example, anhydrous / glacial acetic acid. Such embodiments may also include, for example, various technical grades (e.g., reagent grade, trace grade, ultra-trace grade, electronics grade, HPLC grade, etc.) of acetic acid, anhydrous / glacial acetic acid, and / or halogenated acetic acids of structure A, having various amounts of impurities. These embodiments may also include trace amounts of metal impurities, for example, present in amounts well below 0.05% by weight (e.g., ppb levels).

[0061] It will also be apparent to those skilled in the art that halogenated acetic acids of structure A that may be used in the disclosed cleaning agents include (i) halogenated acetic acid compounds of structure A in which R1 and R2 are each hydrogen and R3 is a halogen selected from fluorine, bromine, iodine, and chlorine, (ii) halogenated acetic acid compounds of structure A in which two or more of R1, R2, and R3 are the same halogen selected from fluorine, bromine, iodine, and chlorine, and (iii) halogenated acetic acid compounds of structure A in which 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 containing two or more different halogens (e.g., when two or more of R1, R2, and R3 in structure A are different halogens).

[0062] The cleaning agents may further comprise a mixture of two or more halogenated acetic acids of structure A. It will be apparent to those skilled in the art that derivatives of anisole, including variously substituted anisole compounds, may also be used in the disclosed cleaning agents. In this regard, the disclosed cleaning agents include mixtures of acetic acid or halogenated acetic acids of structure A with anisole and / or derivatives of anisole of structure B.

[0063] [ka] In the formula, R a , R b , R c , R d , R e , R f , R g and R hmay each independently be hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted halogenated alkyl group, a substituted or unsubstituted alkylcarbonyl group, a halogen, and a hydroxy group, as previously described. Examples of specific derivatives of anisole suitable for use in the disclosed and / or claimed cleaning agents include, but are not limited to, halogenated anisole compounds (e.g., R a , R b , R c , R d and R e wherein one or more of are each independently fluorine, iodine, bromine or chlorine).

[0064] EPL masking agent The disclosed cleaning materials are suitable for removing EPL formed on the edge and adjacent surfaces of a wafer / substrate. In one embodiment, the disclosed cleaning materials are adapted for removing EPL formed from maskants or compositions such as those described and / or claimed in PCT / EP2018 / 056322 (Patent Document 2) that include the following components: a. A polymer comprising units having structure (I):

[0065] [ka] [In the formula, X is selected from the group of -SO2-, -C(=O)- and -O-; A is a direct bond or A is selected from the group of structures (II):

[0066] [ka] (Wherein R1, R2, R3, R4 and R5 are each independently H, halo, (C 1~3 ) alkyl, (C 1~3 ) Fluorinated alkyl, hydroxy, (C 1~3 ) alkoxy, and (C 1~3 ) alkylcarbonyl) q, r, s, and t are each independently selected from the group consisting of 0, 1, 2, 3, and 4; and b. organic solvents, However, the polymer has an average molecular weight of less than 50,000.

[0067] In a further embodiment, where the EPL is formed from a composition disclosed and / or claimed in PCT / EP2018 / 056322, the cleaning agent is particularly effective when the polymeric unit having structure (I) shown above comprises one of the following, preferably one of the following:

[0068] [ka] When applied, the EPL can be applied, for example, in a width of at least approximately 0.5 mm. Alternatively, the EPL can be applied in a width of at least approximately 0.75 mm. Furthermore, the EPL can be applied in a width of no more than approximately 2.0 mm. Alternatively, the EPL can be applied in a width of no more than approximately 1.0 mm.

[0069] 1, when EPL is applied to a wafer / substrate 1, it is applied to the edge 2 of the wafer / substrate and to one or more surfaces proximate the edge of the wafer / substrate (i.e., top surface 3 and / or bottom surface 4). Thus, the EPL can be positioned to cover the edge of the substrate and extend onto the front and / or back surface of the substrate. For example, the EPL can be applied on the surface proximate the edge and extend from approximately 0.5 mm to approximately 2.0 mm wide on the top surface of the wafer and substrate, and then extend over the edge and then to approximately 2.5 mm wide on the back surface of the wafer / substrate edge.

[0070] Hard Mask As previously indicated, the disclosed cleaning materials advantageously provide for the simultaneous removal of applied EPL and residual hardmask components from the edge and adjacent surfaces of the wafer / substrate (e.g., where the hardmask has penetrated or removed underneath the EPL). Examples of residual hardmask components that can be removed using the disclosed cleaning materials include components of both metal hardmask compositions and metal oxide photoresist compositions used in lithographic manufacturing processes. Suitable metal hard mask and metal oxide photoresist compositions include, but are not limited to, those described in U.S. Pat. No. 9,315,636, U.S. Pat. No. 8,568,958, U.S. Pat. No. 9,201,305, U.S. Pat. No. 9,296,922, U.S. Pat. No. 9,409,793, and U.S. Pat. No. 9,499,698, and U.S. Pat. No. 62 / 437,449 (filed December 21, 2016) and U.S. Pat. No. 14 / 978,232 (filed December 22, 2015), the contents of which are incorporated herein in their entirety. Hard mask components that are or can be removed by the disclosed cleaners 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.

[0071] The cleaning agent is effective in removing residual hard mask components regardless of the method used to apply the hard mask. In this regard, in the disclosed method / process, any of a variety of techniques can be used to apply the hard mask composition to the wafer / substrate surface to form the hard mask. Suitable techniques include, but are not limited to, spin-on coating, chemical vapor deposition (CVD), and atomic layer deposition (ALD). When using spin coating, at least one casting solvent is preferably used, but 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.

[0072] In the disclosed method / process, any of a variety of techniques can be used to remove the portion of the hardmask composition in contact with the EPL. Those skilled in the art will understand that removal of the portion of the hardmask composition in contact with the EPL should not adversely affect the portion of the hardmask composition 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 used, any of a variety of solvents (e.g., EBR) can be used, provided that the solvent does not adversely affect the EPL or the hardmask. Suitable EBRs include, but are not limited to, PGMEA, PGME, ethyl lactate, methoxyethanol, ethoxypropanol, ethoxyethanol, 1-pentanol, 4-methyl-2-pentanol, and mixtures thereof.

[0073] 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 approximately 150° C. and approximately 450° C. and / or for a time between approximately 60 seconds and approximately 120 seconds.

[0074] Typical electronic devices that can be manufactured using the compositions and methods of the disclosed invention include, but are not limited to, computer chips, integrated circuits, and semiconductor devices. [Example]

[0075] More specific aspects of the present disclosure and experimental results supporting such aspects are described below. These examples are provided below to more fully explain the disclosed invention, and should not be construed as limiting the disclosed invention in any way.

[0076] It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed invention and the specific examples provided herein without departing from the spirit and scope of the disclosed invention. Thus, the disclosed invention, including the description provided by way of example below, is intended to cover modifications and variations of the disclosed invention that come within the scope of any claims and their equivalents.

[0077] Materials and Methods: MHM082 is a titanium-containing metal hardmask composition available from EMD Performance Materials Corp.

[0078] EPL003 is a polysulfone in anisole available from EMD Performance Materials Corp.

[0079] U98 polymer is a high carbon content polymer available from EMD Performance Materials Corp.

[0080] The ArF thinner is a 70 / 30 (by weight) mixture of PGMEA / PGME available from EMD Performance Materials Corp.

[0081] Metal content was determined by ICP-MS on an Elan DRCII using the following operating parameters:

[0082] TIFF0007792461000013.tif101170

[0083] Metal Hard Mask ("MHM") Formulation: To evaluate the effectiveness of removing remaining residual components of the hard mask, an MHM formulation ("MHM Formulation") containing a maskant for application to a wafer / substrate was prepared by dissolving MHM082 (2514.285 g), triethanolamine (314.285 g), and U-96 polymer (78.57 g) in ArF thinner (12,092.857 g) and filtering through a 0.2 micron filter.

[0084] Example 1: The MHM formulation was spin-coated (7500 rpm) onto a wafer without baking, and the wafer was immersed in 100% anisole on a laboratory hotplate until all film was removed. The wafer was then cleaned for 6 minutes using an acid solution of HCl and hydrogen peroxide. The acid solution was prepared by adding approximately 30.4 g of water to a flask and adding 35.7 g of hydrogen peroxide (30%) and 33.9 g of HCl (37%) with stirring (approximately 1 hour). The titanium content of the extracted solution was determined to be 89.14 ppb by ICP-MS as previously described.

[0085] Example 2: The MHM formulation was spin-coated (7500 rpm) onto a wafer without baking, and the wafer was immersed in a mixture of 5% (by weight) acetic acid and 95% (by weight) anisole on a laboratory hotplate until all the film was removed. The wafer was then cleaned for 6 minutes using an acid solution of HCl and hydrogen peroxide. The acid solution was prepared by adding approximately 30.4 g of water to a flask and adding 35.7 g of hydrogen peroxide (30%) and 33.9 g of HCl (37%) with stirring (approximately 1 hour). The titanium content of the extracted solution was determined to be 89.14 ppb by ICP-MS as previously described.

[0086] Example 3: The MHM formulation was spin-coated (7500 rpm) onto a wafer without baking, and the wafer was immersed in a mixture of 10% (by weight) acetic acid and 90% (by weight) anisole on a laboratory hotplate until all of the film was removed. The wafer was then cleaned for 6 minutes using an acid solution of HCl and hydrogen peroxide. The acid solution was prepared by adding approximately 30.4 g of water to a flask and adding 35.7 g of hydrogen peroxide (30%) and 33.9 g of HCl (37%) with stirring (approximately 1 hour). The titanium content of the extracted solution was determined to be 90.33 ppb by ICP-MS as previously described.

[0087] Example 4: The MHM formulation was spin-coated (7500 rpm) onto a wafer without baking, and the wafer was immersed in a mixture of 20% (by weight) acetic acid and 80% (by weight) anisole on a laboratory hotplate until all the film was removed. The wafer was then cleaned for 6 minutes using an acid solution of HCl and hydrogen peroxide. The acid solution was prepared by adding approximately 30.4 g of water to a flask and adding 35.7 g of hydrogen peroxide (30%) and 33.9 g of HCl (37%) with stirring (approximately 1 hour). The titanium content of the extracted solution was determined to be 58.73 ppb by ICP-MS as previously described.

[0088] Example 5: The MHM formulation was spin-coated (7500 rpm) onto a wafer without baking, and the wafer was immersed in a mixture of 30% (by weight) acetic acid and 70% (by weight) anisole on a laboratory hotplate until all the film was removed. The wafer was then cleaned for 6 minutes using an acid solution of HCl and hydrogen peroxide. The acid solution was prepared by adding approximately 30.4 g of water to a flask and adding 35.7 g of hydrogen peroxide (30%) and 33.9 g of HCl (37%) with stirring (approximately 1 hour). The titanium content of the extracted solution was determined to be 58.84 ppb by ICP-MS as previously described.

[0089] Example 6: The MHM formulation was spin-coated (7500 rpm) onto a wafer without baking, and the wafer was immersed in a mixture of 2% (by weight) trifluoroacetic acid and 98% (by weight) anisole on a laboratory hotplate until all the film was removed. The wafer was then cleaned for 6 minutes using an acid solution of HCl and hydrogen peroxide. The acid solution was prepared by adding approximately 30.4 g of water to a flask and adding 35.7 g of hydrogen peroxide (30%) and 33.9 g of HCl (37%) with stirring (approximately 1 hour). The titanium content of the extracted solution was determined to be 49.2 ppb by ICP-MS as previously described.

[0090] Example 7: The MHM formulation was spin-coated (7500 rpm) onto a wafer without baking, and the wafer was immersed in a mixture of 4% (by weight) trifluoroacetic acid and 96% (by weight) anisole on a laboratory hotplate until all the film was removed. The wafer was then cleaned for 6 minutes using an acid solution of HCl and hydrogen peroxide. The acid solution was prepared by adding approximately 30.4 g of water to a flask and adding 35.7 g of hydrogen peroxide (30%) and 33.9 g of HCl (37%) with stirring (approximately 1 hour). The titanium content of the extracted solution was determined to be 50.89 ppb by ICP-MS as previously described.

[0091] Example 8: The MHM formulation was spin-coated (7500 rpm) onto a wafer without baking, and the wafer was immersed in a mixture of 10% (by weight) trifluoroacetic acid and 90% (by weight) anisole on a laboratory hotplate until all the film was removed. The wafer was then cleaned for 6 minutes using an acid solution of HCl and hydrogen peroxide. The acid solution was prepared by adding approximately 30.4 g of water to a flask and adding 35.7 g of hydrogen peroxide (30%) and 33.9 g of HCl (37%) with stirring (approximately 1 hour). The titanium content of the extracted solution was determined to be 49.13 ppb by ICP-MS as previously described.

[0092] result As shown in Table 1 below, an unexpectedly significant reduction in the residual amount (i.e., amount of metal residue) of the applied hard mask is observed in a cleaning agent containing between approximately 15% and 35% by weight acetic acid and between approximately 85% and 65% by weight anisole.

[0093] [Table 1]

[0094] As shown in Table 1, for example, a cleaning agent containing approximately between 20% and 30% by weight acetic acid and approximately between 80% and 70% by weight anisole unexpectedly reduced residual metal content by approximately 35% compared to other mixtures of acetic acid and anisole.

[0095] As shown in Table 2 below, trifluoroacetic acid (i.e., the use of halogenated acetic acid compounds of Structure A) also demonstrates an unexpectedly significant reduction in the amount of residual metal (i.e., the amount of metal residue) on the applied hard mask. In particular, a reduction in the amount of residual titanium was observed when using a cleaning agent comprising between approximately 1% and 10% by weight trifluoroacetic acid and between approximately 99% and 90% by weight anisole.

[0096] [Table 2]

[0097] As shown in Table 2, for example, cleaning agents containing approximately between 2% and 10% by weight trifluoroacetic acid and approximately between 98% and 90% by weight anisole were unexpectedly somewhat more effective at removing residual metal content than the acetic acid formulations of Table 1. In particular, the trifluoroacetic acid-containing cleaners demonstrated approximately 15% more effective at removing applied hard mask residues, based on the average residual metal residue (58.76 ppb) of the most effective acetic acid / anisole cleaners (i.e., 20 / 80 and 30 / 70) of Table 1, compared to the average residual metal residue (49.74 ppm) of the trifluoroacetic acid / anisole cleaners of Table 2.

[0098] Although the disclosed and claimed invention has been described and illustrated with a certain degree of detail, It should be understood that this disclosure is given by way of example only, and that numerous variations in the conditions and order of the steps can be reconstructed by one skilled in the art without departing from the spirit and scope of the disclosed and claimed invention. While this application is directed to the invention set forth in the claims, the disclosure of this application also includes: 1. (i) between approximately 15% and approximately 35% by weight of acetic acid, and (ii) between approximately 85% and approximately 65% ​​by weight of a compound having structure B; Cleaning agent containing [ka] In the formula, R a 、R b 、R c 、R d 、R e 、R f 、R g and R h are each independently hydrogen, substituted or unsubstituted (C1~6 ) alkyl groups, substituted or unsubstituted halogenated (C 1~6 ) alkyl groups, substituted or unsubstituted (C 1~6 ) may be an alkylcarbonyl group, a halogen or a hydroxy group. 2. R in structure B a 、R b 、R c 、R d 、R e 、R f 、R g and R h and each represents hydrogen. 3. The cleaning agent according to 1. or 2. above, which contains approximately 15% by weight of acetic acid. 4. The cleaning agent according to 1. or 2. above, which contains approximately 20% by weight of acetic acid. 5. The cleaning agent according to 1. or 2. above, which contains approximately 25% by weight of acetic acid. 6. The cleaning agent according to 1. or 2. above, which contains approximately 30% by weight of acetic acid. 7. The cleaning agent according to 1. or 2. above, which contains approximately 35% by weight of acetic acid. 8. The cleaning agent according to any one of 1. to 7. above, which consists essentially of acetic acid and a compound having structure B. 9. The cleaning agent according to any one of 1. to 7. above, which comprises acetic acid and a compound having the structure B. 10. a. A polymer comprising units having structure (I):

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Claims

1. (i) between approximately 1% and approximately 10% by weight of a halogenated acetic acid of structure A below; 【Chemistry 1】 [In the formula, R １ and R ２ are independently hydrogen or halogen, and R ３ is a halogen; and (ii) between approximately 99% and approximately 90% by weight of a compound having structure B: 【Chemistry 2】 [In the formula, R ａ , R ｂ , R ｃ , R ｄ , R ｅ , R ｆ , R ｇ and R ｈ are each independently hydrogen, substituted or unsubstituted (C １～６ ) alkyl groups, substituted or unsubstituted halogenated (C １～６ ) alkyl group, substituted or unsubstituted (C １～６ ) may be an alkylcarbonyl group, a halogen, or a hydroxy group.

1. A cleaning agent for removing edge protection layers and residual hard mask components from the edge of a wafer / substrate surface in a lithography process, comprising:

2. R in Structure B ａ , R ｂ , R ｃ , R ｄ , R ｅ , R ｆ , R ｇ and R ｈ 10. The cleaning agent of claim 1, wherein each of is hydrogen.

3. In the halogenated acetic acid of structure A, R １ and R ２ are each hydrogen, and R ３ 3. The cleaning agent according to claim 1, wherein is a halogen selected from fluorine, bromine, iodine and chlorine.

4. In the halogenated acetic acid of structure A, R １ , R ２ and R ３ 3. The cleaning agent according to claim 1, wherein two or more of the following are halogens selected from fluorine, bromine, iodine and chlorine.

5. The halogenated acetic acid in structure A is difluoroacetic acid, and R in structure B is ａ , R ｂ , R ｃ , R ｄ , R ｅ , R ｆ , R ｇ and R ｈ 10. The cleaning agent of claim 1, wherein each of is hydrogen.

6. The halogenated acetic acid in structure A is trifluoroacetic acid, and R in structure B is ａ , R ｂ , R ｃ , R ｄ , R ｅ , R ｆ , R ｇ and R ｈ 10. The cleaning agent of claim 1, wherein each of is hydrogen.

7. A method for cleaning a wafer or substrate to remove edge protection layers and residual hard mask components from the edge of the wafer / substrate surface in a lithography process, comprising cleaning the wafer or substrate with the cleaning agent of any one of claims 1 to 6.

8. (a) applying a maskant to the edge and at least one adjacent surface of a wafer or substrate; (b) heating the applied maskant to form an edge protection layer on the edge and at least one adjacent 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 applied hard mask composition in contact with the edge protection layer, wherein the removing comprises washing the hard mask 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-applied bake; The method of claim 7 , further comprising one or more steps selected from the group consisting of:

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