Tungsten-compatible TiN hard mask removal composition

Abstract

Compositions, methods, and systems for removing TiN hard masks from electronic circuit devices such as advanced patterned wafers are disclosed. The etching formulation comprises, essentially consists of, or comprises (a) at least one phosphorus-containing acid or a salt thereof, (b) at least one oxidizing agent, (c) at least one cationic polymer anticorrosion agent, and (d) at least one solvent.

Description

Technical Field

[0001] Field

[0002] The disclosed and claimed subject matter relates to formulations that selectively etch TiN layers over tungsten (W), and to methods of making the same and / or methods of using the same in the manufacture of semiconductor devices.

Background Art

[0003] Related Art

[0004] As scaling progresses and the dimensions of the microstructures become even smaller, the reliability of integrated circuits (ICs) has become an even more important issue in IC manufacturing technology. The impact of the failure mechanisms of wiring interconnects on the performance and reliability of devices places further requirements on the integration scheme, wiring materials, and processes. Titanium nitride (TiN) has been used as a hard mask layer for depositing other material layers in various applications. For example, to form a dual damascene wiring pattern, an optimal low-k dielectric material and its associated deposition, pattern lithography, etching, and cleaning are required. In the dual damascene process, a photoresist mask, typically titanium or titanium nitride (TiN), is formed on a low-k dielectric layer over a metal conductor layer such as a copper or cobalt layer. Next, the low-k dielectric layer is etched in regions not protected by the photoresist mask to form vias and / or trenches that expose the metal conductor layer. The vias and trenches, commonly known as a dual damascene structure, are typically defined using two lithography steps. Thereafter, the photoresist mask is removed from the low-k dielectric layer, and a conductive material is deposited in the vias and / or trenches to form wiring. The hard mask approach in wafer manufacturing for wiring patterning enables pattern transfer to the underlying layer with the most precise and optimal dimensional control.

[0005] In other applications, the TiN layer may be deposited directly onto layers of different metallic materials without a dielectric layer in between for dimensional control. These metallic materials may include aluminum, copper, cobalt, molybdenum, tungsten, and the like.

[0006] Compositions have been developed for partially etching or completely removing these types of metal hard masks from a substrate without damaging the exposed material.

[0007] To protect these exposed metal layers, inhibitors are typically added to the composition to prevent loss of the metal layers and obtain a better metal surface for subsequent metal deposition. Unlike compositions for selectively removing TiN hard masks over exposed copper or cobalt, many excellent inhibitors exist for protecting their surfaces, but inhibitors for protecting tungsten (W) are limited, and therefore, there are very few compositions that can selectively remove the TiN layer over tungsten. Consequently, there is a need to develop a composition that can etch a large amount of titanium nitride mask layer while protecting the exposed tungsten layer from etching. [Overview of the Initiative]

[0008] The subject matter disclosed and claimed relates to a formulation that selectively etches a TiN layer more than tungsten (W), and a method for manufacturing the same and / or a method for using the same in the manufacture of a semiconductor device.

[0009] In one embodiment, the etching compound is (a) at least one phosphorus-containing acid or a salt thereof, (b) at least one oxidizing agent, (c) at least one cationic polymer corrosion inhibitor, (d) containing, essentially consisting of, or comprising at least one solvent.

[0010] The disclosed and claimed subject matter further includes a method for selectively removing a TiN layer while minimizing the etching rate of a W layer using the disclosed and claimed etching composition, and a method for manufacturing a semiconductor comprising an etching process using the disclosed and claimed etching composition. [Modes for carrying out the invention]

[0011] All references cited herein, including publications, patent applications, and patents, are incorporated herein by reference to the same extent as they are incorporated herein in whole, with each reference being individually and specifically indicated as being incorporated herein by reference.

[0012] In the context of describing the subject matter disclosed and claimed (particularly in the context of the following claims), the use of the terms “a,” “an,” and “the,” and similar references, should be interpreted as encompassing both singular and plural forms unless otherwise indicated herein or explicitly refuted by the context. The terms “comprising,” “having,” “including,” and “containing” should be interpreted as open-ended terms (i.e., “including, but not limited to”) unless otherwise indicated herein. Enumerations of value ranges herein are merely intended to serve as abbreviations for referring individually to each individual value within that range, unless otherwise indicated herein, and each individual value is incorporated herein as if it were individually enumerated herein. All methods described herein may be carried out in any preferred order unless otherwise indicated herein or explicitly refuted by the context. Any and all examples or illustrative language provided herein (e.g., "etc.") are intended solely to better illustrate the subject matter disclosed and claimed, and not to limit the scope of the subject matter disclosed and claimed, unless otherwise claimed. No language in this specification should be construed as indicating that any unclaimed element is essential to the practice of the subject matter disclosed and claimed.

[0013] Preferred embodiments of the Subject Matter Disclosed and Claimed herein are described herein, including the best modes known to the inventors for carrying out the Subject Matter Disclosed and Claimed herein. Variations of these preferred embodiments may become apparent to those skilled in the art by reading the foregoing description. The inventors anticipate that those skilled in the art will use such variations as needed, and the inventors intend that the Subject Matter Disclosed and Claimed herein will be practiced in ways other than those specifically described herein. Accordingly, the Subject Matter Disclosed and Claimed herein includes all modifications and equivalents of the Subject Matter enumerated in the claims appended herein, as permitted by applicable law. Furthermore, any combination of all possible variations of the above elements is encompassed by the Subject Matter Disclosed and Claimed herein unless otherwise indicated herein or expressly rejected by the context.

[0014] For ease of reference, “microelectronic devices” or “semiconductor substrates” refer to semiconductor wafers, flat panel displays, phase-change memory devices, solar panels and other products including solar substrates, photovoltaics, and microelectromechanical systems (MEMS) manufactured for use in microelectronics, integrated circuits, or computer chip applications. Examples of solar substrates include, but are not limited to, silicon, amorphous silicon, polycrystalline silicon, monocrystalline silicon, CdTe, copper indium selenide, copper indium sulfide, and gallium arsenide on gallium. Solar substrates may be doped or undoped. The term “microelectronic devices” is not intended to be limiting and should be understood to include any substrate that ultimately becomes a microelectronic device or microelectronic assembly. Microelectronic devices or semiconductor substrates may include low-k dielectric materials, barrier materials, and metals such as AlCu alloys, W, Ti, TiN, and other materials on them.

[0015] As defined herein, “low-k dielectric material” refers to any material used as a dielectric material in layered microelectronic devices, which has a dielectric constant of less than about 3.5. Preferably, low-k dielectric materials include 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 should be understood that low-k dielectric materials can have a variety of densities and porosities.

[0016] Where defined herein, the term “barrier material” refers to any material used in the art to seal a metal wire, such as copper wiring, to minimize the diffusion of the metal, such as copper, into a dielectric material. Preferred barrier layer materials include tantalum, titanium, ruthenium, hafnium, and other high-melting-point metals, as well as their nitrides and silicides.

[0017] "Substantially contained" is defined herein as less than 2% by weight, preferably less than 1% by weight, more preferably less than 0.5% by weight, and most preferably less than 0.1% by weight. "Substantially contained" also includes 0.0% by weight. The term "contains" means 0.0% by weight.

[0018] As used herein, the terms “about” and “approximately” are intended to correspond to ±5% of the stated value, respectively.

[0019] As used herein, "neat" refers to the weight percentage of an undiluted acid or other material. For example, 100 g of 85% phosphoric acid content constitutes 85 g of acid and 15 g of diluent.

[0020] In all such compositions in which a particular component of the composition is discussed with reference to a weight percentage range including a lower limit of 0, it is understood that such component may or may not be present in various specific embodiments of the composition, and if such component is present, it may be present at a low concentration of 0.001 weight percent based on the total weight of the composition in which such component is used. Note that all defined weight percentages of components are based on the total weight of the composition unless otherwise indicated. Furthermore, all weight percentages are “neat” unless otherwise indicated, meaning they do not include aqueous components present when added to the composition. Any reference to “at least one” may be replaced with “one or more.” “At least one” and / or “one or more” include “at least two” or “two or more” and “at least three” and “three or more,” etc.

[0021] In a broader implementation, the subject matter disclosed and claimed relates to etching compositions comprising, essentially comprising, or consisting of components (a), (b), (c), and (d). In some embodiments, the etching compositions may include other components. In some embodiments, the etching compositions disclosed herein are formulated to be free of, or substantially free of, at least one of the following: inorganic bases, quaternary ammonium hydroxides, ammonium hydroxides, amino acids, organic acids, azoles, halide ions (e.g., fluoride ions, chloride ions), metal-containing chemicals, reducing agents, alkanolamines, hydroxylamines, hydroxylamine derivatives, amidoxime compounds, organic solvents, surfactants, and abrasives.

[0022] In further embodiments, the etching composition essentially consists of (a), (b), (c), and (d) in varying concentrations. In such embodiments, the total amount of (a), (b), (c), and (d) is not equal to 100% by weight and may include other components that do not substantially alter the effectiveness of the etching composition.

[0023] In another embodiment, the etching composition comprises (a), (b), (c), and (d) in various concentrations. In such an embodiment, the total amount of (a), (b), (c), and (d) is equal to or about 100% by weight, but may also contain small amounts of other small and / or trace amounts of impurities that do not substantially alter the effectiveness of the composition. 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 less than 1% by weight of impurities. In a further embodiment, the etching composition may contain less than 0.05% by weight of impurities.

[0024] When referring to the compositions of the present invention as 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 never exceed 100% by weight. In compositions "essentially consisting of" the listed components, such components may collectively amount to 100% by weight of the composition or less than 100% by weight. If the components collectively amount to less than 100% by weight, such compositions may contain 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 less than 1% by weight of impurities. In a further embodiment, the etching composition may contain less than 0.05% by weight 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. Otherwise, it is understood that, in the absence of significant non-essential impurity components, the combination of all essential components will essentially total 100% by weight.

[0025] The following detailed description provides only exemplary embodiments and is not intended to limit the scope, applicability, or configuration of the disclosed and claimed subject matter. Rather, the detailed description of the exemplary embodiments provides those skilled in the art with a description enabling them to implement the exemplary embodiments of the disclosed and claimed subject matter. Various changes may be made to the function and configuration of the elements without departing from the spirit and scope of the disclosed and claimed subject matter as set forth in the appended claims.

[0026] Etching formulation

[0027] Disclosed herein is an etching formulation of a chemical stripper for removing or etching (the terms "removing" and "etching" are used synonymously herein) a TiN hard mask or a TiN thin layer on a wafer having integrated circuits. The TiN hard mask or TiN thin layer is used to provide control of the microstructure during plasma etching. A suitable stripper / washing chemical needs to be able to strip or completely remove the TiN hard mask or TiN thin layer, as well as residues from the plasma etching process. However, it is also desirable for such a chemical to be compatible with tungsten within the device.

[0028] In particular, the disclosed and claimed etching formulation comprises, (a) at least one phosphorus-containing acid or a salt thereof, (b) at least one oxidizing agent, (c) at least one cationic polymer corrosion inhibitor, (d) at least one solvent, and consists of, consists essentially of, or comprises these.

[0029] In some aspects of this embodiment, the etching formulation can include other optional components.

[0030] (a) Phosphorus-containing acid or a salt thereof

[0031] The disclosed and claimed etching formulations comprise at least one phosphorus-containing acid or a salt thereof as an etching agent. The phosphorus-containing acid and its salts may include, but are not limited to, phosphoric acid, tetramethylammonium phosphate, tetrabutylammonium phosphate, tetraethylammonium phosphate, tetrapropylammonium phosphate, etidronic acid, aminotrimethylenephosphonic acid, tripolyphosphate, tetrapolyphosphate, pyrophosphate, polymetaphosphate, hypophosphorous acid, phosphorous acid, diphosphorous acid, triphosphorous acid, (aminomethyl)phosphonic acid, (aminoethyl)phosphonic acid, (aminopropyl)phosphonic acid, mono-n-dodecyl phosphate, tetramethylammonium phosphate, tetrabutylammonium phosphate, tetraethylammonium phosphate, tetrapropylammonium phosphate, and combinations thereof. In one embodiment, at least one phosphorus-containing acid or its salt comprises phosphoric acid.

[0032] The amount of at least one phosphorus-containing acid or a salt thereof in the composition of the disclosed and claimed subject matter is a weight percent (neat) based on the total weight of the composition and is within any range having a starting and ending point selected from 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95. These include, but are not limited to, about 5-95%, 10-90%, 20-90%, 30-90%; about 9-70%; about 25-50%; about 40-90%; about 50-90%; about 60-90%; and about 30-8 The composition contains 0% by weight; approximately 40% to 80% by weight of the composition; approximately 45% to 80% by weight of the composition; approximately 50% to 80% by weight of the composition; approximately 60% to 80% by weight of the composition; approximately 9% to 75% by weight of the composition; approximately 30% to 75% by weight of the composition; approximately 40% to 75% by weight of the composition; approximately 45% to 75% by weight of the composition; and approximately 50% to 75% by weight of the composition. In one embodiment, at least one phosphorus-containing acid or a salt thereof is present in approximately 30% to 75% by weight of the composition. In one embodiment, at least one phosphorus-containing acid or a salt thereof is present in approximately 40% to 75% by weight of the composition. In one embodiment, at least one phosphorus-containing acid or a salt thereof is present in approximately 45% to 75% by weight of the composition. In one embodiment, at least one phosphorus-containing acid or its salt is present in about 30% to about 55% by weight of the composition. In one embodiment, at least one phosphorus-containing acid or its salt is present in about 25% to about 50% by weight of the composition. In one embodiment, at least one phosphorus-containing acid or its salt is present in about 25% to about 45% by weight of the composition. In one embodiment, at least one phosphorus-containing acid or its salt is present in about 30% to about 50% by weight of the composition. These proportions and ranges represent the neat amount of at least one phosphorus-containing acid or its salt in the composition.

[0033] (b) Oxidizing agent

[0034] The disclosed and claimed etching formulations comprise at least one oxidizing agent. The cleaning composition uses a peroxide, such as hydrogen peroxide, as an oxidizing agent for removing the TiN hard mask. Peroxides used in the composition include hydrogen peroxide, ammonium persulfate, peracetic acid, peroxybenzoic acid, oxone (2KHSO5·KHSO4·K2SO4), n-methylmorpholine oxide (NMMO or NMO), benzoyl peroxide, tetrabutylammonium peroxymonosulfate, ferric chloride, permanganate, peroxoborate, periodic acid, iodic acid, vanadium(V) oxide, vanadium(IV,V) oxide, ammonium vanadate, perchlorate, persulfate, ammonium peroxydisulfate, peracetic acid, urea hydroperoxide, nitric acid (HNO3), ammonium hypochlorite (NH4ClO), and ammonium tungstate ((NH4)). 10 H2(W2O7), ammonium chlorite (NH4ClO2), ammonium chlorate (NH4ClO3), ammonium iodate (NH4IO3), ammonium perborate (NH4BO3), ammonium perchlorate (NH4ClO4), ammonium periodate (NH4IO3), ammonium persulfate ((NH4)2S2O8), tetramethylammonium chlorite ((N(CH3)4)ClO2), tetramethylammonium chlorate ((N(CH3)4)ClO3), iodic acid The oxidizing agent may include, but is not limited to, tetramethylammonium ((N(CH3)4)IO3), tetramethylammonium perborate ((N(CH3)4)BO3), tetramethylammonium perchlorate ((N(CH3)4)ClO4), tetramethylammonium periodate ((N(CH3)4)IO4), tetramethylammonium persulfate ((N(CH3)4)S2O8), ((CO(NH2)2)H2O2), peracetic acid (CH(CO)OOH), and combinations thereof. In one embodiment, the oxidizing agent includes hydrogen peroxide.

[0035] The amount of at least one oxidizing agent in the composition of the subject matter disclosed and claimed is a weight percent (neat) based on the total weight of the composition and is within any range having a starting point and an ending point selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 24, 26, 28, 30, 35, 40, 45, 50, 55, 60, 65, 70. For example, the amount of the compound is approximately 1% to 20% by weight, or approximately 1% to 15% by weight, or approximately 1% to 10% by weight, approximately 1% to 6% by weight, or approximately 3% to 20% by weight, or approximately 3% to 15% by weight, or approximately 3% to 6% by weight, or approximately 6% to 20% by weight, or approximately 6% to 15% by weight, preferably approximately 3% to 15% by weight, and more preferably approximately 6% to 15% by weight.

[0036] In one embodiment, at least one oxidizing agent contains hydrogen peroxide in an amount of about 15% to about 70% by weight in the formulation. In one embodiment, at least one oxidizing agent contains hydrogen peroxide in an amount of about 15% to about 65% by weight in the formulation. In one embodiment, at least one oxidizing agent contains hydrogen peroxide in an amount of about 15% to about 50% by weight in the formulation. In one embodiment, at least one oxidizing agent contains hydrogen peroxide in an amount of about 15% to about 40% by weight in the formulation. In one embodiment, at least one oxidizing agent contains hydrogen peroxide in an amount of about 15% to about 30% by weight in the formulation. In one embodiment, at least one oxidizing agent contains hydrogen peroxide in an amount of about 20% to about 65% by weight in the formulation. In one embodiment, at least one oxidizing agent contains hydrogen peroxide in an amount of about 45% to about 65% by weight in the formulation. In one embodiment, at least one oxidizing agent contains hydrogen peroxide in an amount of about 20% to about 45% by weight in the formulation. In one embodiment, the oxidizing agent contains about 13.5% by weight of hydrogen peroxide in the formulation. In one embodiment, the oxidizing agent contains about 19.5% by weight of hydrogen peroxide in the formulation. In one embodiment, the oxidizing agent contains about 6% by weight of hydrogen peroxide in the formulation. In one embodiment, at least one oxidizing agent contains about 45% by weight of hydrogen peroxide in the formulation. In one embodiment, at least one oxidizing agent contains about 65% by weight of hydrogen peroxide in the formulation. These percentages and ranges represent the neat amount of at least one oxidizing agent in the formulation.

[0037] (c) Corrosion inhibitors

[0038] The disclosed and claimed etching formulations comprise at least one cationic polymer inhibitor. The at least one cationic polymer inhibitor helps minimize the loss of a metal substrate, such as tungsten. Examples of cationic polymer inhibitors used in the formulations include, but are not limited to, polyalkyleneimines and their derivatives, poly(diallyldimethylammonium chloride), diallyldimethylammonium chloride, and combinations thereof.

[0039] Polyalkyleneimines may be linear or branched, and may be charged or uncharged. They may contain primary, secondary, and / or tertiary amino groups. They may be substituted by reaction with, for example, fatty acids, carboxylic acids and / or carboxylic acid derivatives (e.g., acrylic acid, maleic acid, maleic anhydride, etc.), alkylene oxides, etc. They may be alkoxylated, amidated, etc. They may be amphiphilic, amphoteric, alkoxylated, etc. In some embodiments, they may have a molecular weight of about 300 to about 2,000,000. A preferred polyalkyleneimine is polyethyleneimine.

[0040] Linear polyethyleneimine (PEI) is a polymer having repeating units composed of an amine group and a two-carbon aliphatic -CH2CH2- spacer. [ka] All linear polyethyleneimines contain secondary amines, whereas branched PEIs contain primary, secondary, and tertiary amino groups. Note that linear and branched polyethyleneimines and mixtures thereof are useful for preventing tungsten etching in the disclosed and claimed formulations.

[0041] Polyethyleneimines may have an average molecular weight (weight average, Mw) of about 100 to about 5,000,000 or more. Any polyethyleneimine is suitable for use in the disclosed and claimed etching formulations. However, when one or more polyethyleneimines are used in the disclosed and claimed etching formulations, it is preferable that they have a typical average molecular weight (weight average, Mw) of up to about 1,000,000, preferably about 200 to about 100,000, more preferably about 300 to about 10,000, and even more preferably about 300 to about 5,000.

[0042] Examples of polyethyleneimines include materials sold by BASF under the trade name Lupasol® and by Nippon Shokubai under the trade name EPOMIN®. Examples include Lupasol® FG, Lupasol® G 20, Lupasol® G 35, Lupasol® G 100, Lupasol® G 500, Lupasol® HF, Lupasol® P, Lupasol® PS, Lupasol® PR 8515, Lupasol® WF, Lupasol® FC, Lupasol® PE, Lupasol® HEO 1, Lupasol® PN 50, Lupasol® PN 60, Lupasol® PO 100, and Lupasol® SK. The preferred Lupasol® FG is a branched polyethyleneimine polymer having a molecular weight of 800 g / mol.

[0043] Polydiallyldimethylammonium chloride is a homopolymer of diallyldimethylammonium chloride. The molecular weight of polyDADMAC typically ranges from several hundred thousand grams per mole, and can reach up to 1 million grams depending on the product. Preferred polydiallyldimethylammonium chloride has a typical average molecular weight (weight average, Mw) of up to about 1,000,000, preferably about 200 to about 100,000, more preferably about 300 to about 10,000, and even more preferably about 300 to about 5,000.

[0044] The amount of at least one cationic polymer anticorrosion agent in the composition of the disclosed and claimed subject matter is a weight percent (neat) based on the total weight of the composition and is within any range having start and end points selected from 0.001, 0.005, 0.1, 0.2, 0.3, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 24, 26, 28. In one embodiment, the cationic polymer is present in an amount of about 0.001% to about 5% by weight. In one embodiment, the cationic polymer is present in an amount of about 0.001% to about 3% by weight. In one embodiment, the cationic polymer is present in an amount of about 0.001% to about 2% by weight. In one embodiment, the cationic polymer is present in an amount of about 0.001% to about 1% by weight. In one embodiment, the cationic polymer is present in an amount of about 0.001% to about 0.5% by weight. In one embodiment, the cationic polymer is present in an amount of about 0.001% to about 0.25% by weight. In one embodiment, the cationic polymer is present in an amount of about 0.001% to about 0.1% by weight. In one embodiment, the cationic polymer is present in an amount of about 0.005% to about 5% by weight. In one embodiment, the cationic polymer is present in an amount of about 0.005% to about 3% by weight. In one embodiment, the cationic polymer is present in an amount of about 0.005% to about 1% by weight. In one embodiment, the cationic polymer is present in an amount of about 0.01% to about 5% by weight. In one embodiment, the cationic polymer is present in an amount of about 0.01% to about 3% by weight. In one embodiment, the cationic polymer is present in an amount of about 0.01% to about 1% by weight. In one embodiment, the cationic polymer is present in an amount of about 0.01% to about 0.5% by weight. In one embodiment, the cationic polymer is present in an amount of about 0.03% to about 0.05% by weight. In one embodiment, the cationic polymer is present in an amount of about 0.03% to about 1.5% by weight. In one embodiment, the cationic polymer is present in an amount of about 0.05% to about 1.5% by weight. In one embodiment, the cationic polymer is present in an amount of about 0.01% by weight.In one embodiment, the cationic polymer is present in an amount of about 0.05% by weight. In one embodiment, the cationic polymer is present in an amount of about 0.15% by weight. In one embodiment, the cationic polymer is present in an amount of about 0.5% by weight. In one embodiment, the cationic polymer is present in an amount of about 1.0% by weight. In one embodiment, the cationic polymer is present in an amount of about 1.5% by weight. These proportions and ranges represent the neat amount of at least one cationic polymer anticorrosion agent in the formulation.

[0045] (d) solvent

[0046] As described above, the disclosed and claimed etching formulation comprises at least one solvent.

[0047] In one embodiment, at least one solvent contains water, is essentially composed of water, or consists of water. The water may be deionized water ("DI water"), purified water, and / or distilled water.

[0048] In another embodiment, at least one solvent comprises water and one or more non-aqueous solvents. Examples of non-aqueous solvents that may be used in the formulation include, but are not limited to, dimethyl sulfoxide (DMSO), dimethyl sulfone (DMSO2), sulfolane ((CH2)4SO2), n-methylpyrrolidone, glycol ethers (e.g., dipropylene glycol methyl ether, tripropylene glycol methyl ether), glycols (e.g., propylene glycol), and combinations thereof. In one embodiment, at least one solvent comprises DMSO.

[0049] In one embodiment, at least one solvent is present in an amount of about 30% to about 80% by weight of the composition. In one embodiment, at least one solvent is present in an amount of about 5% to about 60% by weight of the composition. In one embodiment, at least one solvent is present in an amount of about 5% to about 50% by weight of the composition. In one embodiment, at least one solvent is present in an amount of about 10% to about 50% by weight of the composition. In one embodiment, at least one solvent is present in an amount of about 20% to about 50% by weight of the composition. In one embodiment, at least one solvent is present in an amount of about 30% to about 50% by weight of the composition. In one embodiment, at least one solvent is present in an amount of about 40% to about 50% by weight of the composition. In one embodiment, at least one solvent is present in an amount of about 5% to about 40% by weight of the composition. In one embodiment, at least one solvent is present in an amount of about 5% to about 45% by weight of the composition. In one embodiment, at least one solvent is present in an amount of about 5% to about 30% by weight of the composition. In one embodiment, at least one solvent is present in an amount of about 5% to about 25% by weight of the composition. In one embodiment, at least one solvent is present in an amount of about 5% to about 20% by weight of the composition. In one embodiment, at least one solvent is present in an amount of about 5% to about 10% by weight of the composition. In one embodiment, at least one solvent is present in an amount of about 5% to about 30% by weight of the composition. In one embodiment, at least one solvent is present in an amount of about 10% to about 30% by weight of the composition. In one embodiment, at least one solvent is present in an amount of about 1% to about 7% by weight of the composition. In one embodiment, at least one solvent is present in an amount of about 1% to about 5% by weight of the composition.

[0050] Optional ingredients

[0051] The disclosed and claimed compositions may contain one or more optional components. Such optional components include, but are not limited to, the following:

[0052] Chelating agents

[0053] The disclosed and claimed etching formulations may optionally contain one or more chelating agents, such as metal chelating agents. Examples of suitable chelating agents include glycine, citric acid, serine, proline, leucine, alanine, asparagine, aspartic acid, glutamine, valine, and lysine, nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid (EDTA), (1,2-cyclohexylenedinitrilo)tetraacetic acid (CDTA), uric acid, tetraglyceride, diethylenetriaminepentaacetic acid, propylenediaminetetraacetic acid, ethylenediamine disuccinic acid, sulfanilamide, 1,4,7,10-tetraazacyclododecane-1,4,7,10tetraacetic acid; ethylene glycol tetraacetic acid (EGTA); 1,2-bis(o-aminophenoxy)ethane-N,N,N',N'-tetraacetic acid; N-2-bis(carboxymethyl)aminoethyl Examples of etching compounds include, but are not limited to, N-(2-hydroxyethyl)glycine (HEDTA); 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); ntrilotris(methylene)triphosphonic acid; tartaric acid; 3,4-dihydroxybenzoic acid; salicylic acid; 8-HQ; N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid; 1,3-propanediamine-N,N,N',N'-tetraacetic acid; glutamic acid; cystine; picolinic acid; and combinations thereof. In one embodiment, the disclosed and claimed etching compound comprises one or more of glycine, citric acid, ethylenediaminetetraacetic acid (EDTA), and picolinic acid.

[0054] Where present in the composition of the disclosed and claimed subject matter, the amount of the chelating agent is a weight percentage (neat) based on the total weight of the composition, and is in the range of about 0.0001% to about 10% by weight, more preferably about 0.0001% to about 5% by weight, and most preferably about 0.01% to about 2% by weight (neat).

[0055] Ammonium salts

[0056] The disclosed and claimed etching formulations may optionally contain one or more ammonium salts. Examples of suitable ammonium salts include, but are not limited to, ammonium salts of weak acids, such as triammonium citrate, ammonium acetate, ammonium malonate, ammonium adipate, ammonium lactate, ammonium iminodiacetate, ammonium chloride, ammonium bromide, ammonium fluoride, ammonium difluoride, ammonium sulfate, ammonium oxalate, ammonium lactate, ammonium tartrate, triammonium citrate, ammonium acetate, ammonium carbamate, ammonium carbonate, ammonium benzoate, tetraammonium EDTA, diammonium ethylenediaminetetraacetate, ammonium succinate, ammonium formate, ammonium 1-H-pyrazole-3-carboxylate, and combinations thereof. In one embodiment, the disclosed and claimed etching formulation contains one or more of triammonium citrate and ammonium acetate.

[0057] The amount of ammonium salt present in the composition of the subject matter disclosed and claimed is a weight percentage (neat) based on the total weight of the composition, and is in the range of about 0.1% to about 20% by weight, more preferably about 0.5% to about 10% by weight, and most preferably about 0.5% to about 5% by weight of the pre-diluted composition.

[0058] Excluded ingredients

[0059] In some embodiments, the etching compositions disclosed herein are formulated to be free of, or substantially free of, at least one of the following compounds: inorganic bases, quaternary ammonium hydroxides, ammonium hydroxides, alkanolamines, amino acids, organic acids, azoles, halide ions (e.g., fluoride ions, chloride ions), metal-containing chemicals, reducing agents, hydroxylamines, hydroxylamine derivatives, amidoxime compounds, organic solvents (e.g., DMSO), surfactants, and abrasives.

[0060] In some embodiments, the formulation may be substantially free of or without halogenated compounds, for example, substantially free of or without one or more of fluorine, bromine, chlorine, or iodine-containing compounds. In other embodiments, the formulation may be substantially free of or without sulfates and / or nitrates and / or sulfites and / or nitrites.

[0061] In some embodiments, the etching formulations disclosed and claimed are substantially free of ammonium hydroxide and / or ethylenediamine (ethyldiamine). In other embodiments, the solution may be substantially free of sodium-containing compounds and / or calcium-containing compounds and / or manganese-containing compounds or magnesium-containing compounds and / or chromium-containing compounds and / or sulfur-containing compounds. In other embodiments, the solution may be substantially free of amidoxime compounds and / or abrasives.

[0062] In some embodiments, the etching formulations disclosed and claimed are substantially free of, or do not contain, other ammonium salts and / or quaternary ammonium hydroxides and metal ions.

[0063] In some embodiments, the etching formulations disclosed and claimed are substantially free of or do not contain alkanolamines.

[0064] pH

[0065] The disclosed and claimed etching formulations preferably have a pH of less than about 7. In one embodiment, the disclosed and claimed etching formulations have a pH of less than 6. In one embodiment, the disclosed and claimed etching formulations have a pH of less than 5. In one embodiment, the disclosed and claimed etching formulations have a pH of less than 4. In one embodiment, the disclosed and claimed etching formulations have a pH of less than 3. In one embodiment, the disclosed and claimed etching formulations have a pH of less than 2. In one embodiment, the disclosed and claimed etching formulations have a pH of less than 1. In one embodiment, the disclosed and claimed etching formulations have a pH of less than 0.5. In another embodiment, the disclosed and claimed etching formulations have a pH of about 0.1 to about 3. In another embodiment, the disclosed and claimed etching formulations have a pH of about 0.1 to about 1. Preferably, the pH is about 0.1 to about 0.5.

[0066] In one embodiment, the disclosed and claimed etching formulation has a pH of about 5. In one embodiment, the disclosed and claimed etching formulation has a pH of about 5. In one embodiment, the disclosed and claimed etching formulation has a pH of about 4. In one embodiment, the disclosed and claimed etching formulation has a pH of about 3. In one embodiment, the disclosed and claimed etching formulation has a pH of about 2. In one embodiment, the disclosed and claimed etching formulation has a pH of about 1. In one embodiment, the disclosed and claimed etching formulation has a pH of about 0. In one embodiment, the disclosed and claimed etching formulation has a pH of about 0.5. In one embodiment, the disclosed and claimed etching formulation has a pH of about 0.3. In one embodiment, the disclosed and claimed etching formulation has a pH of about 0.1.

[0067] Exemplary Embodiments

[0068] In one exemplary embodiment, the disclosed and claimed etching formulation is: (a) Approximately 30% to 75% by weight of neat phosphate, (b) Neat H2O2 in an amount of approximately 1.5% to 19.5% by weight, (c) Approximately 0.001% to approximately 3.0% by weight of at least one neat cationic polymer corrosion inhibitor, (d) the remainder of the solvent, and the remaining solvent, which includes, essentially consists of, or comprises the same. In a further embodiment of this embodiment, the solvent comprises water. In a further embodiment of this embodiment, the solvent is essentially derived from water. In a further embodiment of this embodiment, the solvent consists of water. In a further embodiment of this embodiment, at least one neat cationic polymer anticorrosion agent comprises polyethyleneimine. In a further embodiment of this embodiment, at least one neat cationic polymer anticorrosion agent is essentially derived from polyethyleneimine. In a further embodiment of this embodiment, at least one neat cationic polymer anticorrosion agent consists of polyethyleneimine. In a further embodiment of this embodiment, at least one neat cationic polymer anticorrosion agent comprises diallyldimethylammonium chloride. In a further embodiment of this embodiment, at least one neat cationic polymer anticorrosion agent consists of diallyldimethylammonium chloride. In a further embodiment of this embodiment, at least one neat cationic polymer anticorrosion agent comprises polydiallyldimethylammonium chloride. In a further embodiment of this embodiment, at least one neat cationic polymer anticorrosion agent essentially consists of polydiallyldimethylammonium chloride.

[0069] In one exemplary embodiment, the disclosed and claimed etching formulation is: (a) Approximately 30% to 75% by weight of neat phosphate, (b) Neat H2O2 in an amount of approximately 6% to 19.5% by weight, (c) Approximately 0.001% to approximately 3.0% by weight of at least one neat cationic polymer corrosion inhibitor, (d) the remainder of the solvent, and the remaining solvent, which includes, essentially consists of, or comprises the same. In a further embodiment of this design, the solvent is essentially water.

[0070] In one exemplary embodiment, the disclosed and claimed etching formulation is: (a) Approximately 42.5% by weight of neat phosphate, (b) Approximately 13.5% by weight of neat H2O2, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.001% by weight, (d) the remainder of the solvent, and the remaining solvent, which includes, essentially consists of, or comprises the same. In a further embodiment of this embodiment, the solvent comprises water. In a further embodiment of this embodiment, the solvent is essentially made from water. In a further embodiment of this embodiment, the solvent consists of water. In a further embodiment of this embodiment, at least one neat cationic polymer corrosion inhibitor comprises Lupasol® FG. In a further embodiment of this embodiment, at least one neat cationic polymer corrosion inhibitor consists of Lupasol® FG.

[0071] In one exemplary embodiment, the disclosed and claimed etching formulation is: (a) Approximately 42.5% by weight of neat phosphate, (b) Approximately 13.5% by weight of neat H2O2, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.005% by weight, (d) the remainder of the solvent, and the remaining solvent, which includes, essentially consists of, or comprises the same. In a further embodiment of this embodiment, the solvent comprises water. In a further embodiment of this embodiment, the solvent is essentially made from water. In a further embodiment of this embodiment, the solvent consists of water. In a further embodiment of this embodiment, at least one neat cationic polymer corrosion inhibitor comprises Lupasol® FG. In a further embodiment of this embodiment, at least one neat cationic polymer corrosion inhibitor consists of Lupasol® FG.

[0072] In one exemplary embodiment, the disclosed and claimed etching formulation is: (a) Approximately 42.5% by weight of neat phosphate, (b) Approximately 13.5% by weight of neat H2O2, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.01% by weight, (d) the remainder of the solvent, and the remaining solvent, which includes, essentially consists of, or comprises the same. In a further embodiment of this embodiment, the solvent comprises water. In a further embodiment of this embodiment, the solvent is essentially made from water. In a further embodiment of this embodiment, the solvent consists of water. In a further embodiment of this embodiment, at least one neat cationic polymer corrosion inhibitor comprises Lupasol® FG. In a further embodiment of this embodiment, at least one neat cationic polymer corrosion inhibitor consists of Lupasol® FG.

[0073] In one exemplary embodiment, the disclosed and claimed etching formulation is: (a) Approximately 42.5% by weight of neat phosphate, (b) Approximately 13.5% by weight of neat H2O2, (c) at least one cationic polymer corrosion inhibitor in an amount of approximately 0.02% by weight, (d) the remainder of the solvent, and the remaining solvent, which includes, essentially consists of, or comprises the same. In a further embodiment of this embodiment, the solvent comprises water. In a further embodiment of this embodiment, the solvent is essentially made from water. In a further embodiment of this embodiment, the solvent consists of water. In a further embodiment of this embodiment, at least one neat cationic polymer corrosion inhibitor comprises Lupasol® FG. In a further embodiment of this embodiment, at least one neat cationic polymer corrosion inhibitor consists of Lupasol® FG.

[0074] In one exemplary embodiment, the disclosed and claimed etching formulation is: (a) Approximately 42.5% by weight of neat phosphate, (b) Approximately 13.5% by weight of neat H2O2, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.06% by weight, (d) the remainder of the solvent, and the remaining solvent, which includes, essentially consists of, or comprises the same. In a further embodiment of this embodiment, the solvent comprises water. In a further embodiment of this embodiment, the solvent is essentially made from water. In a further embodiment of this embodiment, the solvent consists of water. In a further embodiment of this embodiment, at least one neat cationic polymer corrosion inhibitor comprises Lupasol® FG. In a further embodiment of this embodiment, at least one neat cationic polymer corrosion inhibitor consists of Lupasol® FG.

[0075] In one exemplary embodiment, the disclosed and claimed etching formulation is: (a) Approximately 62% by weight of neat phosphate, (b) Approximately 6% by weight of neat H2O2, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.015% by weight, (d) the remainder of the solvent, and the remaining solvent, which includes, essentially consists of, or comprises the same. In a further embodiment of this embodiment, the solvent comprises water. In a further embodiment of this embodiment, the solvent is essentially made from water. In a further embodiment of this embodiment, the solvent consists of water. In a further embodiment of this embodiment, at least one neat cationic polymer corrosion inhibitor comprises Lupasol® FG. In a further embodiment of this embodiment, at least one neat cationic polymer corrosion inhibitor consists of Lupasol® FG.

[0076] In one exemplary embodiment, the disclosed and claimed etching formulation is: (a) Approximately 27% by weight of neat phosphate, (b) Approximately 19.5% by weight of neat H2O2, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.006% by weight, (d) the remainder of the solvent, and the remaining solvent, which includes, essentially consists of, or comprises the same. In a further embodiment of this embodiment, the solvent comprises water. In a further embodiment of this embodiment, the solvent is essentially made from water. In a further embodiment of this embodiment, the solvent consists of water. In a further embodiment of this embodiment, at least one neat cationic polymer corrosion inhibitor comprises Lupasol® FG. In a further embodiment of this embodiment, at least one neat cationic polymer corrosion inhibitor consists of Lupasol® FG.

[0077] In one exemplary embodiment, the disclosed and claimed etching formulation is: (a) Approximately 25.5% by weight of neat phosphate, (b) Approximately 13.5% by weight of neat H2O2, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.01% by weight, (d) the remainder of the solvent, and the remaining solvent, which includes, essentially consists of, or comprises the same. In a further embodiment of this embodiment, the solvent comprises water. In a further embodiment of this embodiment, the solvent is essentially made from water. In a further embodiment of this embodiment, the solvent consists of water. In a further embodiment of this embodiment, at least one neat cationic polymer corrosion inhibitor comprises Lupasol® FG. In a further embodiment of this embodiment, at least one neat cationic polymer corrosion inhibitor consists of Lupasol® FG.

[0078] In one exemplary embodiment, the disclosed and claimed etching formulation is: (a) Approximately 46.3% by weight of neat phosphate, (b) Approximately 13.5% by weight of neat H2O2, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.01% by weight, (d) the remainder of the solvent, and the remaining solvent, which includes, essentially consists of, or comprises the same. In a further embodiment of this embodiment, the solvent comprises water. In a further embodiment of this embodiment, the solvent is essentially made from water. In a further embodiment of this embodiment, the solvent consists of water. In a further embodiment of this embodiment, at least one neat cationic polymer corrosion inhibitor comprises Lupasol® FG. In a further embodiment of this embodiment, at least one neat cationic polymer corrosion inhibitor consists of Lupasol® FG.

[0079] In one exemplary embodiment, the disclosed and claimed etching formulation is: (a) Approximately 42.5% by weight of neat phosphate, (b) Approximately 13.5% by weight of neat H2O2, (c) Approximately 0.0175% by weight of at least one neat cationic polymer corrosion inhibitor, (d) the remainder of the solvent, and the remaining solvent, which includes, essentially consists of, or comprises the same. In a further embodiment of this embodiment, the solvent comprises water. In a further embodiment of this embodiment, the solvent is essentially made from water. In a further embodiment of this embodiment, the solvent consists of water. In a further embodiment of this embodiment, at least one neat cationic polymer anticorrosion agent comprises diallyldimethylammonium chloride. In a further embodiment of this embodiment, at least one neat cationic polymer anticorrosion agent is essentially made from diallyldimethylammonium chloride. In a further embodiment of this embodiment, at least one neat cationic polymer anticorrosion agent consists of diallyldimethylammonium chloride.

[0080] In one exemplary embodiment, the disclosed and claimed etching formulation is: (a) Approximately 42.5% by weight of neat phosphate, (b) Approximately 13.5% by weight of neat H2O2, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.0525% by weight, (d) the remainder of the solvent, and the remaining solvent, which includes, essentially consists of, or comprises the same. In a further embodiment of this embodiment, the solvent comprises water. In a further embodiment of this embodiment, the solvent is essentially made from water. In a further embodiment of this embodiment, the solvent consists of water. In a further embodiment of this embodiment, at least one neat cationic polymer anticorrosion agent comprises diallyldimethylammonium chloride. In a further embodiment of this embodiment, at least one neat cationic polymer anticorrosion agent is essentially made from diallyldimethylammonium chloride. In a further embodiment of this embodiment, at least one neat cationic polymer anticorrosion agent consists of diallyldimethylammonium chloride.

[0081] In one exemplary embodiment, the disclosed and claimed etching formulation is: (a) Approximately 42.5% by weight of neat phosphate, (b) Approximately 13.5% by weight of neat H2O2, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.175% by weight, (d) the remainder of the solvent, and the remaining solvent, which includes, essentially consists of, or comprises the same. In a further embodiment of this embodiment, the solvent comprises water. In a further embodiment of this embodiment, the solvent is essentially made from water. In a further embodiment of this embodiment, the solvent consists of water. In a further embodiment of this embodiment, at least one neat cationic polymer anticorrosion agent comprises diallyldimethylammonium chloride. In a further embodiment of this embodiment, at least one neat cationic polymer anticorrosion agent is essentially made from diallyldimethylammonium chloride. In a further embodiment of this embodiment, at least one neat cationic polymer anticorrosion agent consists of diallyldimethylammonium chloride.

[0082] In one exemplary embodiment, the disclosed and claimed etching formulation is: (a) Approximately 42.5% by weight of neat phosphate, (b) Approximately 13.5% by weight of neat H2O2, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.525% by weight, (d) the remainder of the solvent, and the remaining solvent, which includes, essentially consists of, or comprises the same. In a further embodiment of this embodiment, the solvent comprises water. In a further embodiment of this embodiment, the solvent is essentially made from water. In a further embodiment of this embodiment, the solvent consists of water. In a further embodiment of this embodiment, at least one neat cationic polymer anticorrosion agent comprises diallyldimethylammonium chloride. In a further embodiment of this embodiment, at least one neat cationic polymer anticorrosion agent is essentially made from diallyldimethylammonium chloride. In a further embodiment of this embodiment, at least one neat cationic polymer anticorrosion agent consists of diallyldimethylammonium chloride.

[0083] In one exemplary embodiment, the disclosed and claimed etching formulation is: (a) Approximately 25.5% by weight of neat phosphate, (b) Approximately 13.5% by weight of neat H2O2, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.0525% by weight, (d) the remainder of the solvent, and the remaining solvent, which includes, essentially consists of, or comprises the same. In a further embodiment of this embodiment, the solvent comprises water. In a further embodiment of this embodiment, the solvent is essentially made from water. In a further embodiment of this embodiment, the solvent consists of water. In a further embodiment of this embodiment, at least one neat cationic polymer anticorrosion agent comprises diallyldimethylammonium chloride. In a further embodiment of this embodiment, at least one neat cationic polymer anticorrosion agent is essentially made from diallyldimethylammonium chloride. In a further embodiment of this embodiment, at least one neat cationic polymer anticorrosion agent consists of diallyldimethylammonium chloride.

[0084] In one exemplary embodiment, the disclosed and claimed etching formulation is: (a) Approximately 46.6% by weight of neat phosphate, (b) Approximately 13.5% by weight of neat H2O2, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.0525% by weight, (d) the remainder of the solvent, and the remaining solvent, which includes, essentially consists of, or comprises the same. In a further embodiment of this embodiment, the solvent comprises water. In a further embodiment of this embodiment, the solvent is essentially made from water. In a further embodiment of this embodiment, the solvent consists of water. In a further embodiment of this embodiment, at least one neat cationic polymer anticorrosion agent comprises diallyldimethylammonium chloride. In a further embodiment of this embodiment, at least one neat cationic polymer anticorrosion agent is essentially made from diallyldimethylammonium chloride. In a further embodiment of this embodiment, at least one neat cationic polymer anticorrosion agent consists of diallyldimethylammonium chloride.

[0085] It should be understood that the subject matter disclosed and claimed includes, but is not limited to, the exemplary embodiments described above.

[0086] Manufacturing method

[0087] The disclosed and claimed subject matter further includes a method for producing the disclosed and claimed etching compound.

[0088] In one embodiment, a method for forming an etching composition is: (a) at least one phosphorus-containing acid or a salt thereof, (b) at least one oxidizing agent, (c) at least one cationic polymer corrosion inhibitor, (d) including combining at least one solvent with

[0089] Therefore, in one embodiment, a method for forming an etching composition is (i) A step of forming composition A by combining (a) at least one phosphorus-containing acid, (c) at least one cationic polymer corrosion inhibitor, and (d) at least one solvent, (ii) The step of combining the A composition with (b) at least one oxidizing agent. In one embodiment of this embodiment, (d) at least one solvent comprises water. In one embodiment of this embodiment, (d) at least one solvent is essentially made of water. In one embodiment of this embodiment, (d) at least one solvent consists of water.

[0090] How to use

[0091] The disclosed and claimed subject matter further includes a method for selectively removing a TiN layer while minimizing the etching rate of the W layer using the disclosed and claimed etching composition, and a method for manufacturing a semiconductor comprising an etching process using the disclosed and claimed etching composition. A wafer device is exposed to the etching composition for a desired time and at a desired temperature. The wafer device is then removed from the etching composition, rinsed with deionized water, and dried by exposure to nitrogen gas.

[0092] In one embodiment, this method a. A step of bringing a composite semiconductor device including a TiN layer and a W layer into contact with one or more etching compositions disclosed and claimed herein, b. The process includes rinsing the composite semiconductor device after the TiN layer has been at least partially removed. In a further embodiment of this design, the contact step is carried out at a temperature of approximately 25°C to approximately 90°C.

[0093] In further embodiments, the method may include a drying step.

[0094] In the methods described, "at least partially removed" means the removal of at least 90% of the material, preferably at least 95%. Most preferably, at least 99% is removed using the compositions of this development.

[0095] In some embodiments, the contact step can be carried out by any preferred means, such as immersion or spraying, or through a single wafer process.

[0096] In some embodiments, the temperature of the composition during the contact process is preferably about 25°C to about 90°C. In further embodiments, the temperature is about 30°C to about 60°C. In further embodiments, the temperature is about 40°C to about 60°C. In further embodiments, the temperature of the composition during the contact process is about 50°C.

[0097] In some embodiments, the etching selectivity of TiN with respect to W in the disclosed and claimed subject etching composition is greater than about 1. In some embodiments, the etching selectivity of TiN with respect to W in the disclosed and claimed subject etching composition is greater than about 5. In some embodiments, the etching selectivity of TiN with respect to W in the disclosed and claimed subject etching composition is greater than about 10. In some embodiments, the etching selectivity of TiN with respect to W in the disclosed and claimed subject etching composition is greater than about 20. In some embodiments, the etching selectivity of TiN with respect to W in the disclosed and claimed subject etching composition is greater than about 50. In some embodiments, the etching selectivity of TiN with respect to W in the disclosed and claimed subject etching composition is greater than about 100.

[0098] In some embodiments, the W etching rate is less than approximately 5 Å / min. In further embodiments, the W etching rate is less than approximately 3 Å / min. In even further embodiments, the W etching rate is less than approximately 1 Å / min.

[0099] In some embodiments, the rinsing step is performed by rinsing the substrate with deionized water by any suitable means, such as immersion or spraying techniques. In another embodiment, the rinsing step is performed using a mixture of deionized water and a water-miscible organic solvent (e.g., isopropyl alcohol).

[0100] In some embodiments, the drying step is carried out by any preferred means, such as isopropyl alcohol (IPA) vapor drying, heat, or centripetal force.

[0101] The disclosed and claimed formulations are intended for use in a “wastewater mode” process. In this process, the cleaning composition is removed from the system by being discharged as waste after a single use. Optionally, the cleaning compositions described herein may be used in a recirculating mode system. In this system, after use on a wafer or device, the composition is recycled for processing additional wafers or devices. In the recirculating mode system, it is preferable that the components of the cleaning composition, other than the solvent and oxidizer, are provided at higher concentrations than required in the wastewater mode system. [Examples]

[0102] Herein, we refer to more specific embodiments of the present disclosure and experimental results supporting such embodiments. The examples are given below to more fully illustrate the disclosed subject matter and should not be construed as limiting the disclosed subject matter.

[0103] It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed subject matter and the specific examples provided herein without departing from the spirit or scope of the disclosed subject matter. Accordingly, the disclosed subject matter, including the descriptions provided by the following examples, is intended to cover modifications and variations of the disclosed subject matter that fall within the scope of any claim and its equivalents.

[0104] Materials and methods:

[0105] All ingredients used in this specification are commercially available.

[0106] All compositions studied in this embodiment were prepared by mixing the ingredients in a 100 mL beaker using a 1-inch Teflon®-coated stirring rod. Typically, the first material added to the beaker was deionized (DI) water. Other ingredients were then added and dissolved in water to prepare the compositions.

[0107] Etching tests were performed by placing 100 g of the etching composition in a 150 mL beaker and stirring it at 400 rpm using a 1-inch round Teflon® stirring rod. The etching composition was heated to 30-60°C on a hot plate, and then a 2 cm × 2 cm wafer coupon was immersed in the solution and treated for 2-10 minutes. Next, the wafer coupon was rinsed in a DI water bath for 3 minutes and then dried using nitrogen gas. The TiN ratio was estimated from the change in thickness before and after etching and measured by spectroscopic ellipsometry (SCI Filmtek 2000 PAR-SE). The W ratio was estimated from the change in thickness before and after etching and measured by CDE 4 probe Resmap. Typical starting layer thicknesses were 1000 Å for W and 3000 Å for TiN.

[0108] The following series of tables shows the evaluation of several aspects of the compositions evaluated. In the tables below, the neat concentration of the components is shown in parentheses where necessary. Water in the tables below is neat.

[0109] Table 1 shows the etching rates of TiN and W at 50°C in formulations with different concentrations of Lupasol® FG and hydrogen peroxide. The pH of these formulations was measured to be approximately 0.3. Coupons coated with W and TiN blanket films were immersed in these formulations at 50°C for 2 to 10 minutes. The results clearly showed that the etching rate of W decreased significantly upon addition of Lupasol® FG, while the etching rate of TiN decreased only slightly. The etching rate of TiN decreased significantly in formulations with high hydrogen peroxide concentrations or low phosphoric acid concentrations. In Table 1, Example 1 is a comparative example. [Table 1]

[0110] Table 2 shows the etching rates of TiN and W at 50°C for formulations with different phosphorus concentrations. Clearly, the etching rate of TiN decreased as the phosphorus concentration decreased, but no significant change was observed in the etching rate of W. [Table 2]

[0111] Table 3 shows the etching rates of TiN and W at 50°C in formulations with different diallyldimethylammonium chloride and phosphoric acid concentrations. The pH of these formulations was measured to be approximately 0.3. Coupons coated with W and TiN blanket films were immersed in these formulations at 50°C for 2 to 10 minutes. The results clearly showed that the addition of diallyldimethylammonium chloride significantly reduced the etching rate of W, while the etching rate of TiN decreased only slightly. Lower phosphorus concentrations reduced the etching rate of TiN, but no significant change was observed in the etching rate of W. In Table 3, Induquat ECR 35L is an aqueous solution of diallyldimethylammonium chloride, and Example 10 is a comparative example. [Table 3]

[0112] The above-described examples and preferred embodiments are for illustrative purposes only and do not limit the invention as defined in the claims. For ease of understanding, numerous variations and combinations of the above-described features can be utilized without departing from the invention as described in the claims. Such variations are not considered to depart from the spirit and scope of the invention, and all such variations are intended to be included within the following claims.

Claims

1. (a) at least one phosphorus-containing acid or a salt thereof, (b) at least one oxidizing agent, (c) at least one cationic polymer corrosion inhibitor, (d) An etching compound comprising at least one solvent.

2. The etching compound according to claim 1, wherein the at least one phosphorus-containing acid or salt thereof comprises one or more of the following: phosphoric acid, tetramethylammonium phosphate, tetrabutylammonium phosphate, tetraethylammonium phosphate, tetrapropylammonium phosphate, etidronic acid, aminotrimethylenephosphonic acid, tripolyphosphate, tetrapolyphosphate, pyrophosphate, polymetaphosphate, hypophosphorous acid, phosphorous acid, diphosphorous acid, triphosphorous acid, (aminomethyl)phosphonic acid, (aminoethyl)phosphonic acid, (aminopropyl)phosphonic acid, mono-n-dodecyl phosphate, tetramethylammonium phosphate, tetrabutylammonium phosphate, tetraethylammonium phosphate, tetrapropylammonium phosphate, and one or more combinations thereof.

3. The etching compound according to claim 1, wherein the at least one phosphorus-containing acid or salt thereof contains phosphoric acid.

4. The etching compound according to claim 1, wherein the at least one phosphorus-containing acid or a salt thereof constitutes about 9% to about 75% by weight of the compound.

5. The etching compound according to claim 1, wherein the at least one phosphorus-containing acid or a salt thereof constitutes about 25% to about 50% by weight of the compound.

6. The etching compound according to claim 1, wherein the compound contains about 25% to about 50% by weight of phosphoric acid.

7. The at least one oxidizing agent is hydrogen peroxide, ammonium persulfate, peracetic acid, peroxybenzoic acid, Oxone (2KHSO ５ ·KHSO ４ ·K ２ SO ４ ), n-methylmorpholine oxide (NMMO or NMO), benzoyl peroxide, tetrabutylammonium peroxymonosulfate, ferric chloride, permanganate, peroxoborate, periodic acid, iodic acid, vanadium(V) oxide, vanadium(IV, V) oxide, ammonium metavanadate, perchlorate, persulfate, ammonium peroxydisulfate, peracetic acid, urea hydrogen peroxide, nitric acid (HNO ３ ), ammonium hypochlorite (NH ４ ClO), ammonium tungstate ((NH ４ ) １０ H ２ (W ２ O ７ ), ammonium chlorite (NH ４ ClO ２ ), ammonium chlorate (NH ４ ClO ３ ), ammonium iodate (NH ４ IO ３ ), ammonium perborate (NH ４ BO ３ ), ammonium perchlorate (NH ４ ClO ４ ), ammonium periodate (NH ４ IO ３ ), ammonium persulfate ((NH ４ ) ２ S ２ O ８ ), tetramethylammonium chlorite ((N(CH ３ ) ４ )ClO ２ ), tetramethylammonium chlorate ((N(CH ３ ) ４ )ClO ３ ), tetramethylammonium iodate ((N(CH ３ ) ４ )IO ３ ) ３ ) ４ ) BO ３ ), tetramethylammonium perchlorate ((N(CH ３ ) ４ )ClO ４ ), tetramethylammonium periodate ((N(CH ３ ) ４ ) IO ４ ), tetramethylammonium persulfate ((N(CH ３ ) ４ ) S ２ O ８ ), ((CO(NH ２ ) ２ ) H ２ O ２ The etching compound according to claim 1, comprising ), peracetic acid (CH(CO)OOH), and combinations thereof.

8. The etching compound according to claim 1, wherein the at least one oxidizing agent comprises hydrogen peroxide.

9. The etching compound according to claim 1, wherein the at least one oxidizing agent constitutes about 6% to about 20% by weight of the compound.

10. The etching compound according to claim 1, wherein the compound contains about 6% to about 20% by weight of neat hydrogen peroxide.

11. The etching compound according to claim 1, wherein the at least one cationic polymer anticorrosion agent comprises one or more of the following: polyalkyleneimines and their derivatives, poly(diallyldimethylammonium chloride), diallyldimethylammonium chloride, and combinations thereof.

12. The etching compound according to claim 1, wherein the at least one cationic polymer corrosion inhibitor comprises polyethyleneimine.

13. The etching compound according to claim 1, wherein the compound comprises about 0.001% by weight to about 5% by weight of at least one cationic polymer corrosion inhibitor.

14. The etching compound according to claim 1, wherein the at least one solvent comprises water.

15. The etching compound according to claim 1, wherein the at least one solvent is water.

16. The etching compound according to claim 1, wherein the at least one solvent comprises one or more non-aqueous solvents.

17. The at least one solvent is dimethyl sulfoxide (DMSO), dimethyl sulfone (DMSO) ２ ), sulfolane ((CH ２ ) ４ SO ２ The etching compound according to claim 1, comprising one or more non-aqueous solvents, one or more of the following: n-methylpyrrolidone, glycol ether, glycol, and combinations thereof.

18. The etching compound according to claim 1, wherein the at least one solvent comprises one or more non-aqueous solvents including dimethyl sulfoxide (DMSO).

19. The etching compound according to claim 1, wherein the at least one solvent comprises water and one or more non-aqueous solvents.

20. The etching compound according to claim 1, wherein the compound comprises about 30% by weight to about 80% by weight of at least one solvent.

21. The etching compound according to claim 1, wherein the compound comprises about 40% by weight to about 50% by weight of at least one solvent.

22. The etching compound according to claim 1, wherein the compound contains about 30% to about 80% by weight of water.

23. The etching compound according to claim 1, wherein the compound contains about 40% to about 50% by weight of water.

24. (a) Approximately 30% to 75% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.001% to approximately 3.0% by weight, (d) The etching compound according to claim 1, comprising the remaining solvent.

25. (a) Approximately 30% to 75% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.001% to approximately 3.0% by weight, (d) The etching compound according to claim 1, comprising the remainder water.

26. (a) Approximately 30% to 75% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.001% to approximately 3.0% by weight, (d) The etching compound according to claim 1, comprising the remaining solvent.

27. (a) Approximately 30% to 75% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.001% to approximately 3.0% by weight, (d) The etching compound according to claim 1, comprising the remainder water.

28. (a) Approximately 42.5% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of about 0.001% by weight, (d) The etching compound according to claim 1, comprising the remaining solvent.

29. (a) Approximately 42.5% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of about 0.001% by weight, (d) The etching compound according to claim 1, comprising the remainder water.

30. (a) Approximately 42.5% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of about 0.005% by weight, (d) The etching compound according to claim 1, comprising the remaining solvent.

31. (a) Approximately 42.5% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of about 0.005% by weight, (d) The etching compound according to claim 1, comprising the remainder water.

32. (a) Approximately 42.5% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of about 0.01% by weight, (d) The etching compound according to claim 1, comprising the remaining solvent.

33. (a) Approximately 42.5% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of about 0.01% by weight, (d) The etching compound according to claim 1, comprising the remainder water.

34. (a) Approximately 42.5% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one cationic polymer corrosion inhibitor in an amount of about 0.02% by weight, (d) The etching compound according to claim 1, comprising the remaining solvent.

35. (a) Approximately 42.5% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of about 0.06% by weight, (d) The etching compound according to claim 1, comprising the remaining solvent.

36. (a) Approximately 42.5% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of about 0.06% by weight, (d) The etching compound according to claim 1, comprising the remainder water.

37. (a) Approximately 62% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of about 0.015% by weight, (d) The etching compound according to claim 1, comprising the remaining solvent.

38. (a) Approximately 62% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of about 0.015% by weight, (d) The etching compound according to claim 1, comprising the remainder water.

39. (a) Approximately 27% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of about 0.006% by weight, (d) The etching compound according to claim 1, comprising the remaining solvent.

40. (a) Approximately 27% by weight of neat phosphate, (b) Approximately 19.5% by weight of neat H ２ O ２ and (c) at least one neat cationic polymer corrosion inhibitor in an amount of about 0.006% by weight, (d) The etching compound according to claim 1, comprising the remainder water.

41. (a) Approximately 25.5% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of about 0.01% by weight, (d) The etching compound according to claim 1, comprising the remaining solvent.

42. (a) Approximately 25.5% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of about 0.01% by weight, (d) The etching compound according to claim 1, comprising the remainder water.

43. (a) Approximately 46.3% by weight of neat phosphate, (b) about 13.5 wt% neat H ２ O ２ and (c) at least one neat cationic polymer corrosion inhibitor in an amount of about 0.01% by weight, (d) The etching compound according to claim 1, comprising the remaining solvent.

44. (a) Approximately 46.3% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of about 0.01% by weight, (d) The etching compound according to claim 1, comprising the remainder water.

45. (a) Approximately 42.5% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.0175% by weight, (d) The etching compound according to claim 1, comprising the remaining solvent.

46. (a) Approximately 42.5% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.0175% by weight, (d) The etching compound according to claim 1, comprising the remainder water.

47. (a) Approximately 42.5% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.0525% by weight, (d) The etching compound according to claim 1, comprising the remaining solvent.

48. (a) Approximately 42.5% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.0525% by weight, (d) The etching compound according to claim 1, comprising the remainder water.

49. (a) Approximately 42.5% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.175% by weight, (d) The etching compound according to claim 1, comprising the remaining solvent.

50. (a) Approximately 42.5% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.175% by weight, (d) The etching compound according to claim 1, comprising the remainder water.

51. (a) Approximately 42.5% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.525% by weight, (d) The etching compound according to claim 1, comprising the remaining solvent.

52. (a) Approximately 42.5% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.525% by weight, (d) The etching compound according to claim 1, comprising the remainder water.

53. (a) Approximately 25.5% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.0525% by weight, (d) The etching compound according to claim 1, comprising the remaining solvent.

54. (a) Approximately 25.5% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.0525% by weight, (d) The etching compound according to claim 1, comprising the remainder water.

55. (a) Approximately 46.6% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.0525% by weight, (d) The etching compound according to claim 1, comprising the remaining solvent.

56. (a) Approximately 46.75% by weight of neat phosphate, (b) Neat H ２ O ２ and, (c) at least one neat cationic polymer corrosion inhibitor in an amount of approximately 0.0525% by weight, (d) The etching compound according to claim 1, comprising the remainder water.

57. A method for forming an etching composition according to any one of claims 1 to 56, (i) A step of forming composition A by combining (a) at least one phosphorus-containing acid, (c) at least one cationic polymer corrosion inhibitor, and (d) at least one solvent, A method comprising (ii) the step of combining the A composition with (b) the at least one oxidizing agent.

58. A method for selectively increasing the etching rate of titanium nitride (TiN) relative to tungsten (W) during the manufacturing of semiconductor devices, a. A step of bringing a semiconductor device including a TiN layer film and a W layer film into contact with one or more etching compounds described in any one of claims 1 to 56, b. A method comprising the step of rinsing the semiconductor device after the TiN layer has been at least partially removed.

59. The method according to claim 58, further comprising the step of drying the semiconductor device after step b.

60. The method according to claim 58, wherein the selectivity of the etching rate of titanium nitride (TiN) to tungsten (W) is greater than about 10.

61. The method according to claim 58, wherein the selectivity of the etching rate of titanium nitride (TiN) to tungsten (W) is greater than approximately 50.

62. The method according to claim 58, wherein the selectivity of the etching rate of titanium nitride (TiN) to tungsten (W) is greater than approximately 100.

63. The method according to claim 58, wherein the etching rate of the tungsten (W) is approximately 5 Å / min.

64. The method according to claim 58, wherein the etching rate of the tungsten (W) is approximately 3 Å / min.

65. The method according to claim 58, wherein the etching rate of the tungsten (W) is approximately 1 Å / min.

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