Etching compositions and methods for EUV mask protection structures

Abstract

A composition and method for removing a portion of a metal-containing layer of an EUV mask or a layer of a pellicle is provided. The composition includes water, one or more oxidizing agents, and one or more acids. The method includes forming one or more layers on a silicon substrate, at least one of which includes a metal-containing layer, and removing the metal-containing layer by contacting the metal-containing layer with a composition of the disclosed and claimed subject matter.

Description

[Technical field]

[0001] Technical Field

[0002] The disclosed and claimed subject matter relates to extreme ultraviolet (EUV) lithography techniques, and more particularly to compositions and methods for fabricating semiconductor structures, including metal-containing mask protection structures on semiconductor devices. [Background technology]

[0003] Related Technology

[0004] As the critical dimensions (CD) of circuits in semiconductor devices become smaller and smaller, the physical limits of using ArF exposure tools to achieve the required resolution required to transfer fine patterns onto wafers have been reached. Therefore, EUV lithography technology has been developed to transfer finer patterns onto wafers. EUV lithography technology is considered as the next generation technology and is used to manufacture slimmer and faster microchips with critical dimensions of 32nm or less by using EUV light with an exposure wavelength of about 13.5nm.

[0005] In some embodiments, since the EUV lithography technique uses light with a very short wavelength, the mask on which the circuit pattern is to be transferred onto the wafer is preferably provided with a mask pattern, and the mask pattern is preferably not a light-transmitting structure but has a light-reflecting structure. Masks used in EUV lithography processes often include a light-reflecting layer having a multilayer structure of Mo / Si layers on a substrate having a low thermal expansion coefficient (LTE) such as quartz, and a light-absorbing layer formed on the light-reflecting layer to partially expose the surface of the light-reflecting layer.

[0006] In order to protect the surface of the EUV mask used in the EUV lithography process from contaminant sources such as particles, a pellicle or protective layer or structure is often provided. However, it is difficult to manufacture a pellicle that meets the requirements of EUV lithography, due to, among other reasons, the difficulty of manufacturing a suitable pellicle film using polymers. In particular, it is difficult to use carbon-fluorine (CF)-based polymers as pellicle films, since it is well known that CF-based polymers absorb EUV light. Therefore, materials with high transmittance to EUV light have been proposed as suitable candidates for pellicle films. For example, the following pellicle manufacturing method can be used: A metal layer or a metal wire mesh, such as nickel (Ni), is formed by electroplating, and this layer or mesh is placed on the polymer film. Silicon (Si) is then deposited to form a silicon membrane layer. The polymer film is then removed, so that the silicon membrane layer remains attached to the mesh. The polymer film is a sacrificial layer.

[0007] In addition, in the case of a pellicle for EUV lithography, a thin film of a material with high EUV transmittance is required, but when a thin film is used, the film is deformed and broken due to repeated use. To solve this problem, a pellicle structure in which a support structure is provided on the thin film has been proposed. The support structure needs to have high transmittance and high mechanical strength.

[0008] For example, Korean Patent No. 1552940(B1) (Korean Patent Application Publication No. 20130157275(A), Applicant: Samsung Electronics Co., Ltd.) discloses a method for producing a graphite-containing thin film having high tensile strength while having high EUV transparency, as well as a pellicle film for extreme ultraviolet lithography.

[0009] EUV mask protection structures are known that include alternative or additional layers, such as a linking layer, a polycrystalline graphene layer, and / or a heat dissipation layer that may be present on the linking layer in some embodiments. In one embodiment disclosed in WO2017183941A1, an EUV pellicle includes a transparent layer, a graphene layer on the EUV transparent layer, defects in the graphene layer (providing a linking material on the defects to form a linking pattern), and a heat dissipation layer on the linking pattern, as well as one or more other layers, such as a sacrificial layer, an insulating layer, a passivation layer, such as a silicon layer, a silicon oxide (insulating) layer, or a silicon nitride (passivation) layer. However, attempts continue to develop EUV pellicles (mask protection structures) and other structures that have excellent mechanical strength, excellent thermal stability, excellent transparency to EUV, and / or excellent chemical resistance to hydrogen.

[0010] In conjunction with the development of new EUV masks and mask protection structures, there is a need for wet compositions for removing material of one or more layers and associated residues after EUV exposure and / or etching step(s). Summary of the Invention [Problem to be solved by the invention]

[0011] The disclosed and claimed subject matter provides metal etching compositions and methods that have high removal rates that also provide good compatibility with silicon nitride (Si3N4) and silicon oxide (SiO2) and other materials on semiconductor substrates. [Means for solving the problem]

[0012] In one embodiment, the disclosed and claimed subject matter comprises: (i) Water; (ii) one or more oxidizing agents; and (iii) one or more acids, wherein the composition is designed for removal of a metal-containing layer in an EUV mask protective structure that includes only the metal-containing layer or further includes one or more additional layers of material. Thus, in some embodiments, the composition for removing a metal-containing layer may include, consist essentially of, or alternatively consist of (i) water, (ii) one or more oxidizing agents, and (iii) one or more acids.

[0013] In another embodiment, the composition further comprises (iv) a source of halogen ions. Thus, in some embodiments, a composition for removing a metal-containing layer may comprise, consist essentially of, or alternatively consist of (i) water, (ii) one or more oxidizing agents, (iii) one or more acids, and (iv) a source of halogen ions.

[0014] In another embodiment, the composition further comprises (v) a chelating agent. Thus, in some embodiments, a composition for removing a metal-containing layer may comprise, consist essentially of, or alternatively consist of (i) water, (ii) one or more oxidizing agents, (iii) one or more acids, and (v) a chelating agent.

[0015] In another embodiment, the composition further comprises (iv) a source of halogen ions and (v) a chelating agent. Thus, in some embodiments, a composition for removing a metal-containing layer may comprise, consist essentially of, or alternatively consist of (i) water, (ii) one or more oxidizing agents, (iii) one or more acids, (iv) a source of halogen ions, and (v) a chelating agent.

[0016] In another embodiment, the one or more oxidizing agents (ii) comprise one or more of peroxomonosulfate, perborate, perchlorate, perchloric acid, peracetate, sulfuric acid, periodate, persulfate, permanganate, chromate, dichromate, benzoquinone, nitric acid, and amine-N-oxides. In a further aspect of this embodiment, the one or more oxidizing agents (ii) are one or more of ammonium persulfate (APS), 2,5-dihydroxy-1,4-benzoquinone, nitrosylsulfuric acid, and pyridine N-oxide, 4-methylmorpholine N-oxide.

[0017] In another embodiment, the one or more acids (iii) include one or more of sulfuric acid, hydrochloric acid, alkylsulfonic acids such as methanesulfonic acid, alkylbenzylsulfonic acids such as 4-methylbenzenesulfonic acid, hydrobromic acid, citric acid, malonic acid, hydrofluoric acid, acetic acid, phosphoric acid, and hydroiodic acid.

[0018] In another aspect, the disclosed and claimed subject matter comprises: a. forming one or more layers, including at least one Ni-containing layer, on a silicon substrate; and b. removing the Ni-containing layer by contacting said Ni-containing layer with at least one of the compositions of the disclosed and claimed subject matter; The present invention relates to a method for manufacturing a semiconductor device, comprising:

[0019] In another aspect, the disclosed and claimed subject matter comprises: a. providing a semiconductor device comprising a substrate and an EUV mask and a metal-containing EUV mask protection structure; b. exposing the semiconductor device to EUV radiation; and c. removing the metal-containing EUV mask protective structure by contacting the semiconductor device with at least one of the compositions of the disclosed and claimed subject matter; In a further aspect of this embodiment, the method further comprises the additional steps of: d. depositing the metal-containing EUV mask protection structure onto the semiconductor device via atomic layer deposition (ALD), e-beam evaporation, chemical vapor deposition, or electroplating; e. performing a selective dry etching process on at least a portion of the semiconductor device prior to the removing step c; Includes one or more of the following.

[0020] In a further aspect of the embodiment for removing the metal-containing layer of the pellicle structure, the metal-containing EUV mask protective structure comprises nickel. In another aspect, the metal-containing EUV mask protective structure comprises a metal-containing heat dissipation layer. In another aspect, the metal-containing EUV mask protective structure comprises a metal-containing tie layer. In another aspect, the semiconductor device further comprises at least one layer selected from a sacrificial layer, an insulating layer, a passivation layer, a low-k layer, a metal-containing layer, and a barrier layer between the substrate and the EUV mask or as part of the EUV mask protective structure. In another aspect, the EUV mask protective structure comprises at least one layer selected from a sacrificial layer, an insulating layer, a passivation layer, a graphene layer, an EUV transparent layer, a tie layer, and a heat dissipation layer.

[0021] In another aspect, the disclosed and claimed subject matter relates to a system including at least one of the compositions of the disclosed and claimed subject matter in combination with the above-mentioned semiconductor device including a metal-containing EUV mask protection structure.

[0022] The compositions, methods, and systems of the disclosed and claimed subject matter provide high removal rates and good compatibility with semiconductor device materials. For example, the metal etchant composition has a Ni etch rate of greater than 300 Å / min and good compatibility with Si3N4 and SiO2. In addition, the compositions, methods, and systems of the disclosed and claimed subject matter provide high solubility of metal oxides. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] All references cited herein, including publications, patent applications, and patents, including WO2017183941(A1) and U.S. Pat. No. 8,535,545, are hereby incorporated by reference to the same extent as if each reference was individually and specifically indicated to be incorporated by reference and was set forth in its entirety herein.

[0024] The use of the terms "a," "an," and "the" and similar referents in the context of describing the disclosed and claimed subject matter (particularly in the context of the claims below) should be construed to encompass both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms "comprising," "having," "including," and "containing" should be construed as open-ended terms (i.e., meaning "including but not limited to"), unless otherwise indicated. The recitation of ranges of values ​​herein is merely intended to be used as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated herein as if it were individually recited herein. All methods described herein may be performed in any suitable order, unless otherwise indicated herein or clearly contradicted by context. The use of any examples or exemplary language (e.g., "such as") provided herein is intended merely to better clarify the disclosed and claimed subject matter and does not pose a limitation on the scope of the disclosed and claimed subject matter unless specifically recited in a claim. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the disclosed and claimed subject matter. Use of the terms "comprising" or "including" in the specification and claims includes the narrower language "consisting essentially of" and "consisting of."

[0025] In a composition "consisting essentially of" listed components, such components may total 100% by weight of the composition or may total less than 100% by weight. When components total less than 100% by weight, such compositions may contain some small amounts of non-essential contaminants or impurities. For example, in one such embodiment, the etching composition may contain 2% by weight or less of impurities. In another embodiment, the etching composition may contain 1% by weight or less of impurities. In a further embodiment, the etching composition may contain 0.05% by weight or less of impurities. In other such embodiments, the components may form at least 90% by weight, more preferably at least 95% by weight, more preferably at least 99% by weight, more preferably at least 99.5% by weight, and most preferably at least 99.9% by weight, and may include other components that do not substantially affect the performance of the etching composition. Alternatively, it is understood that the combination of all essential components essentially totals 100% by weight when there are no significant amounts of non-essential impurity components.

[0026] Embodiments of the disclosed and claimed subject matter are described herein, including the best mode known to the inventors for carrying out the disclosed and claimed subject matter. Variations of these embodiments will become apparent to those skilled in the art upon reading the above description. The inventors contemplate that such variations will be employed by those skilled in the art as appropriate, and the inventors intend that the disclosed and claimed subject matter may be practiced differently than specifically described herein. Accordingly, the disclosed and claimed subject matter includes all modifications and equivalents of the subject matter recited in the appended claims as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the disclosed and claimed subject matter unless otherwise indicated herein or otherwise clearly contradicted by context.

[0027] The term "silicon" when deposited as a material on a microelectronic device is understood to include polysilicon.

[0028] For ease of reference, "microelectronic device" or "semiconductor device" refers to semiconductor wafers on which integrated circuits, memories, and other electronic structures are fabricated, as well as flat panel displays, phase change memory devices, solar panels and other products including solar substrates, photovoltaic devices, and microelectromechanical systems (MEMS) fabricated for use in microelectronic, integrated circuit, or computer chip applications. Solar substrates include, but are not limited to, silicon, amorphous silicon, polycrystalline silicon, single crystal silicon, CdTe, copper indium selenide, copper indium sulfide, and gallium arsenide on gallium. Solar substrates may be doped or undoped. The terms "microelectronic device" or "semiconductor device" are not intended to be limiting in any way and include any substrate that will ultimately become a microelectronic device or microelectronic assembly.

[0029] As defined herein, "low-k dielectric material" refers to any material having a dielectric constant less than about 3.5 that is used as a dielectric material in layered microelectronic devices. Preferably, the low-k dielectric material includes low polarity materials such as silicon-containing organic polymers, silicon-containing hybrid organic / inorganic materials, organosilicate glass (OSG), TEOS, fluorinated silicate glass (FSG), silicon dioxide, and carbon-doped oxide (CDO) glass. It is understood that low-k dielectric materials can have different densities and different porosities.

[0030] As defined herein, the term "barrier material" refers to any material used in the art to seal metal lines, e.g., copper wiring, to minimize the diffusion of said metal, e.g., copper, into dielectric materials. Preferred barrier layer materials include tantalum, titanium, ruthenium, hafnium, and other refractory metals, as well as their nitrides and silicides.

[0031] "Substantially free" is defined herein as less than 0.001% by weight. "Substantially free" also includes 0.000% by weight. The term "free" means 0.000% by weight.

[0032] As used herein, "about" or "approximately" is intended to correspond to within ±5% of the stated value.

[0033] In all compositions where specific components of a composition are discussed with reference to a weight percent (or "weight %") range including a lower limit of zero, it is understood that such components may or may not be present in various specific embodiments of the composition, and that when such components are present, they may be present in concentrations as low as 0.001 weight percent, based on the total weight of the composition in which such component is used. It should be noted that all percentages of components are weight percents and are based on the total weight of the composition, i.e., 100%. Any reference to "one or more" or "at least one" includes "two or more" and "three or more," etc.

[0034] Where applicable, all weight percentages are "neat" meaning that the weight percentage does not include the aqueous solution in which it is present when added to the composition unless otherwise noted. As used herein, for example, "neat" refers to the weight percentage amount of undiluted acid or other material (i.e., including 100 g of 85% phosphoric acid is equivalent to 85 g of acid and 15 g of diluent).

[0035] Further, when referring to compositions described herein in terms of weight percent, it is understood that the weight percent of all components, including non-essential components such as impurities, will not total more than 100 weight percent. In a composition "consisting essentially of" listed components, such components may total 100 weight percent of the composition, or may total less than 100 weight percent. When components total less than 100 weight percent, such compositions may contain some minor amounts of non-essential contaminants or impurities. For example, in one such embodiment, the formulation may contain 2 weight percent or less of impurities. In another embodiment, the formulation may contain 1 weight percent or less of impurities. In a further embodiment, the formulation may contain 0.05 weight percent or less of impurities. In other such embodiments, the components may form at least 90 weight percent, more preferably at least 95 weight percent, more preferably at least 99 weight percent, more preferably at least 99.5 weight percent, and most preferably at least 99.9 weight percent, and may include other components that do not substantially affect the performance of the wet etchant. Conversely, it is understood that a composition of all essential components essentially totals 100 wt. %, unless significant amounts of non-essential impurity components are present.

[0036] The headings used herein are not intended to be limiting; they are included for organizational purposes only.

[0037] composition

[0038] As noted above, one aspect of the disclosed and claimed subject matter provides metal etching compositions and methods that have high removal rates that also provide good compatibility with silicon nitride (Si3N4) and silicon oxide (SiO2) and other materials on semiconductor substrates.

[0039] In one embodiment, the disclosed and claimed subject matter comprises: (i) Water; (ii) one or more oxidizing agents; and (iii) one or more acids, With respect to compositions comprising, the compositions are designed for removal of a metal-containing layer in an EUV mask protective structure that includes only the metal-containing layer or further includes one or more additional layers of material. Thus, in some embodiments, compositions for removing a metal-containing layer may include, consist essentially of, or alternatively consist of water, at least one oxidizing agent, and at least one acid, as described below.

[0040] In other embodiments, the composition further comprises (iv) a source of halogen ions. Thus, as described in more detail below, in some embodiments, a composition for removing a metal-containing layer may comprise, consist essentially of, or alternatively consist of (i) water, (ii) one or more oxidizing agents, (iii) one or more acids, and (iv) a source of halogen ions.

[0041] In other embodiments, the composition further comprises (v) a chelating agent. Thus, as described in more detail below, in some embodiments, a composition for removing a metal-containing layer may comprise, consist essentially of, or alternatively consist of (i) water, (ii) one or more oxidizing agents, (iii) one or more acids, and (v) a chelating agent.

[0042] In other embodiments, the composition further comprises (iv) a source of halogen ions and (v) a chelating agent. Thus, as described in more detail below, in some embodiments, a composition for removing a metal-containing layer may comprise, consist essentially of, or alternatively consist of (i) water, (ii) one or more oxidizing agents, (iii) one or more acids, (iv) a source of halogen ions, and (v) a chelating agent.

[0043] In one embodiment, the composition comprises (i) water, (ii) one or more oxidizing agents, and (iii) one or more acids in various concentrations.

[0044] In a further embodiment, the composition comprises (i) water, (ii) one or more oxidizing agents, (iii) one or more acids, and (iv) a source of halogen ions in various concentrations.

[0045] In a further embodiment, the composition comprises (i) water, (ii) one or more oxidizing agents, (iii) one or more acids, and (v) a chelating agent, in various concentrations.

[0046] In a further embodiment, the composition comprises (i) water, (ii) one or more oxidizing agents, (iii) one or more acids, (iv) a source of halogen ions, and (v) a chelating agent, in various concentrations.

[0047] In one embodiment, the composition consists essentially of various concentrations of (i) water, (ii) one or more oxidizing agents, and (iii) one or more acids. In such embodiments, the combined amounts of (i), (ii), and (iii) are not 100% by weight and may include other components (e.g., additional solvents, common additives, and / or impurities) that do not substantially change the effectiveness of the composition.

[0048] In further embodiments, the composition consists essentially of various concentrations of (i) water, (ii) one or more oxidizing agents, (iii) one or more acids, and (iv) a halogen ion source. In such embodiments, the combined amounts of (i), (ii), (iii), and (iv) are not 100% by weight and may include other components (e.g., additional solvents, common additives, and / or impurities) that do not substantially change the effectiveness of the composition.

[0049] In further embodiments, the composition consists essentially of various concentrations of (i) water, (ii) one or more oxidizing agents, (iii) one or more acids, and (v) chelating agents. In such embodiments, the combined amounts of (i), (ii), (iii), and (v) are not 100% by weight and may include other components (e.g., additional solvents, common additives, and / or impurities) that do not substantially change the effectiveness of the composition.

[0050] In further embodiments, the composition consists essentially of various concentrations of (i) water, (ii) one or more oxidizing agents, (iii) one or more acids, (iv) a halogen ion source, and (v) a chelating agent. In such embodiments, the combined amounts of (i), (ii), (iii), (iv), and (v) are not 100% by weight and may include other components (e.g., additional solvents, common additives, and / or impurities) that do not substantially change the effectiveness of the composition.

[0051] In further embodiments, the composition comprises various concentrations of (i) water, (ii) one or more oxidizing agents, and (iii) one or more acids. In such embodiments, the combined amounts of (i), (ii), and (iii) are approximately equal to 100% by weight, but may include other minor and / or trace amounts of impurities present in such small amounts that do not substantially alter the effectiveness of the composition. For example, in one such embodiment, the composition may contain 2% or less by weight of impurities. In another embodiment, the composition may contain 1% or less by weight of impurities. In a further embodiment, the composition may contain 0.05% or less by weight of impurities.

[0052] In further embodiments, the composition comprises various concentrations of (i) water, (ii) one or more oxidizing agents, (iii) one or more acids, and (iv) a halogen ion source. In such embodiments, the combined amounts of (i), (ii), (iii), and (iv) are approximately equal to 100% by weight, but may include other minor and / or trace amounts of impurities present in such small amounts that do not substantially alter the effectiveness of the composition. For example, in one such embodiment, the composition may contain 2% or less by weight of impurities. In another embodiment, the composition may contain 1% or less by weight of impurities. In a further embodiment, the composition may contain 0.05% or less by weight of impurities.

[0053] In further embodiments, the composition is comprised of various concentrations of (i) water, (ii) one or more oxidizing agents, (iii) one or more acids, and (v) chelating agents. In such embodiments, the combined amounts of (i), (ii), (iii), and (v) are approximately equal to 100% by weight, but may include other minor and / or trace amounts of impurities present in such small amounts that do not substantially alter the efficacy of the composition. For example, in one such embodiment, the composition may contain 2% or less by weight of impurities. In another embodiment, the composition may contain 1% or less by weight of impurities. In a further embodiment, the composition may contain 0.05% or less by weight of impurities.

[0054] In further embodiments, the composition comprises various concentrations of (i) water, (ii) one or more oxidizing agents, (iii) one or more acids, (iv) a halogen ion source, and (v) a chelating agent. In such embodiments, the combined amounts of (i), (ii), (iii), (iv), and (v) are approximately equal to 100% by weight, but may include other minor and / or trace amounts of impurities present in such small amounts that do not substantially alter the effectiveness of the composition. For example, in one such embodiment, the composition may contain 2% or less by weight of impurities. In another embodiment, the composition may contain 1% or less by weight of impurities. In a further embodiment, the composition may contain 0.05% or less by weight of impurities.

[0055] (i) Water

[0056] The etching compositions of the disclosed and claimed subject matter are aqueous and therefore include water. In the disclosed and claimed subject matter, water functions in various ways, such as to dissolve one or more solid components of the residue, as a carrier for the components, as an aid in the removal of metals, such as Ni, as a viscosity modifier for the composition, and as a diluent. Preferably, the water used in the etching composition is deionized (DI) water. Water may be added directly to the composition, or water may be added to the composition via a component that is added to the etching composition as an aqueous solution. The portion of water added to the etching composition via an aqueous component is reported as part of the weight percent of water in the composition.

[0057] Water is included in an amount within a range having beginning and ending points selected from the following list of weight percents: 30, 33, 35, 38, 40, 42, 45, 50, 55, 60, 63, 65, 67, 68, 70, 72, 75, 77, 80, 83, 85, 87, 90, 92, 94, and 96, e.g., about 30% to about 94%, or about 40% to about 90%, or about 45% to about 70%, or about 45% to about 85%, or about 35% to about 75%, or about 40% to about 60%, or about 60% to about 92% water by weight. Still other preferred embodiments of the disclosed and claimed subject matter include water in an amount that achieves the desired weight percent of the other components.

[0058] (ii) Oxidizing agent

[0059] The etching compositions of the disclosed and claimed subject matter include at least one oxidizing agent. As used herein, the term "oxidizing agent" corresponds to a compound that oxidizes exposed metals resulting in corrosion of the metals or formation of oxides on the metals. In the etching compositions, oxidizing agents are used to oxidize any metals present to metal oxides to make it / them soluble in the etching solution. Oxidizing agents include, but are not limited to, hydrogen peroxide; other percompounds such as peroxomonosulfates, perborates, perchlorates, perchloric acid, peracetate anion, sulfuric acid, periodates, persulfates, permanganates, and other compounds such as chromates, dichromates, benzoquinones, nitric acid, and amine-N-oxides. Specific examples of useful oxidizing agents include nitric acid, ammonium persulfate (APS), 2,5-dihydroxy-1,4-benzoquinone, nitrosylsulfuric acid, and pyridine N-oxide, 4-methylmorpholine N-oxide. If an acid has a reduction potential greater than 0, it is considered an oxidizing agent and is referred to as an "oxidizing agent" rather than an acid.

[0060] The oxidizers are listed in the following mass percent list: 0.001, 0.003, 0.005, 0.008, 0.01, 0.03, 0.05, 0.07, 0.09, 0.1, 0.3, 0.5, 0.8, 1, 1.3, 1.5, 1.8, 2.0, 2.3, 2.5, 2.8, 3, 3.3, 3.5, 3.7, 4, 4.3, 4.5, 4.8, 5, 5.3, 5.5, 5.8, 6.0, 6.3, 6.5, 6 0.8, 7, 7.3, 7.5, 7.7, 8, 8.3, 8.5, 8.8, 9, 9.3, 9.5, 9.7, 10, for example, about 0.001% to about 10%, or about 0.005% to about 5%, or about 0.008% to about 3%, or about 0.1% to about 7%, or about 0.1% to about 6% by weight of oxidizer. Still other preferred embodiments of the disclosed and claimed subject matter include oxidizer in various amounts depending on the strength of the oxidizer selected and the desired results. It should be noted that if the oxidizer is added to the composition as an aqueous solution, water is excluded from the weight percent. Thus, when 1 gram of 60% aqueous nitric acid is added to a composition, 0.6 grams of nitric acid and 0.4 grams of water are added to the solution (i.e., 0.4 grams of water are added and are reflected in the (total) amount of water in the section above).

[0061] (iii) acid

[0062] The Ni etching compositions of the disclosed and claimed subject matter include one or more inorganic and / or organic acids. Useful acids include sulfuric acid, hydrochloric acid, alkylsulfonic acids such as methanesulfonic acid (MSA), alkylbenzylsulfonic acids such as 4-methylbenzenesulfonic acid, hydrobromic acid, citric acid, malonic acid, hydrofluoric acid, acetic acid, phosphoric acid, and hydroiodic acid. In preferred embodiments, two or more acids are present.

[0063] The one or more acids include amounts within a range having beginning and ending points selected from the following list of weight percents: 10, 12, 15, 17, 20, 23, 25, 27, 30, 33, 35, 38, 40, 42, 45, 50, 55, 60, 63, 65, 67, 68, 70, 73, 75, 77, and 80, such as from about 10% to about 80% by weight, or from about 20% to about 70% by weight, or from about 35% to about 75% by weight, or from about 40% to about 65% by weight, or from about 30% to about 70% by weight of the one or more acids. Still other preferred embodiments of the disclosed and claimed subject matter include one or more acids in varying amounts depending on the strength of the acid selected and the results desired. Please note that if one or more acids are added to the composition as an aqueous solution, water is excluded from the weight percent (i.e., thus, if 10 grams of a 35% aqueous HCl solution is added to a composition, 3.5 grams of HCl and 6.5 grams of water are added to the solution).

[0064] In some compositions, two or more acids are present therein, in some embodiments, a first acid is present in the composition in an amount that is 2x or more, or 5x or more, or 10x or more, or 20x or more, or 25x or more than the amount of a second acid present in the composition.

[0065] (iv) A source of halogen ions

[0066] The disclosed and claimed subject matter compositions may also include a halogen ion source. The halogen ion source may be a chloride ion source, a bromide ion source, an iodide ion source, a fluoride ion source, etc., such as hydrobromic acid (HBr), hydroiodic acid (HI), hydrogen chloride, HF, HCl, ammonium chloride, ammonium bromide, ammonium fluoride, and ammonium iodide. For example, HCl, HBr, HF, and HI may be used as the acid present in the etching composition, or as at least one acid, for the benefit of adding halogen ions to the solution. Additionally or alternatively, NH4Cl, NHI, NHF, and NH4Br may be added to the etching composition. The one or more halogen ion sources include amounts within a range having beginning and ending points selected from the following list of weight percents: 0.01, 0.05, 0.07, 0.1, 0.3, 0.5, 0.7, 1, 1.3, 1.5, 1.7, 2, 3, 5, 7, 10, 12, and 15, e.g., from about 0.01% to about 15% by weight, or from about 0.1% to about 10% by weight, or from about 0.05% to about 12% by weight, or from about 0.01% to about 7% by weight, or from about 0.1% to about 5% by weight of the one or more halogen ion sources.

[0067] If an acid is present, for example HCl, HBr, HF, or HI, it is included in the amount reported for the acid in the section above (but not in the amount of metal chelator).

[0068] In some embodiments, the compositions disclosed herein are formulated to be substantially free or free of inorganic bases and / or quaternary ammonium fluorides and / or quaternary ammonium hydroxides, e.g., the compositions may be free of one or more of fluorine-containing compounds, metal hydroxides, tetramethylammonium fluoride, tetraethylammonium fluoride, methyltriethylammonium fluoride, and tetrabutylammonium fluoride, tetramethylammonium hydroxide, tetraethylammonium hydroxide, methyltriethylammonium hydroxide, and / or tetrabutylammonium hydroxide, abrasives, organic solvents, surfactants, metal-containing compounds. The compositions may be free of alkanolamines, or primary, secondary, or tertiary amines, or organic solvents, or organic acids.

[0069] (v) Chelating agent

[0070] The compositions of the disclosed and claimed subject matter may also include a metal chelating agent. One function of the chelating agent is to increase the dissolution rate of metals or metal-containing compounds by forming a complex between the chelating agent and the metal ion. It is also believed that the metal chelating agent stabilizes the composition by forming a complex with trace metals that may accumulate in the composition during the course of use of the composition, thereby preventing the trace metals from decomposing the oxidizing agent of the composition. For example, free trace metal cations such as copper ions catalyze the decomposition of hydrogen peroxide into oxygen and water, which leads to an accelerated deterioration of the etching and cleaning performance of the composition over time.

[0071] Examples of suitable chelating agents include, but are not limited to, glycine, serine, proline, leucine, alanine, asparagine, aspartic acid, glutamine, glutamic acid, valine, lysine, cystine, nitrilotriacetic acid (NTA), iminodiacetic acid (IDA), ethylenediaminetetraacetic acid (EDTA), (1,2-cyclohexylenedinitrilo)tetraacetic acid (CDTA), uric acid, tetraglyme, diethylenetriaminepentaacetic acid (DTPA), propylenediamine-N,N,N',N'-tetraacetic acid, ethylenediaminedisuccinic acid (EDDS), sulfanilamide, 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid; ethylene glycol tetraacetic acid (EGTA); 1,2-bis(o-aminophenoxy)ethane-N,N,N',N'-tetraacetic acid; N-2-bis( carboxymethyl)aminoethyl-N-(2-hydroxyethyl)glycine (HEDTA); and ethylenediamine-N,N'-bis(2-hydroxyphenylacetic acid) (EDDHA), 1,3-diaminopropane-N,N,N',N'-tetraacetic acid, gluconic acid, N,N,N',N'-ethylenediaminetetrakis(methylenephosphonic acid) (EDTMP), diethylenetriaminepenta(methylenephosphonic acid) (ETDMP), nitrilotris(methylene)triphosphonic acid (ATMP), tartaric acid, 3,4-dihydroxybenzoic acid, salicylic acid, 8-hydroxyquinoline (8-HQ), etidronic acid (HEDP), 1,3-propanediamine-N,N,N',N'-tetraacetic acid, triethylenetetraminehexaacetic acid (TTHA), picolinic acid, and combinations thereof.

[0072] When present, the composition comprises 0 to 10 weight percent of the chelating agent, more preferably 50 ppm to 5 weight percent, and most preferably 100 ppm to 3 weight percent. In alternative embodiments, the optional chelating agent may be present in the composition in an amount within a weight percent range having any of the following starting and ending points: 0, 0.000001, 0.000005, 0.00001, 0.00005, 0.0001, 0.0005, 0.001, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. For example, the composition may comprise 0.0001 to 8 weight percent, or 0.001 to about 5 weight percent, or 0.01 to 2 weight percent of the chelating agent.

[0073] Exemplary Formulations

[0074] Non-limiting embodiments of the disclosed and claimed cleaning formulations are described below, along with examples.

[0075] In one embodiment of the cleaning composition, the one or more oxidizing agents comprise nitric acid. In a further aspect of this embodiment, the one or more oxidizing agents consist essentially of nitric acid. In a further aspect of this embodiment, the one or more oxidizing agents consist of nitric acid. In a further aspect of this embodiment, the one or more oxidizing agents comprise from about 0.1% to about 1.0% by weight pure nitric acid. In a further aspect of this embodiment, the one or more oxidizing agents consist essentially of from about 0.1% to about 1.0% by weight pure nitric acid. In a further aspect of this embodiment, the one or more oxidizing agents consist essentially of from about 0.1% to about 1.0% by weight pure nitric acid. In a further aspect of this embodiment, the one or more oxidizing agents comprise from about 0.9% by weight pure nitric acid. In a further aspect of this embodiment, the one or more oxidizing agents consist essentially of from about 0.9% by weight pure nitric acid. In a further aspect of this embodiment, the one or more oxidizing agents consist of approximately 0.9% by weight pure nitric acid. In a further aspect of this embodiment, the one or more oxidizing agents include approximately 0.6% by weight pure nitric acid. In a further aspect of this embodiment, the one or more oxidizing agents consist essentially of approximately 0.6% by weight pure nitric acid. In a further aspect of this embodiment, the one or more oxidizing agents consist of approximately 0.6% by weight pure nitric acid.

[0076] In another embodiment of the cleaning composition, the one or more oxidizing agents comprise 2,5-dihydroxy-1,4-benzoquinone. In a further aspect of this embodiment, the one or more oxidizing agents consist essentially of 2,5-dihydroxy-1,4-benzoquinone. In a further aspect of this embodiment, the one or more oxidizing agents consist of 2,5-dihydroxy-1,4-benzoquinone. In a further aspect of this embodiment, the one or more oxidizing agents comprise approximately 0.01% by weight of 2,5-dihydroxy-1,4-benzoquinone. In a further aspect of this embodiment, the one or more oxidizing agents consist essentially of approximately 0.01% by weight of 2,5-dihydroxy-1,4-benzoquinone. In a further aspect of this embodiment, the one or more oxidizing agents consist of approximately 0.01% by weight of 2,5-dihydroxy-1,4-benzoquinone.

[0077] In another embodiment of the cleaning composition, the one or more oxidizing agents comprise ammonium persulfate. In a further aspect of this embodiment, the one or more oxidizing agents consist essentially of ammonium persulfate. In a further aspect of this embodiment, the one or more oxidizing agents consist of ammonium persulfate. In a further aspect of this embodiment, the one or more oxidizing agents comprise approximately 1.0 wt.% ammonium persulfate. In a further aspect of this embodiment, the one or more oxidizing agents consist essentially of approximately 1.0 wt.% ammonium persulfate. In a further aspect of this embodiment, the one or more oxidizing agents consist of approximately 1.0 wt.% ammonium persulfate.

[0078] In another embodiment of the cleaning composition, the total weight percent of the pure acid in the composition is about 15% to about 50% by weight. In a further aspect of this embodiment, the total weight percent of the pure acid in the composition is about 30% to about 45% by weight. In a further aspect of this embodiment, the total weight percent of the pure acid in the composition is about 35% to about 45% by weight. In a further aspect of this embodiment, the total weight percent of the pure acid in the composition is about 30% to about 40% by weight. In a further aspect of this embodiment, the total weight percent of the pure acid in the composition is about 35% to about 40% by weight. In a further aspect of this embodiment, the total weight percent of the pure acid in the composition is about 40% to about 45% by weight.

[0079] In another embodiment of the cleaning composition, the one or more acids comprise sulfuric acid. In a further aspect of this embodiment, the one or more acids consist essentially of sulfuric acid. In a further aspect of this embodiment, the one or more acids consist of sulfuric acid. In a further aspect of this embodiment, the one or more acids comprise approximately 38.8% by weight pure sulfuric acid. In a further aspect of this embodiment, the one or more acids consist essentially of approximately 38.8% by weight pure sulfuric acid. In a further aspect of this embodiment, the one or more acids consist of approximately 38.8% by weight pure sulfuric acid.

[0080] In another embodiment of the cleaning composition, the one or more acids comprise hydrochloric acid. In a further aspect of this embodiment, the one or more acids consist essentially of hydrochloric acid. In a further aspect of this embodiment, the one or more acids consist of hydrochloric acid. In a further aspect of this embodiment, the one or more acids comprise approximately 4.725% by weight pure hydrochloric acid. In a further aspect of this embodiment, the one or more acids consist essentially of approximately 4.725% by weight hydrochloric acid. In a further aspect of this embodiment, the one or more acids consist of approximately 4.725% by weight hydrochloric acid. In a further aspect of this embodiment, the one or more acids comprise approximately 3.5% by weight pure hydrochloric acid. In a further aspect of this embodiment, the one or more acids consist essentially of approximately 3.5% by weight hydrochloric acid. In a further aspect of this embodiment, the one or more acids consist of approximately 3.5% by weight hydrochloric acid.

[0081] In another embodiment of the cleaning composition, the one or more acids include sulfuric acid and hydrochloric acid. In a further aspect of this embodiment, the one or more acids consist essentially of sulfuric acid and hydrochloric acid. In a further aspect of this embodiment, the one or more acids consist of sulfuric acid and hydrochloric acid. In a further aspect of this embodiment, the one or more acids comprise approximately 38.8% by weight pure sulfuric acid and approximately 4.725% by weight pure hydrochloric acid. In a further aspect of this embodiment, the one or more acids consist essentially of approximately 38.8% by weight pure sulfuric acid and approximately 4.725% by weight pure hydrochloric acid. In a further aspect of this embodiment, the one or more acids consist of approximately 38.8% by weight pure sulfuric acid and approximately 4.725% by weight pure hydrochloric acid. In a further aspect of this embodiment, the one or more acids consist of approximately 38.8% by weight pure sulfuric acid and approximately 4.725% by weight pure hydrochloric acid. In a further aspect of this embodiment, the one or more acids comprise approximately 38.8% by weight pure sulfuric acid and approximately 3.5% by weight pure hydrochloric acid. In a further aspect of this embodiment, the one or more acids consist essentially of approximately 38.8% by weight pure sulfuric acid and approximately 3.5% by weight pure hydrochloric acid. In a further aspect of this embodiment, the one or more acids consist essentially of approximately 38.8% by weight pure sulfuric acid and approximately 3.5% by weight pure hydrochloric acid.

[0082] In another embodiment, the cleaning composition comprises water, sulfuric acid, and nitric acid. In a further aspect of this embodiment, the cleaning composition consists essentially of water, sulfuric acid, and nitric acid. In a further aspect of this embodiment, the cleaning composition consists of water, sulfuric acid, and nitric acid. In a further aspect of this embodiment, the cleaning composition comprises water, about 33.5% to about 50% by weight of pure sulfuric acid, and about 0.9% by weight of pure nitric acid. In a further aspect of this embodiment, the cleaning composition consists essentially of water, about 33.5% to about 50% by weight of pure sulfuric acid, and about 0.9% by weight of pure nitric acid. In a further aspect of this embodiment, the cleaning composition consists of water, about 33.5% to about 50% by weight of pure sulfuric acid, and about 0.9% by weight of pure nitric acid.

[0083] In another embodiment, the cleaning composition comprises water, hydrochloric acid, and nitric acid. In a further aspect of this embodiment, the composition consists essentially of water, hydrochloric acid, and nitric acid. In a further aspect of this embodiment, the composition consists of water, hydrochloric acid, and nitric acid. In a further aspect of this embodiment, the composition comprises water, about 3.0% to about 5.0% by weight of pure hydrochloric acid, and about 0.6% to about 0.9% by weight of pure nitric acid. In a further aspect of this embodiment, the composition consists essentially of water, about 3.0% to about 5.0% by weight of pure hydrochloric acid, and about 0.6% to about 0.9% by weight of pure nitric acid. In a further aspect of this embodiment, the composition consists of water, about 3.0% to about 5.0% by weight of pure hydrochloric acid, and about 0.6% to about 0.9% by weight of pure nitric acid.

[0084] In another embodiment, the composition comprises water, hydrochloric acid, nitric acid, and methanesulfonic acid. In a further aspect of this embodiment, the composition consists essentially of water, hydrochloric acid, nitric acid, and methanesulfonic acid. In a further aspect of this embodiment, the composition consists essentially of water, hydrochloric acid, nitric acid, and methanesulfonic acid. In a further aspect of this embodiment, the composition comprises water, about 3.0% to about 5.0% by weight of pure hydrochloric acid, about 0.6% to about 0.9% by weight of pure nitric acid, and about 40% by weight of methanesulfonic acid. In a further aspect of this embodiment, the composition consists essentially of water, about 3.0% to about 5.0% by weight of pure hydrochloric acid, about 0.6% to about 0.9% by weight of pure nitric acid, and about 40% by weight of methanesulfonic acid. In a further aspect of this embodiment, the composition consists of water, approximately 3.0% to approximately 5.0% by weight of pure hydrochloric acid, approximately 0.6% to approximately 0.9% by weight of pure nitric acid, and approximately 40% by weight of methanesulfonic acid.

[0085] In another embodiment, the composition comprises water, hydrochloric acid, nitric acid, methanesulfonic acid, and 2,5-dihydroxy-1,4-benzoquinone. In a further aspect of this embodiment, the composition consists essentially of water, hydrochloric acid, nitric acid, methanesulfonic acid, and 2,5-dihydroxy-1,4-benzoquinone. In a further aspect of this embodiment, the composition consists of water, hydrochloric acid, nitric acid, methanesulfonic acid, and 2,5-dihydroxy-1,4-benzoquinone. In a further aspect of this embodiment, the composition comprises water, about 3.0% to about 5.0% by weight of pure hydrochloric acid, about 0.6% to about 0.9% by weight of pure nitric acid, about 40% by weight of methanesulfonic acid, and 2,5-dihydroxy-1,4-benzoquinone. In a further aspect of this embodiment, the composition consists essentially of water, about 3.0% to about 5.0% by weight of pure hydrochloric acid, about 0.6% to about 0.9% by weight of pure nitric acid, about 40% by weight of methanesulfonic acid, and 2,5-dihydroxy-1,4-benzoquinone. In a further aspect of this embodiment, the composition consists essentially of water, about 3.0% to about 5.0% by weight of pure hydrochloric acid, about 0.6% to about 0.9% by weight of pure nitric acid, about 40% by weight of methanesulfonic acid, and 2,5-dihydroxy-1,4-benzoquinone.

[0086] In another embodiment, the composition comprises water, hydrochloric acid, methanesulfonic acid, and 2,5-dihydroxy-1,4-benzoquinone. In a further aspect of this embodiment, the composition consists essentially of water, hydrochloric acid, methanesulfonic acid, and 2,5-dihydroxy-1,4-benzoquinone. In a further aspect of this embodiment, the composition consists essentially of water, hydrochloric acid, methanesulfonic acid, and 2,5-dihydroxy-1,4-benzoquinone. In a further aspect of this embodiment, the composition comprises water, about 3.0% to about 5.0% by weight of pure hydrochloric acid, about 40% by weight of methanesulfonic acid, and 2,5-dihydroxy-1,4-benzoquinone. In a further aspect of this embodiment, the composition consists essentially of water, about 3.0% to about 5.0% by weight of pure hydrochloric acid, about 40% by weight of methanesulfonic acid, and 2,5-dihydroxy-1,4-benzoquinone. In a further aspect of this embodiment, the composition consists of water, approximately 3.0% to approximately 5.0% by weight of pure hydrochloric acid, approximately 40% by weight of methanesulfonic acid, and 2,5-dihydroxy-1,4-benzoquinone.

[0087] In another embodiment, the composition comprises water, sulfuric acid, hydrochloric acid, and nitric acid. In a further aspect of this embodiment, the composition consists essentially of water, sulfuric acid, hydrochloric acid, and nitric acid. In a further aspect of this embodiment, the composition consists of water, sulfuric acid, hydrochloric acid, and nitric acid. In a further aspect of this embodiment, the composition comprises water and about 40% to about 45% by weight, combined, of pure sulfuric acid, pure hydrochloric acid, and pure nitric acid. In a further aspect of this embodiment, the composition consists essentially of water and about 40% to about 45% by weight, combined, of pure sulfuric acid, pure hydrochloric acid, and pure nitric acid. In a further aspect of this embodiment, the composition consists of water and about 40% to about 45% by weight, combined, of pure sulfuric acid, pure hydrochloric acid, and pure nitric acid. In a further aspect of this embodiment, the composition comprises ...3% to about 45% by weight, combined, of pure sulfuric acid, pure hydrochloric acid, and pure nitric acid. In a further aspect of this embodiment, the composition consists essentially of water and about 43% to about 45% by weight of pure sulfuric acid, pure hydrochloric acid, and pure nitric acid, taken together. In a further aspect of this embodiment, the composition consists essentially of water and about 43% to about 45% by weight of pure sulfuric acid, pure hydrochloric acid, and pure nitric acid, taken together. In a further aspect of this embodiment, the composition comprises water, about 38.8% by weight of pure sulfuric acid, about 4.725% by weight of pure hydrochloric acid, and about 0.6% by weight of pure nitric acid. In a further aspect of this embodiment, the composition consists essentially of ... In a further aspect of this embodiment, the composition comprises water, approximately 38.8% by weight pure sulfuric acid, approximately 4.725% by weight pure hydrochloric acid, and approximately 0.9% by weight pure nitric acid. In a further aspect of this embodiment, the composition consists essentially of water, approximately 38.8% by weight pure sulfuric acid, approximately 4.725% by weight pure hydrochloric acid, and approximately 0.9% by weight pure nitric acid. In a further aspect of this embodiment, the composition consists of water, approximately 38.8% by weight pure sulfuric acid, approximately 4.725% by weight pure hydrochloric acid, and approximately 0.9% by weight pure nitric acid.In a further aspect of this embodiment, the composition comprises water, approximately 38.8% by weight pure sulfuric acid, approximately 3.5% by weight pure hydrochloric acid, and approximately 0.6% by weight pure nitric acid. In a further aspect of this embodiment, the composition consists essentially of water, approximately 38.8% by weight pure sulfuric acid, approximately 3.5% by weight pure hydrochloric acid, and approximately 0.6% by weight pure nitric acid. In a further aspect of this embodiment, the composition consists essentially of water, approximately 38.8% by weight pure sulfuric acid, approximately 3.5% by weight pure hydrochloric acid, and approximately 0.6% by weight pure nitric acid. In a further aspect of this embodiment, the composition comprises water, approximately 38.8% by weight pure sulfuric acid, approximately 3.5% by weight pure hydrochloric acid, and approximately 0.9% by weight pure nitric acid. In a further aspect of this embodiment, the composition consists essentially of water, approximately 38.8% by weight pure sulfuric acid, approximately 3.5% by weight pure hydrochloric acid, and approximately 0.9% by weight pure nitric acid. In a further aspect of this embodiment, the composition consists of water, approximately 38.8% by weight pure sulfuric acid, approximately 3.5% by weight pure hydrochloric acid, and approximately 0.9% by weight pure nitric acid.

[0088] In another embodiment, the composition comprises water, sulfuric acid, hydrochloric acid, nitric acid, and ammonium chloride. In a further aspect of this embodiment, the composition consists essentially of water, sulfuric acid, hydrochloric acid, nitric acid, and ammonium chloride. In a further aspect of this embodiment, the composition consists of water, sulfuric acid, hydrochloric acid, nitric acid, and ammonium chloride. In a further aspect of this embodiment, the composition comprises water, approximately 38.8% by weight pure sulfuric acid, approximately 4.725% by weight pure hydrochloric acid, approximately 0.6% by weight pure nitric acid, and ammonium chloride. In a further aspect of this embodiment, the composition consists essentially of ... of water, approximately 38.8% by weight pure sulfuric acid, approximately 4.725% by weight pure hydrochloric acid, approximately 0.6% by weight pure nitric acid, and ammonium chloride. In a further aspect of this embodiment, the composition comprises water, approximately 38.8% by weight pure sulfuric acid, approximately 4.725% by weight pure hydrochloric acid, approximately 0.9% by weight pure nitric acid, and ammonium chloride. In a further aspect of this embodiment, the composition consists essentially of water, approximately 38.8% by weight pure sulfuric acid, approximately 4.725% by weight pure hydrochloric acid, approximately 0.9% by weight pure nitric acid, and ammonium chloride. In a further aspect of this embodiment, the composition consists of water, approximately 38.8% by weight pure sulfuric acid, approximately 4.725% by weight pure hydrochloric acid, approximately 0.9% by weight pure nitric acid, and ammonium chloride.

[0089] In another embodiment of the cleaning composition, the one or more halogen ion sources include one or more of hydrobromic acid, hydroiodic acid, hydrogen chloride, hydrofluoric acid, hydrochloric acid, ammonium chloride, ammonium bromide, ammonium fluoride, and ammonium iodide. In a further aspect of this embodiment, the one or more halogen ion sources essentially consist of one or more of hydrobromic acid, hydroiodic acid, hydrogen chloride, hydrofluoric acid, hydrochloric acid, ammonium chloride, ammonium bromide, ammonium fluoride, and ammonium iodide. In a further aspect of this embodiment, the one or more halogen ion sources consist of one or more of hydrobromic acid, hydroiodic acid, hydrogen chloride, hydrofluoric acid, hydrochloric acid, ammonium chloride, ammonium bromide, ammonium fluoride, and ammonium iodide. In a further aspect of this embodiment, the one or more halogen ion sources include approximately 2% by weight ammonium chloride. In a further aspect of this embodiment, the one or more sources of halogen ions consist essentially of approximately 2% by weight ammonium chloride. In a further aspect of this embodiment, the one or more sources of halogen ions consist of approximately 2% by weight ammonium chloride.

[0090] performance

[0091] The disclosed and claimed cleaning compositions have high Ni etch rates (at approximately 30° C.).

[0092] In one embodiment, the disclosed and claimed cleaning compositions have a Ni etch rate of about 200 to about 700. In a further aspect of this embodiment, the composition has a Ni etch rate of about 300 to about 700. In a further aspect of this embodiment, the composition has a Ni etch rate of about 400 to about 700. In a further aspect of this embodiment, the composition has a Ni etch rate of about 500 to about 700. In a further aspect of this embodiment, the composition has a Ni etch rate of about 600 to about 700. In a further aspect of this embodiment, the composition has a Ni etch rate of about 200 or greater. In a further aspect of this embodiment, the composition has a Ni etch rate of about 300 or greater. In a further aspect of this embodiment, the composition has a Ni etch rate of about 400 or greater. In a further aspect of this embodiment, the composition has a Ni etch rate of about 500 or greater. In a further aspect of this embodiment, the composition has a Ni etch rate of about 600 or greater.

[0093] The disclosed and claimed cleaning compositions also have high Fe2O3 solubility.

[0094] In one embodiment, the disclosed and claimed cleaning compositions have a Fe2O3 solubility of about 2 mg / 100 ml or more to about 11 mg / 100 ml or more. In a further aspect of this embodiment, the composition has a Fe2O3 solubility of about 5 mg / 100 ml or more to about 10 mg / 100 ml or more. In a further aspect of this embodiment, the composition has a Fe2O3 solubility of about 2 mg / 100 ml or more. In a further aspect of this embodiment, the composition has a Fe2O3 solubility of about 3 mg / 100 ml or more. In a further aspect of this embodiment, the composition has a Fe2O3 solubility of about 4 mg / 100 ml or more. In a further aspect of this embodiment, the composition has a Fe2O3 solubility of about 5 mg / 100 ml or more. In a further aspect of this embodiment, the composition has a Fe2O3 solubility of about 6 mg / 100 ml or more. In a further aspect of this embodiment, the composition has a Fe2O3 solubility of about 7 mg / 100 ml or more. In a further aspect of this embodiment, the composition has a Fe2O3 solubility of about 8 mg / 100 ml or more. In a further aspect of this embodiment, the composition has a Fe2O3 solubility of about 9 mg / 100 ml or more. In a further aspect of this embodiment, the composition has a Fe2O3 solubility of about 10 mg / 100 ml or more. In a further aspect of this embodiment, the composition has a Fe2O3 solubility of about 11 mg / 100 ml or more.

[0095] How to use

[0096] The disclosed and claimed subject matter further includes the use of the disclosed and claimed cleaning compositions to remove one or more metal-containing layers in a mask protection structure for EUV lithography. The EUV mask protection structure may include any number of layers on a semiconductor device, which are deposited or formed and removed or partially removed by methods known to those skilled in the art, such as by one or more deposition steps, followed by one or more lithography steps, followed by one or more wet or dry etching steps. One or more layers may be present between the semiconductor substrate and the EUV mask. The semiconductor device on which the EUV mask and EUV mask protection structure (the mask protection structure may be referred to as a "pellicle structure") are present may include any number of material layers thereon, in addition to the EUV mask and EUV mask protection structure.

[0097] Thus, in another aspect, the disclosed and claimed subject matter comprises: a. forming one or more layers, including at least one Ni-containing layer, on a silicon substrate; and b. removing the Ni-containing layer by contacting said Ni-containing layer with at least one of the compositions of the disclosed and claimed subject matter; The present invention relates to a method for manufacturing a semiconductor device, comprising:

[0098] In another aspect, the disclosed and claimed subject matter comprises: a. providing a semiconductor device comprising a substrate and an EUV mask and a metal-containing EUV mask protection structure; b. exposing the semiconductor device to EUV radiation; and c. removing the metal-containing EUV mask protective structure by contacting the semiconductor device with at least one of the compositions of the disclosed and claimed subject matter; In a further aspect of this embodiment, the method further comprises the additional steps of: d. depositing the metal-containing EUV mask protection structure onto the semiconductor device via atomic layer deposition (ALD), e-beam evaporation, chemical vapor deposition, or electroplating; e. performing a selective dry etching process on at least a portion of the semiconductor device prior to the removing step c; Includes one or more of the following.

[0099] In one embodiment, the EUV mask protection structure may include multiple layers, with at least one layer including a metal-containing layer, which may be a film or mesh or any type of metal-containing layer. In a further aspect, the metal-containing layer may be a tie layer or a heat dissipation layer.

[0100] In further embodiments, the one or more metal-containing layers may be applied by atomic layer deposition (ALD), e-beam evaporation, or chemical vapor deposition (CVD), or electroplating, or any method known to those of skill in the art of depositing or otherwise forming a metal on a surface.

[0101] In further embodiments, the EUV pellicle structure may include one or more of an EUV transparent layer, a graphene layer (which may be formed on the EUV transparent layer), an interconnect pattern provided on the defects, and / or a heat dissipation layer that may be on the graphene layer. In further aspects of this embodiment, the graphene layer may include a polycrystalline structure. In further aspects of this embodiment, the interconnect pattern may include interconnected crystals of the graphene layer in a polycrystalline structure. An additional sacrificial layer made of a polymer may also be added.

[0102] In a further embodiment, the EUV pellicle structure may include a metal layer or a metal wire mesh layer.

[0103] In further embodiments, the EUV pellicle structure may additionally or alternatively include one or more of an insulating layer, a passivation layer, a graphene layer, an interconnect layer, an EUV transparent layer, and a heat dissipation layer, so long as one layer or a portion of a layer is a metal-containing layer. In a further aspect of this embodiment, the semiconductor device may include a substrate, such as a silicon substrate, on which a layer is deposited or formed.

[0104] In further embodiments, the heat spreader layer comprises molybdenum and / or zirconium and / or a material with an emissivity of 0.1 or greater at temperatures of 700 K or greater. Thus, for example, in some aspects of the present embodiment, the heat spreader layer may comprise titanium (Ti), tantalum (Ta), tungsten (W), molybdenum (Mo), chromium (Cr), cobalt (Co), boron (B), and carbon (C), nickel (Ni), and oxides and mixtures thereof. In other aspects of the present embodiment, the heat spreader layer may comprise gold (Au), platinum (Pt), mixtures thereof, and carbon nanostructures.

[0105] In a further embodiment, a heat dissipation layer may be formed on the interconnect pattern, including a material with high thermal emissivity and excellent chemical resistance to hydrogen. The heat dissipation layer minimizes thermal deformation of the EUV pellicle structure that would otherwise be caused by EUV radiation. By doing so, the reliability and life characteristics of the pellicle structure may be improved. In addition, the interconnect pattern and / or the heat dissipation layer may be formed from a material that provides a low extinction coefficient value, high transmittance to EUV light, high mechanical strength, and thermal stability. In one embodiment, the heat dissipation layer includes a metal, for example nickel (Ni).

[0106] In further embodiments, the EUV mask protective structure may include an EUV transmissive layer including a material having an extinction coefficient for EUV of 0.01 or less. In such embodiments, the EUV transmissive layer may include beryllium (Be), boron (B), carbon (C), silicon (Si), and phosphorus (P), sulfur (S), potassium (K), calcium (Ca), scandium (Sc), bromine (Br), rubidium (Rb), strontium (Sr), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), barium (Ba), lanthanum (La), cerium (Ce), praseodymium (Pr), and uranium (U). In such embodiments, the EUV transmissive layer may comprise oxides, nitrides, carbides, or borides of the above-mentioned materials having an extinction coefficient for EUV of 0.01 or less, which are stabilized compounds of materials having an extinction coefficient of 0.01 or less and / or an emissivity of 0.1 or greater at temperatures of 700 K or greater.

[0107] In further embodiments, the EUV mask protection structure may include a graphene layer. In such embodiments, the graphene layer may be formed on the EUV transparent layer. In one aspect of this embodiment, the graphene layer may be formed on the EUV transparent layer by chemical vapor deposition (CVD), atomic layer deposition (ALD), or the like. When formed by one of these processes, the graphene layer may have a polycrystalline structure. Thus, the graphene layer may include a plurality of defects, such as point defects, such as vacancies present in the graphene layer, or line defects present in the graphene layer, or grain boundaries due to changes in crystal orientation.

[0108] In further embodiments, the EUV mask protection structure may include a heat dissipation layer, alone or with other layers. In such embodiments, the heat dissipation layer may be formed on the interconnect pattern. In one aspect of this embodiment, the heat dissipation layer may be formed by e-beam evaporation. If the heat dissipation layer is formed on the interconnect pattern by a plasma process or a thermal evaporation process, it may be difficult to deposit a material with high transmittance to EUV. On the other hand, if the heat dissipation layer is formed on the interconnect pattern by an e-beam deposition method, a material with high transmittance to EUV is produced, so that the EUV pellicle structure also has high transmittance.

[0109] In further embodiments, the heat dissipation layer may include a material with a high thermal emissivity, a low extinction coefficient value, and a thermal expansion coefficient that is similar to the interconnect pattern (if present) in order to minimize thermal deformation of the EUV pellicle structure. In such embodiments, the heat dissipation layer may be formed from a material that has excellent chemical resistance to hydrogen, thereby improving the reliability and life characteristics of the pellicle structure. In one aspect of this embodiment, the heat dissipation layer may include a material with a thermal expansion coefficient that is similar to the interconnect pattern.

[0110] In further embodiments, the heat dissipation layer and / or the tie layer may include molybdenum and / or zirconium and / or other metal(s) as discussed above. Additionally, according to one embodiment, the heat dissipation layer may include a material having an emissivity of 0.1 or greater at temperatures of 700K or greater in addition to molybdenum and zirconium. The heat dissipation layer may be formed by electron beam evaporation, which facilitates deposition of materials with high EUV transparency. An EUV pellicle structure according to one embodiment of the disclosed and claimed subject matter may be used to protect masks used in EUV lithography in the manufacture of various semiconductor devices.

[0111] In some embodiments, the EUV protective structure may include nickel, either alone or in combination with other metals. EXAMPLES

[0112] example

[0113] More specific embodiments of the present disclosure, as well as experimental results supporting such embodiments, are described below. These examples are provided below to more fully illustrate the disclosed subject matter, and should not be construed as limiting the disclosed subject matter in any way.

[0114] It will be apparent to those skilled in the art that various modifications and variations can be made in the disclosed subject matter and the specific examples provided without departing from the spirit or scope of the disclosed subject matter. Thus, the disclosed subject matter, including the description provided by the following examples, is intended to cover modifications and variations of the disclosed subject matter that come within the scope of any claims and their equivalents.

[0115] Materials and Methods:

[0116] All chemicals used herein are commercially available (eg, from Sigma-Aldrich).

[0117] The acid was weighed and dissolved in DIW in a beaker. If a second acid was used, it was added slowly to the solution. The oxidizer was added to the solution, followed by the remaining ingredients. The solution was stirred to uniformly dissolve the solid reagents and produce a homogenous mixture. The mixture was heated to the specified temperature.

[0118] The wafer was immersed in the mixture at the test temperature for the time indicated in the example below. The wafer was then removed from the mixture and rinsed with DIW for about 3 minutes. The rinsed wafer was then subjected to drying under nitrogen gas. The dried wafer was tested. Etch rates were measured at temperatures indicated in the examples from about 25° C. to about 50° C., with the time frame for etching Ni being 0 to about 1 minute, and the time frame for etching silicon oxide (SiOx) and silicon nitride (SiNx) being about 10 minutes.

[0119] The etch rate of Ni was measured using a ResMap4 tip probe resistivity meter, and the etch rates of silicon oxide and silicon nitride were measured using a Filmtek PAR 2000SE from Scientific Computing International. The etch rate was calculated by dividing the difference in thickness before and after treatment by the immersion time.

[0120] Separately, the solubility of metal oxides was measured using a weighing method where the iron oxide was dissolved and kept in solution until the solution became heterogeneous.

[0121] In the tables below, the numerical values ​​given for acids in parentheses (eg, "(30.8)") are for the pure acid, if such acid is present in the illustrated embodiment.

[0122] Example of a formulation

[0123] The following formulation examples demonstrate representative embodiments of the disclosed and claimed subject matter that provide metal etching compositions and methods with high removal rates, such as greater than 300 Å / min, or greater than 400 Å / min, and slightly greater than 500 Å / min at 30° C. These etching compositions also provide good Fe2O3 solubility, greater than 2 mg / 100 mL (i.e., greater than 2 mg of Fe2O3 can be dissolved in 100 mL of the formulation examples). These etching compositions also provide good compatibility with silicon nitride (Si3N4) and silicon oxide (SiO2) and other materials on semiconductor substrates. The etch rate of silicon nitride is less than 1 Å / min at 30° C.

[0124] In Table 1, three acid component formulations were tested, including H2SO4 as a strong acid, HNO3 as an oxidizer, and HCl as a second acid and halogen source (chloride ion source). They all provided metal (Ni) etching rates of over 340 Å / min at 30° C. and had good metal oxide (Fe2O3) solubility of over 8 mg / 100 mL. NH4Cl can also act as a halogen source (chloride ion source) to aid in metal chelate formation and metal oxide (Fe2O3) solubility. Example 2 has the best metal oxide (Fe2O3) solubility with the addition of 2% NH4Cl. All three acid component formulations provided good silicon oxide and SiN compatibility. The bath life of Example 4 was tested and had a long bath life of over 168 hours at 30° C. without losing its metal (Ni) etching ability. [Table 1]

[0125] The examples in Table 2 show that H2SO4 and HNO3 have high Ni etch rates. In the absence of chloride ions, the metal oxide (Fe2O3) solubility was less than 2 mg / 100 mL. [Table 2]

[0126] Table 3 compares ammonium persulfate (APS) and 2,5-dihydroxy-1,4-benzoquinone (oxidizer) in H2SO4 or HCl systems. In the H2SO4 system, APS provides a higher metal (Ni) etch rate than 2,5-dihydroxy-1,4-benzoquinone. Both APS and 2,5-dihydroxy-1,4-benzoquinone also provide a higher metal (Ni) etch rate and better metal oxide (Fe2O3) solubility in HCl. [Table 3]

[0127] In Table 4, methanesulfonic acid (MSA) provided high metal (Ni) etch rate and good metal oxide (Fe2O3) solubility. MSA and 2,5-dihydroxy-1,4-benzoquinone together in the formulation provided the highest metal (Ni) etch rate and good metal oxide (Fe2O3) solubility. [Table 4]

[0128] While embodiments of the disclosed and claimed subject matter have been disclosed above for purposes of illustration, those skilled in the art will recognize that various modifications, additions, and substitutions may be made thereto without departing from the scope and spirit of the disclosed and claimed subject matter, as set forth in the appended claims. The present invention includes the following aspects. (1) (i) Water; (ii) one or more oxidizing agents; and (iii) one or more acids, A composition comprising: (2) (i) Water; (ii) one or more oxidizing agents; and (iii) one or more acids, A composition consisting essentially of. (3) (i) Water; (ii) one or more oxidizing agents; and (iii) one or more acids, A composition consisting of: (4) (iv) The composition according to any one of (1) to (3), further comprising one or more halogen ion sources. (5) (v) The composition according to any one of (1) to (3), further comprising one or more chelating agents. (6) The composition according to any one of (1) to (3), further comprising (iv) one or more halogen ion sources and (v) one or more chelating agents. (7) The composition according to any one of (1) to (3), wherein the one or more acids include a halogen ion source. (8) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents include one or more of peroxomonosulfates, perborates, perchlorates, perchloric acid, peracetate anion, sulfuric acid, periodates, persulfates, permanganates, chromates, dichromates, benzoquinones, nitric acid, and amine-N-oxides. (9) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents include one or more of ammonium persulfate (APS), 2,5-dihydroxy-1,4-benzoquinone, nitrosylsulfuric acid, pyridine N-oxide, and 4-methylmorpholine N-oxide. (10) The composition according to any one of (1) to (3), wherein the one or more acids include one or more of sulfuric acid, hydrochloric acid, an alkylsulfonic acid such as methanesulfonic acid, an alkylbenzylsulfonic acid such as 4-methylbenzenesulfonic acid, hydrobromic acid, citric acid, malonic acid, hydrofluoric acid, acetic acid, phosphoric acid, and hydroiodic acid. (11) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents include nitric acid. (12) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents consist essentially of nitric acid. (13) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents comprise nitric acid. (14) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents comprise about 0.1% by mass to about 1.0% by mass of pure nitric acid. (15) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents consist essentially of about 0.1% by weight to about 1.0% by weight of pure nitric acid. (16) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents consist of about 0.1% by weight to about 1.0% by weight of pure nitric acid. (17) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents comprise approximately 0.9% by mass of pure nitric acid. (18) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents consist essentially of approximately 0.9% by weight of pure nitric acid. (19) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents comprise approximately 0.9% by weight of pure nitric acid. (20) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents comprise approximately 0.6% by mass of pure nitric acid. (21) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents consist essentially of approximately 0.6% by weight of pure nitric acid. (22) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents comprise approximately 0.6% by weight of pure nitric acid. (23) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents include 2,5-dihydroxy-1,4-benzoquinone. (24) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents consist essentially of 2,5-dihydroxy-1,4-benzoquinone. (25) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents comprise 2,5-dihydroxy-1,4-benzoquinone. (26) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents include approximately 0.01% by mass of 2,5-dihydroxy-1,4-benzoquinone. (27) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents consist essentially of approximately 0.01% by weight of 2,5-dihydroxy-1,4-benzoquinone. (28) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents comprise approximately 0.01% by weight of 2,5-dihydroxy-1,4-benzoquinone. (29) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents include ammonium persulfate. (30) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents consist essentially of ammonium persulfate. (31) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents comprise ammonium persulfate. (32) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents include approximately 1.0 mass % ammonium persulfate. (33) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents consist essentially of approximately 1.0 wt. % ammonium persulfate. (34) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents comprise approximately 1.0% by weight of ammonium persulfate. (35) The composition according to any one of (1) to (3), wherein the total mass percentage of the pure acids in the composition is about 15 mass% to about 50 mass%. (36) The composition according to any one of (1) to (3), wherein the total mass percentage of the pure acids in the composition is about 30 mass% to about 45 mass%. (37) The composition according to any one of (1) to (3), wherein the total mass percent of the pure acids in the composition is about 35 mass% to about 45 mass%. (38) The composition according to any one of (1) to (3), wherein the total mass percentage of the pure acids in the composition is about 30 mass% to about 40 mass%. (39) The composition according to any one of (1) to (3), wherein the total mass percent of the pure acids in the composition is about 35 mass% to about 40 mass%. (40) The composition according to any one of (1) to (3), wherein the total mass percent of the pure acids in the composition is about 40 mass% to about 45 mass%. (41) The composition according to any one of (1) to (3), wherein the one or more acids include sulfuric acid. (42) The composition according to any one of (1) to (3), wherein the one or more acids consist essentially of sulfuric acid. (43) The composition according to any one of (1) to (3), wherein the one or more acids comprise sulfuric acid. (44) The composition according to any one of (1) to (3), wherein the one or more acids comprise approximately 38.8% by mass of pure sulfuric acid. (45) The composition according to any one of (1) to (3), wherein the one or more acids consist essentially of approximately 38.8% by weight of pure sulfuric acid. (46) The composition according to any one of (1) to (3), wherein the one or more acids comprise approximately 38.8% by weight of pure sulfuric acid. (47) The composition according to any one of (1) to (3), wherein the one or more acids include hydrochloric acid. (48) The composition according to any one of (1) to (3), wherein the one or more acids consist essentially of hydrochloric acid. (49) The composition according to any one of (1) to (3), wherein the one or more acids comprise hydrochloric acid. (50) The composition according to any one of (1) to (3), wherein the one or more acids comprise approximately 4.725% by weight of pure hydrochloric acid. (51) The composition according to any one of (1) to (3), wherein the one or more acids consist essentially of approximately 4.725% by weight of hydrochloric acid. (52) The composition according to any one of (1) to (3), wherein the one or more acids comprise approximately 4.725% by weight of hydrochloric acid. (53) The composition according to any one of (1) to (3), wherein the one or more acids comprise approximately 3.5% by mass of pure hydrochloric acid. (54) The composition according to any one of (1) to (3), wherein the one or more acids consist essentially of approximately 3.5% by weight of hydrochloric acid. (55) The composition according to any one of (1) to (3), wherein the one or more acids comprise approximately 3.5% by weight of hydrochloric acid. (56) The composition according to any one of (1) to (3), wherein the one or more acids include sulfuric acid and hydrochloric acid. (57) The composition according to any one of (1) to (3), wherein the one or more acids consist essentially of sulfuric acid and hydrochloric acid. (58) The composition according to any one of (1) to (3), wherein the one or more acids consist of sulfuric acid and hydrochloric acid. (59) The composition according to any one of (1) to (3), wherein the one or more acids comprise approximately 38.8% by weight of pure sulfuric acid and approximately 4.725% by weight of pure hydrochloric acid. (60) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents consist essentially of approximately 38.8% by weight of pure sulfuric acid and approximately 4.725% by weight of pure hydrochloric acid. (61) The composition according to any one of (1) to (3), wherein the one or more acids consist of approximately 38.8% by weight of pure sulfuric acid and approximately 4.725% by weight of pure hydrochloric acid. (62) The composition according to any one of (1) to (3), wherein the one or more acids comprise approximately 38.8% by weight of pure sulfuric acid and approximately 3.5% by weight of pure hydrochloric acid. (63) The composition according to any one of (1) to (3), wherein the one or more oxidizing agents consist essentially of approximately 38.8% by weight of pure sulfuric acid and approximately 3.5% by weight of pure hydrochloric acid. (64) The composition according to any one of (1) to (3), wherein the one or more acids consist of approximately 38.8% by weight of pure sulfuric acid and approximately 3.5% by weight of pure hydrochloric acid. (65) The composition according to any one of (1) to (3), comprising water, sulfuric acid, and nitric acid. (66) The composition according to any one of (1) to (3), consisting essentially of water, sulfuric acid, and nitric acid. (67) The composition according to any one of (1) to (3), which consists of water, sulfuric acid, and nitric acid. (68) The composition according to any one of (1) to (3), comprising water, approximately 33.5% by mass to approximately 50% by mass of pure sulfuric acid, and approximately 0.9% by mass of pure nitric acid. (69) The composition according to any one of (1) to (3), consisting essentially of water, approximately 33.5% by weight to approximately 50% by weight of pure sulfuric acid, and approximately 0.9% by weight of pure nitric acid. (70) The composition according to any one of (1) to (3), comprising water, approximately 33.5% by mass to approximately 50% by mass of pure sulfuric acid, and approximately 0.9% by mass of pure nitric acid. (71) The composition according to (1), comprising water, hydrochloric acid, and nitric acid. (72) The composition described in (2), consisting essentially of water, hydrochloric acid, and nitric acid. (73) The composition according to (3), which consists of water, hydrochloric acid, and nitric acid. (74) The composition according to (1), comprising water, about 3.0% by weight to about 5.0% by weight of pure hydrochloric acid, and about 0.6% by weight to about 0.9% by weight of pure nitric acid. (75) The composition according to (2), consisting essentially of water, approximately 3.0% to approximately 5.0% by weight of pure hydrochloric acid, and approximately 0.6% to approximately 0.9% by weight of pure nitric acid. (76) The composition according to (3), comprising water, approximately 3.0% to approximately 5.0% by weight of pure hydrochloric acid, and approximately 0.6% to approximately 0.9% by weight of pure nitric acid. (77) The composition according to (1), comprising water, hydrochloric acid, nitric acid, and methanesulfonic acid. (78) The composition described in (2), consisting essentially of water, hydrochloric acid, nitric acid, and methanesulfonic acid. (79) The composition according to (3), which consists of water, hydrochloric acid, nitric acid, and methanesulfonic acid. (80) The composition according to (1), comprising water, about 3.0% by weight to about 5.0% by weight of pure hydrochloric acid, about 0.6% by weight to about 0.9% by weight of pure nitric acid, and about 40% by weight of methanesulfonic acid. (81) The composition according to (2), consisting essentially of water, approximately 3.0% to approximately 5.0% by weight of pure hydrochloric acid, approximately 0.6% to approximately 0.9% by weight of pure nitric acid, and approximately 40% by weight of methanesulfonic acid. (82) The composition according to (3), comprising water, approximately 3.0% by weight to approximately 5.0% by weight of pure hydrochloric acid, approximately 0.6% by weight to approximately 0.9% by weight of pure nitric acid, and approximately 40% by weight of methanesulfonic acid. (83) The composition according to (1), comprising water, hydrochloric acid, nitric acid, methanesulfonic acid, and 2,5-dihydroxy-1,4-benzoquinone. (84) The composition described in (2), consisting essentially of water, hydrochloric acid, nitric acid, methanesulfonic acid, and 2,5-dihydroxy-1,4-benzoquinone. (85) The composition according to (3), which consists of water, hydrochloric acid, nitric acid, methanesulfonic acid, and 2,5-dihydroxy-1,4-benzoquinone. (86) The composition according to (1), comprising water, approximately 3.0% by weight to approximately 5.0% by weight of pure hydrochloric acid, approximately 0.6% by weight to approximately 0.9% by weight of pure nitric acid, approximately 40% by weight of methanesulfonic acid, and 2,5-dihydroxy-1,4-benzoquinone. (87) The composition according to (2), consisting essentially of water, approximately 3.0% to approximately 5.0% by weight of pure hydrochloric acid, approximately 0.6% to approximately 0.9% by weight of pure nitric acid, approximately 40% by weight of methanesulfonic acid, and 2,5-dihydroxy-1,4-benzoquinone. (88) The composition according to (3), comprising water, approximately 3.0% by mass to approximately 5.0% by mass of pure hydrochloric acid, approximately 0.6% by mass to approximately 0.9% by mass of pure nitric acid, approximately 40% by mass of methanesulfonic acid, and 2,5-dihydroxy-1,4-benzoquinone. (89) The composition described in (1), comprising water, hydrochloric acid, methanesulfonic acid, and 2,5-dihydroxy-1,4-benzoquinone. (90) The composition described in (2), consisting essentially of water, hydrochloric acid, methanesulfonic acid, and 2,5-dihydroxy-1,4-benzoquinone. (91) The composition according to (3), which consists of water, hydrochloric acid, methanesulfonic acid, and 2,5-dihydroxy-1,4-benzoquinone. (92) The composition according to (1), comprising water, approximately 3.0% by mass to approximately 5.0% by mass of pure hydrochloric acid, approximately 40% by mass of methanesulfonic acid, and 2,5-dihydroxy-1,4-benzoquinone. (93) The composition according to (2), consisting essentially of water, approximately 3.0% by weight to approximately 5.0% by weight of pure hydrochloric acid, approximately 40% by weight of methanesulfonic acid, and 2,5-dihydroxy-1,4-benzoquinone. (94) The composition according to (3), comprising water, approximately 3.0% by mass to approximately 5.0% by mass of pure hydrochloric acid, approximately 40% by mass of methanesulfonic acid, and 2,5-dihydroxy-1,4-benzoquinone. (95) The composition according to (1), comprising water, sulfuric acid, hydrochloric acid, and nitric acid. (96) The composition described in (2), consisting essentially of water, sulfuric acid, hydrochloric acid, and nitric acid. (97) The composition according to (3), which consists of water, sulfuric acid, hydrochloric acid, and nitric acid. (98) The composition according to (1), comprising water and about 40% to about 45% by weight of pure sulfuric acid, pure hydrochloric acid, and pure nitric acid in total. (99) The composition described in (2), consisting essentially of water and approximately 40% to approximately 45% by weight of pure sulfuric acid, pure hydrochloric acid, and pure nitric acid combined. (100) The composition according to (3), comprising water and about 40% to about 45% by weight of pure sulfuric acid, pure hydrochloric acid, and pure nitric acid in total. (101) The composition according to (1), comprising water and about 43% to about 45% by weight of pure sulfuric acid, pure hydrochloric acid, and pure nitric acid in total. (102) The composition described in (2), consisting essentially of water and approximately 43% to approximately 45% by weight of pure sulfuric acid, pure hydrochloric acid, and pure nitric acid combined. (103) The composition according to (3), comprising water and about 43% to about 45% by weight of pure sulfuric acid, pure hydrochloric acid, and pure nitric acid. (104) 1. The composition of claim 1, comprising water, approximately 38.8% by weight of pure sulfuric acid, approximately 4.725% by weight of pure hydrochloric acid, and approximately 0.6% by weight of pure nitric acid. (105) The composition of (2), consisting essentially of water, approximately 38.8% by weight of pure sulfuric acid, approximately 4.725% by weight of pure hydrochloric acid, and approximately 0.6% by weight of pure nitric acid. (106) The composition of (3), comprising water, approximately 38.8% by weight of pure sulfuric acid, approximately 4.725% by weight of pure hydrochloric acid, and approximately 0.6% by weight of pure nitric acid. (107) 1. The composition of claim 1, comprising water, approximately 38.8% by weight of pure sulfuric acid, approximately 4.725% by weight of pure hydrochloric acid, and approximately 0.9% by weight of pure nitric acid. (108) The composition of (2), consisting essentially of water, approximately 38.8% by weight of pure sulfuric acid, approximately 4.725% by weight of pure hydrochloric acid, and approximately 0.9% by weight of pure nitric acid. (109) The composition of (3), consisting of water, approximately 38.8% by weight of pure sulfuric acid, approximately 4.725% by weight of pure hydrochloric acid, and approximately 0.9% by weight of pure nitric acid. (110) 1. The composition of claim 1, comprising water, approximately 38.8% by weight of pure sulfuric acid, approximately 3.5% by weight of pure hydrochloric acid, and approximately 0.6% by weight of pure nitric acid. (111) The composition of (2), consisting essentially of water, approximately 38.8% by weight of pure sulfuric acid, approximately 3.5% by weight of pure hydrochloric acid, and approximately 0.6% by weight of pure nitric acid. (112) The composition of (3), comprising water, approximately 38.8% by weight of pure sulfuric acid, approximately 3.5% by weight of pure hydrochloric acid, and approximately 0.6% by weight of pure nitric acid. (113) 1. The composition of claim 1, comprising water, approximately 38.8% by weight of pure sulfuric acid, approximately 3.5% by weight of pure hydrochloric acid, and approximately 0.9% by weight of pure nitric acid. (114) The composition of (2), consisting essentially of water, approximately 38.8% by weight of pure sulfuric acid, approximately 3.5% by weight of pure hydrochloric acid, and approximately 0.9% by weight of pure nitric acid. (115) The composition of (3), consisting of water, approximately 38.8% by weight of pure sulfuric acid, approximately 3.5% by weight of pure hydrochloric acid, and approximately 0.9% by weight of pure nitric acid. (116) The composition according to (1), comprising water, sulfuric acid, hydrochloric acid, nitric acid, and ammonium chloride. (117) The composition described in (2), consisting essentially of water, sulfuric acid, hydrochloric acid, nitric acid, and ammonium chloride. (118) The composition according to (3), which consists of water, sulfuric acid, hydrochloric acid, nitric acid, and ammonium chloride. (119) 1. The composition of claim 1, comprising water, approximately 38.8% by weight of pure sulfuric acid, approximately 4.725% by weight of pure hydrochloric acid, approximately 0.6% by weight of pure nitric acid, and ammonium chloride. (120) The composition of (2), consisting essentially of water, approximately 38.8% by weight of pure sulfuric acid, approximately 4.725% by weight of pure hydrochloric acid, and approximately 0.6% by weight of pure nitric acid, and ammonium chloride. (121) The composition according to (3), consisting of water, approximately 38.8% by weight of pure sulfuric acid, approximately 4.725% by weight of pure hydrochloric acid, approximately 0.6% by weight of pure nitric acid, and ammonium chloride. (122) 1. The composition of claim 1, comprising water, approximately 38.8% by weight of pure sulfuric acid, approximately 4.725% by weight of pure hydrochloric acid, approximately 0.9% by weight of pure nitric acid, and ammonium chloride. (123) The composition of (2), consisting essentially of water, approximately 38.8% by weight pure sulfuric acid, approximately 4.725% by weight pure hydrochloric acid, approximately 0.9% by weight pure nitric acid, and ammonium chloride. (124) The composition according to (3), consisting of water, approximately 38.8% by weight of pure sulfuric acid, approximately 4.725% by weight of pure hydrochloric acid, approximately 0.9% by weight of pure nitric acid, and ammonium chloride. (125) The composition according to (4) or (6), wherein the one or more halogen ion sources include one or more of hydrobromic acid, hydroiodic acid, hydrogen chloride, hydrofluoric acid, hydrochloric acid, ammonium chloride, ammonium bromide, ammonium fluoride, and ammonium iodide. (126) The composition of claim 4 or 6, wherein the one or more sources of halogen ions consist essentially of one or more of hydrobromic acid, hydroiodic acid, hydrogen chloride, hydrofluoric acid, hydrochloric acid, ammonium chloride, ammonium bromide, ammonium fluoride, and ammonium iodide. (127) The composition according to (4) or (6), wherein the one or more halogen ion sources comprise one or more of hydrobromic acid, hydroiodic acid, hydrogen chloride, hydrofluoric acid, hydrochloric acid, ammonium chloride, ammonium bromide, ammonium fluoride, and ammonium iodide. (128) The composition according to (4) or (6), wherein the one or more halogen ion sources comprise approximately 2% by weight of ammonium chloride. (129) The composition of claim 4 or 6, wherein the one or more halogen ion sources consist essentially of approximately 2% by weight ammonium chloride. (130) The composition according to (4) or (6), wherein the one or more halogen ion sources comprise approximately 2% by weight of ammonium chloride. (131) The composition according to any one of (1) to (130), having a Ni etching rate of approximately 200 or more. (132) The composition according to any one of (1) to (130), having a Ni etching rate of approximately 300 or more. (133) The composition according to any one of (1) to (130), having a Ni etching rate of approximately 400 or more. (134) The composition according to any one of (1) to (130), having a Ni etching rate of approximately 500 or more. (135) The composition according to any one of (1) to (130), having a Ni etching rate of approximately 600 or more. (136) The composition according to any one of (1) to (130), having a Ni etching rate of about 200 to about 700. (137) The composition according to any one of (1) to (130), having a Ni etching rate of about 300 to about 700. (138) The composition according to any one of (1) to (130), having a Ni etching rate of about 400 to about 700. (139) The composition according to any one of (1) to (130), having a Ni etching rate of about 500 to about 700. (140) The composition according to any one of (1) to (130), having a Ni etching rate of about 600 to about 700. (141) Approximately 2 mg / 100 ml or more of Fe 2 O 3 The composition according to any one of (1) to (130), having solubility. (142) Approximately 3 mg / 100 ml or more of Fe 2 O 3 The composition according to any one of (1) to (130), having solubility. (143) Approximately 4 mg / 100 ml or more of Fe 2 O 3 The composition according to any one of (1) to (130), having solubility. (144) Approximately 5 mg / 100 ml or more of Fe 2 O 3 The composition according to any one of (1) to (130), having solubility. (145) Approximately 6 mg / 100 ml or more of Fe 2 O 3 The composition according to any one of (1) to (130), having solubility. (146) Approximately 7 mg / 100 ml or more of Fe 2 O 3 The composition according to any one of (1) to (130), having solubility. (147) Approximately 8 mg / 100 ml or more of Fe 2 O 3 The composition according to any one of (1) to (130), having solubility. (148) Approximately 9 mg / 100 ml or more of Fe 2 O 3 The composition according to any one of (1) to (130), having solubility. (149) Approximately 10 mg / 100 ml or more of Fe 2 O 3 The composition according to any one of (1) to (130), having solubility. (150) Approximately 11 mg / 100 ml or more of Fe 2 O 3 The composition according to any one of (1) to (130), having solubility. (151) Approximately 2mg / 100ml to approximately 11mg / 100ml of Fe 2 O 3 The composition according to any one of (1) to (130), having solubility. (152) Approximately 5mg / 100ml or more to approximately 10mg / 100ml or more of Fe 2 O 3 The composition according to any one of (1) to (130), having solubility. (153) a. forming one or more layers, including at least one Ni-containing layer, on a silicon substrate; and b. removing the Ni-containing layer by contacting the Ni-containing layer with the composition according to any one of (1) to (152); 1. A method for manufacturing a semiconductor device on a semiconductor wafer, comprising: (154) a. providing a semiconductor device comprising a substrate, an EUV mask, and a metal-containing EUV mask protection structure; b. exposing the semiconductor device to EUV radiation; and c. removing the metal-containing EUV mask protective structure by contacting the semiconductor device with the composition according to any one of (1) to (152); 1. A method for removing a metal-containing layer of a pellicle structure, comprising: (155) 15. The method of claim 153, further comprising performing a selective dry etching process on at least a portion of the semiconductor device before removing the metal-containing EUV mask protection structure. (156) 15. The method of claim 14, wherein the metal-containing EUV mask protection structure comprises nickel. (157) 5. The method of claim 4, wherein the metal-containing EUV mask protection structure comprises a metal-containing heat dissipation layer. (158) 15. The method of claim 14, wherein the metal-containing EUV mask protection structure comprises a metal-containing tie layer. (159) 15. The method of claim 154, wherein the metal-containing EUV mask protection structure comprises one or more metals deposited by atomic layer deposition (ALD), e-beam evaporation, chemical vapor deposition (CVD), or electroplating. (160) 15. The method of claim 154, wherein the semiconductor device further comprises at least one of a sacrificial layer, an insulating layer, a passivation layer, a low-k layer, a metal-containing layer, or a barrier layer (i) between the substrate and the EUV mask or (ii) as part of the EUV mask protection structure. (161) 154. The method of claim 154, wherein the metal-containing EUV mask protection structure comprises at least one of a sacrificial layer, an insulating layer, a passivation layer, a graphene layer, an EUV transparent layer, an interconnect layer, and a heat dissipation layer.

Claims

1. (i) water; (ii) one or more oxidizing agents comprising about 0.1% to about 1.0% by weight of pure nitric acid; (iii) one or more acids other than nitric acid, the one or more acids comprising from about 3.0% to about 5.0% by weight of pure hydrochloric acid; and (iv) one or more halogen ion sources; A composition comprising:

2. The composition of claim 1 further comprising: (v) one or more chelating agents.

3. 2. The composition of claim 1, wherein the one or more oxidizing agents further comprise one or more of peroxomonosulfates, perborates, perchlorates, perchloric acid, peracetate anion, periodates, persulfates, permanganates, chromates, dichromates, benzoquinones, and amine-N-oxides.

4. 2. The composition of claim 1, wherein the one or more oxidizing agents further comprise one or more of ammonium persulfate, 2,5-dihydroxy-1,4-benzoquinone, nitrosylsulfuric acid, and one or more of pyridine N-oxide, 4-methylmorpholine N-oxide.

5. 2. The composition of claim 1, wherein the one or more acids comprise one or more of sulfuric acid, hydrochloric acid, methanesulfonic acid, 4-methylbenzenesulfonic acid, hydrobromic acid, citric acid, malonic acid, hydrofluoric acid, acetic acid, phosphoric acid, and hydroiodic acid.

6. 10. The composition of claim 1, wherein the total weight percent of pure acids in the composition is from about 30% to about 45% by weight.

7. 10. The composition of claim 1, wherein the total weight percent of pure acids in the composition is from about 35% to about 45% by weight.

8. 10. The composition of claim 1, wherein the one or more acids comprise approximately 38.8% by weight pure sulfuric acid.

9. 10. The composition of claim 1, wherein the one or more acids comprise approximately 3.5% by weight pure hydrochloric acid.

10. The composition of claim 1 , wherein the one or more acids comprise sulfuric acid and hydrochloric acid.

11. 10. The composition of claim 1, wherein the one or more acids comprise approximately 38.8% by weight pure sulfuric acid and approximately 3.5% by weight pure hydrochloric acid.

12. 10. The composition of claim 1 comprising water, approximately 33.5% to approximately 50% by weight of pure sulfuric acid, and approximately 0.9% by weight of pure nitric acid.

13. 10. The composition of claim 1 comprising water and about 0.6% to about 0.9% by weight of pure nitric acid.

14. 10. The composition of claim 1 comprising water, approximately 0.6% to approximately 0.9% by weight of pure nitric acid, and approximately 33.5% to approximately 50% by weight of pure sulfuric acid.

15. 10. The composition of claim 1 comprising water and about 40% to about 45% by weight combined of pure sulfuric acid, pure hydrochloric acid, and pure nitric acid.

16. 10. The composition of claim 1 comprising water and approximately 43% to approximately 45% by weight combined of pure sulfuric acid, pure hydrochloric acid, and pure nitric acid.

17. 10. The composition of claim 1 comprising water, approximately 38.8% by weight pure sulfuric acid, approximately 3.5% by weight pure hydrochloric acid, and approximately 0.9% by weight pure nitric acid.

18. 10. The composition of claim 1 consisting of water, approximately 38.8% by weight pure sulfuric acid, approximately 3.5% by weight pure hydrochloric acid, and approximately 0.9% by weight pure nitric acid.

19. 2. The composition of claim 1, wherein the one or more sources of halogen ions comprise one or more of hydrobromic acid, hydroiodic acid, hydrogen chloride, hydrofluoric acid, hydrochloric acid, ammonium chloride, ammonium bromide, ammonium fluoride, and ammonium iodide.

20. 10. The composition of claim 1, wherein the one or more sources of halogen ions comprise one or more of ammonium chloride, ammonium bromide, ammonium fluoride, and ammonium iodide.

21. (i) water; (ii) one or more oxidizing agents comprising about 0.1% to about 1.0% by weight of pure nitric acid; (iii) one or more acids other than nitric acid, and (iv) one or more halogen ion sources; A composition comprising: Approximately 2 mg / 100 ml or more to approximately 11 mg / 100 ml or more of Fe ２ O ３ A composition having solubility.

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