阅读说明：本技术 蚀刻后残留物清洁组合物及其使用方法 (Post etch residue cleaning compositions and methods of use thereof ) 是由 孙来生 李翊嘉 *** 吴爱萍 于 2019-07-24 设计创作，主要内容包括：本发明提供一种微电子器件(半导体衬底)清洁组合物及其使用方法,该清洁组合物包含水、草酸和两种或更多种腐蚀抑制剂。(The present invention provides a microelectronic device (semiconductor substrate) cleaning composition and method of using the same, the cleaning composition comprising water, oxalic acid, and two or more corrosion inhibitors.)

1. A semiconductor substrate cleaning composition comprising water, oxalic acid, and two or more types of corrosion inhibitors selected from the following three types of corrosion inhibitors: (a) an amino acid; (b) non-phenolic organic acids, non-phenolic organic acid salts or other derivatives of non-phenolic organic acids, and (c) phenols and phenol derivatives.

2. The cleaning composition of claim 1, comprising one or more corrosion inhibitors of the type (a) and one or more corrosion inhibitors of the type (b).

3. The cleaning composition of claim 1, comprising one or more corrosion inhibitors of the type (a) and one or more corrosion inhibitors of the type (c).

4. The cleaning composition of claim 1, comprising one or more corrosion inhibitors of the type (b) and one or more corrosion inhibitors of the type (c).

5. The cleaning composition of claim 2, further comprising one or more corrosion inhibitors of the type (c).

6. The cleaning composition of any one of claims 1-3 and 5, wherein one or more of the corrosion inhibitors of type (a) is selected from the group consisting of glycine, histidine, lysine, alanine, leucine, threonine, serine, valine, aspartic acid, glutamic acid, arginine, cysteine, asparagine, glutamine, isoleucine, methionine, phenylalanine, proline, tryptophan, and tyrosine.

7. The cleaning composition of any of claims 1-2 and 4-6, wherein one or more of the corrosion inhibitors of type (b) are selected from ascorbic acid and ascorbic acid derivatives.

8. The cleaning composition according to any one of claims 1 and 3-7, wherein the one or more corrosion inhibitors of the type (c) are selected from catechol, tert-butylcatechol, resorcinol, pyrogallol, hydroquinone, 1,2, 4-benzenetriol and 1,3, 5-benzenetriol, gallic acid and gallic acid derivatives, and/or cresol, xylenol, salicyl alcohol, p-hydroxybenzyl alcohol, o-hydroxybenzyl alcohol, p-aminophenol, m-aminophenol, diaminophenol, p-hydroxybenzoic acid, o-hydroxybenzoic acid, 2, 4-dihydroxybenzoic acid, 2, 5-dihydroxybenzoic acid, 3, 4-dihydroxybenzoic acid and 3, 5-dihydroxybenzoic acid.

9. The cleaning composition of any one of claims 1-8, wherein one or more of the corrosion inhibitors of type (a) comprises glycine, wherein one or more of the corrosion inhibitors of type (b) comprises ascorbic acid, and wherein one or more of the corrosion inhibitors of type (c) comprises gallic acid or a gallic acid derivative.

10. A method of cleaning a microelectronic device or semiconductor substrate, the method comprising the steps of: contacting one or more microelectronic devices or semiconductor substrates with a composition according to any of claims 1-9.

Background

The fabrication of microelectronic structures involves a number of steps. In a manufacturing scheme for manufacturing integrated circuits, it is sometimes desirable to selectively etch different surfaces of a semiconductor. Historically, many very different types of etching processes have been successfully utilized to selectively remove material. Furthermore, the selective etching of different layers within a microelectronic structure is considered to be an important step in the integrated circuit manufacturing process.

In the manufacture of semiconductors and semiconductor microcircuits, it is often necessary to coat the substrate material with polymeric organic substances. Examples of some substrate materials include aluminum, titanium, copper, silicon dioxide coated silicon wafers, optionally with a metallic element of aluminum, titanium or copper, and the like. Typically, the polymeric organic substance is a photoresist material. This is the material that forms the etch mask upon development after exposure. At least a portion of the photoresist is removed from the substrate surface in a subsequent processing step. One common method of removing photoresist from a substrate is by wet chemistry. The wet chemical composition formulated for removing photoresist from a substrate should not corrode, dissolve and/or passivate the surface of any metallic circuitry; chemically altering the inorganic substrate; and/or attack the substrate itself to remove the photoresist from the substrate. Another method of removing photoresist is by a dry ashing process, in which photoresist is removed by plasma ashing using oxygen or a forming gas such as hydrogen. The residue or by-product remaining on the substrate after plasma ashing may be the photoresist itself or a combination of the photoresist, the underlying substrate, and/or the etching gas. These residues or byproducts are commonly referred to as sidewall polymers, veils, or spacers (ferces).

Increasingly, Reactive Ion Etching (RIE) is the process of choice for pattern transfer during via, metal line and trench formation. For example, complex semiconductor devices such as advanced DRAMs and microprocessors, which require multiple layers of back-end-of-line interconnect wiring, utilize RIE to create via, metal line, and trench structures. Vias are used to provide contact between one level of silicon, silicide or metal wiring and the next level of wiring through an interlayer dielectric. The metal lines serve as conductive structures for device interconnects. The trench structure is used for forming a metal line structure. Vias, metal lines, and trench structures typically expose metals and alloys, such as Al, Al and Cu alloys, Cu, Ti, TiN, Ta, TaN, W, TiW, silicon, or silicides, such as tungsten, titanium, or cobalt silicides. The RIE process typically leaves residues or complex mixtures (which may include resputtering oxide materials, organic materials from photoresist, and/or antireflective coating materials used to lithographically define via, metal line, and/or trench structures).

It is possible to remove the polymer (photoresist and/or antireflective coating material and post etch residue) by treatment with an inorganic aqueous solution. An example of such a solution is a dilute solution of sulfuric acid, hydrogen peroxide, ammonium fluoride or chromophoric phosphoric acid (EP 0068277). Dilute sulfuric acid peroxide (DSP) is commonly used to remove post-etch resist from aluminum surfaces. DSP is a water-based dilute solution of sulfuric acid and hydrogen peroxide. Dilution of the DSP makes the cleaning process on the aluminum surface more controllable. Small amounts of fluoride, such as HF, accelerate the etching process, making these mixtures preferred for use in spin etchers in single wafer processes. DSP + is DSP with fluoride ion source added. (other acids, such as nitric acid (EP1139401a1) or phosphoric acid, or ammonium hydrogen phosphate (EP1063689a1) can also be used in these solutions.) in the case of all these solutions, the AlCu metallization under the polymer is slightly "underetched" so that the polymer (or post-etch residue or PER) can be mechanically removed (stripped) in a first step. Dissolution of the polymer or PER then takes place. This process allows only a relatively small process window between complete cleaning and initial etching of the metal or metals thereon, particularly AlCu. In many cases, the cleaning of the through-holes is particularly unsatisfactory, since the short process times are often insufficient for the polymer to dissolve completely and for the underlying SiO layer ₂Not as low etched by the solution as is the case with AlCu and/or other metals present on the substrate. In addition, the presence of metal structures is subject to overetching due to intentionally low etching of the metal structures under the polymer or PERThe risk of attack of multiple etches, known as overetching, which can lead to pitting that damages the metal structure.

Accordingly, it is desirable to provide selective cleaning compositions and methods that are capable of removing residues (e.g., residual photoresist and/or processing residues, such as those produced by selective etching using plasma and/or RIE). Moreover, it would be desirable to provide selective cleaning compositions and methods capable of removing residues such as photoresist (polymers) and etch residues (collectively, "PERs") that exhibit high selectivity to PERs compared to metals, high dielectric constant materials (referred to herein as "high-k"), silicon, silicides, and/or interlayer dielectric materials (including low dielectric constant materials (referred to herein as "low-k"), such as deposited oxides) that may also be exposed to the cleaning compositions. It is desirable to provide compositions that are compatible with and can be used with sensitive low-k films such as HSQ, MSQ, Fox, black diamond, and TEOS (tetraethyl silicate).

Accordingly, there is a need for a cleaning solution for cleaning substrates that has improved corrosion protection for aluminum, copper, other metals, and other structures and films present on semiconductor substrates, wherein the cleaning solution prevents pitting from occurring while removing or substantially removing all residues from the substrate.

Disclosure of Invention

The compositions disclosed herein relate to aqueous compositions for removing photoresist, etch and ash residues and contaminants from semiconductor substrates without attacking, to any undesirable extent, metal, low-k dielectric and/or high-k dielectric materials that may also be exposed to the compositions. The compositions and methods of the present invention remove photoresist and residues from a substrate without attacking, dissolving and/or passivating the surface of any metallic circuit and/or chemically altering the inorganic substrate; and/or attack the substrate itself. In addition, the compositions of the present invention provide stable bath life. The compositions of the present invention provide stable pH levels and/or consistent and effective cleaning of microelectronic devices after aging, use and/or exposure to air.

In one aspect of the invention, a semiconductor substrate cleaning composition comprises water, oxalic acid, and two or more types of corrosion inhibitors selected from the following three types of corrosion inhibitors: (a) an amino acid; (b) non-phenolic organic acids, non-phenolic organic acid salts or other derivatives of non-phenolic organic acids, and (c) phenols and phenol derivatives. In another aspect of the invention, the cleaning composition comprises one or more of said corrosion inhibitors of type (a) and one or more of said corrosion inhibitors of type (b). In another aspect, the type (a) corrosion inhibitor is selected from the group consisting of glycine, histidine, lysine, alanine, leucine, threonine, serine, valine, aspartic acid, glutamic acid, and arginine, alone or in combination with others. In another aspect, alone or in combination with the other aspects, the type (a) corrosion inhibitor is selected from the group consisting of glycine, histidine, lysine, alanine, leucine, threonine, serine, valine, aspartic acid, glutamic acid, arginine. Other amino acids that may be used in the compositions of the present invention include cysteine, asparagine, glutamine, isoleucine, methionine, phenylalanine, proline, tryptophan and tyrosine. In another aspect, alone or in combination with the other aspects, the corrosion inhibitor of type (b) is selected from ascorbic acid and ascorbic acid derivatives. In another aspect, alone or in combination with other aspects of the invention, the cleaning composition comprises one or more corrosion inhibitors of said type (a) and one or more corrosion inhibitors of said type (c). In another aspect of the invention, alone or in combination with the other aspects, the corrosion inhibitor of type (c) is selected from catechol, tert-butylcatechol, resorcinol, pyrogallol, hydroquinone, 1,2, 4-and 1,3, 5-benzenetriols, gallic acid and gallic acid derivatives, and/or cresol, xylenol, salicyl alcohol, p-hydroxybenzyl alcohol, o-hydroxybenzyl alcohol, p-aminophenol, m-aminophenol, diaminophenol, p-hydroxybenzoic acid, o-hydroxybenzoic acid, 2, 4-dihydroxybenzoic acid, 2, 5-dihydroxybenzoic acid, 3, 4-dihydroxybenzoic acid and 3, 5-dihydroxybenzoic acid. In another aspect of the invention, alone or in combination with other aspects, the cleaning composition comprises one or more corrosion inhibitors of said type (b) and one or more corrosion inhibitors of said type (c). In another aspect of the invention, alone or in combination with the other aspects, the corrosion inhibitor of type (c) is selected from catechol, tert-butylcatechol, resorcinol, pyrogallol, hydroquinone, 1,2, 4-and 1,3, 5-benzenetriols, gallic acid and gallic acid derivatives, and/or cresol, xylenol, salicyl alcohol, p-hydroxybenzyl alcohol, o-hydroxybenzyl alcohol, p-aminophenol, m-aminophenol, diaminophenol, p-hydroxybenzoic acid, o-hydroxybenzoic acid, 2, 4-dihydroxybenzoic acid, 2, 5-dihydroxybenzoic acid, 3, 4-dihydroxybenzoic acid and 3, 5-dihydroxybenzoic acid. In another aspect of the invention, alone or in combination with other aspects, the cleaning composition comprises water, oxalic acid, and one or more of the corrosion inhibitors of type (a), one or more of the corrosion inhibitors of type (b), and one or more of the corrosion inhibitors of type (c).

In another aspect, alone or in combination with the other aspects, the corrosion inhibitor of type (b) includes 2-O-alkyl ascorbic acid ether, 3-O-alkyl ascorbic acid ether, 5-6-O-alkylene-ascorbic acid, 2-O-alkanoyl-ascorbic acid, 3-O-alkanoyl-ascorbic acid, or 6-O-alkanoyl-ascorbic acid. In another aspect of the invention, alone or in combination with other aspects, the cleaning composition comprises from about 20% to about 99.5% water, from about 0.1% to about 10% oxalic acid, and from about 0.1% to about 15% of one or more corrosion inhibitors. In another aspect of the invention, the cleaning composition is free of substituted or unsubstituted ammonium hydroxide. In one aspect of the invention, alone or in combination with the other aspects, the corrosion inhibitor of type (c) is selected from gallic acid or a derivative of gallic acid, or from gallic acid, methyl gallate, phenyl gallate, 3,4, 5-triacetoxy gallic acid, methyl trimethyl gallate, ethyl gallate or gallic acid anhydride.

In another aspect of the invention, alone or in combination with other aspects of the invention, the cleaning composition comprises a corrosion inhibitor selected from the group consisting of: one or more of gallic acid and gallic acid derivatives, or one or more of ascorbic acid and ascorbic acid derivatives, or a mixture of one or more of gallic acid and gallic acid derivatives and one or more of ascorbic acid and ascorbic acid derivatives.

In another aspect of the invention, alone or with other aspects of the invention, the cleaning composition may comprise from about 0.1 to about 10 wt.% of two or more corrosion inhibitors. In another aspect of the invention, alone or in combination with other aspects of the invention, the cleaning composition may comprise from about 0.1 to about 5 wt.% or from about 0.1 to about 2 wt.% of the phenol and/or phenol derivative, and/or from about 1 to about 15 wt.% or from about 2 to about 5 wt.% of the non-phenolic organic acid or non-phenolic organic acid derivative. In another aspect of the invention, alone or in combination with other aspects of the invention, the cleaning composition may comprise from about 1 to about 10 wt% of one or more non-phenolic organic acids or non-phenolic organic acid derivatives in the composition, and the phenol and/or phenol derivatives are present in the composition from about 0.1 to about 8 wt%. In another aspect of the invention, alone or in combination with other aspects of the invention, the cleaning compositions of the invention comprise from about 80 to about 99 wt.% or from about 90 to about 99 wt.% water present in the composition. In another aspect of the invention, alone or in combination with other aspects of the invention, the cleaning composition comprises from about 0.8 to about 10 wt.% or from about 0.5 to about 6 wt.% of oxalic acid present in the composition. In another aspect of the invention, alone or with other aspects of the invention, the cleaning composition has a pH of 0.1 to 7 or 0.5 to 3.

In another aspect of the invention, alone or in combination with other aspects of the invention, the cleaning composition is substantially free of fluorine-containing compounds and peroxides, and/or may be substantially free of amines (other than the one or more amino acids), and/or may be substantially free of nitrogen-containing compounds, and/or may be substantially free of formic acid and citric acid, and/or other components that may be excluded as described below.

In another aspect of the invention, a method of cleaning a microelectronic device or semiconductor substrate is provided, comprising the steps of: contacting one or more microelectronic devices or semiconductor substrates with any of the compositions described herein. In another aspect of the invention, a method of cleaning a microelectronic device or semiconductor substrate is provided, comprising the steps of: contacting one or more microelectronic devices or semiconductor substrates with a composition comprising water, oxalic acid, and two or more types of corrosion inhibitors selected from the three types of corrosion inhibitors: (a) an amino acid; (b) non-phenolic organic acids, non-phenolic organic acid salts or other derivatives of non-phenolic organic acids, and (c) phenols and phenol derivatives. The method of the invention may (further) comprise the steps of: contacting the substrate with any of the cleaning compositions of the present invention at a temperature of from about 20 ℃ to about 80 ℃ for from about 0.1 minute to about 90 minutes; and rinsing the cleaned substrate to remove the cleaning composition. Alone or in combination with other aspects, the methods of the present invention provide for etching metal on a substrate at a rate of less than 10 angstroms per minute.

The compositions of the present invention comprise water, oxalic acid, two or more corrosion inhibitors and optionally, an organic solvent, and optionally, other components. The composition may be acidic, i.e. the composition may have a pH of less than 7.

Detailed Description

All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.

The use of the terms "a" and "an" and "the" and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms "comprising," having, "" including, "and" containing "are to be construed as open-ended terms (i.e.," including, but not limited to ") but also encompass partially closed or closed-ended terms that" consist essentially of "and" consist of. Recitation of ranges of values herein are merely intended to serve 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 into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention. All percentages are weight percentages, and all weight percentages are based on the total weight of the composition (prior to any optional concentration and/or dilution). Reference to "one or more" includes "two or more" and "three or more" and the like.

Preferred embodiments of the present invention are described herein. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.

For ease of reference, "microelectronic device" corresponds to semiconductor substrates, flat panel displays, phase change memory devices, solar panels, and other products, including solar substrates, photovoltaic devices, and micro-electro-mechanical systems (MEMS), which are fabricated for microelectronic, integrated circuit, or computer chip applications. 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. The solar substrate may be doped or undoped. It should be understood that the term "microelectronic device" is not meant to be limiting in any way, and includes any substrate that will ultimately become a microelectronic device or microelectronic assembly.

As defined herein, a "low-k dielectric material" corresponds to any material used as a dielectric material in a layered microelectronic device, wherein the material has a dielectric constant of less than about 3.5. Preferably, the low-k dielectric material comprises a low polarity material, 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 may have different densities and different porosities.

As defined herein, the term "barrier material" corresponds to any material used in the art to seal metal lines (e.g., copper interconnects) to minimize diffusion of the metal (e.g., copper) into the dielectric material. Preferred barrier layer materials include tantalum, titanium, ruthenium, hafnium and other refractory metals and their nitrides and silicides.

"substantially free" is defined herein as less than 0.1 wt%, or less than 0.01 wt%, most preferably less than 0.001 wt%, or less than 0.0001 wt%, or less than 1 ppb. "substantially free" also includes 0.0000 wt% and 0 ppb. The term "free" means 0.0000 wt% or 0 ppb.

As used herein, "about" is intended to correspond to ± 5% of the stated value.

In all such compositions (where particular components of the composition are discussed with reference to weight percent ranges including a zero lower limit), it is understood that such components may or may not be present in various embodiments of the composition, and where such components are present, they may be present at concentrations as low as 0.001 weight percent, based on the total weight of the composition in which they are used.

The present invention provides compositions and methods comprising the same for selectively removing residues such as, for example, ashed photoresist and/or processing residues from microelectronic devices. In cleaning processes involving articles such as substrates useful in microelectronic devices, typical contaminants to be removed may include, for example, organic compounds such as exposed and ashed photoresist materials, ashed photoresist residues, UV or X-ray hardened photoresists, C-F containing polymers, low and high molecular weight polymers, and other organic etch residues; inorganic compounds from Chemical Mechanical Planarization (CMP) slurries, such as metal oxides, ceramic particles, and other inorganic etch residues; metal-containing compounds, such as organometallic residues and metal-organic compounds; ionic and neutral, light and heavy inorganic (metal) species, moisture and insoluble species, including particles produced by processes such as planarization and etching processes. In a particular embodiment, the residues removed are processing residues, such as those produced by reactive ion etching.

Furthermore, ashed photoresist and/or processing residues are typically present on semiconductor substrates (microelectronic devices) that also include metals (e.g., copper, aluminum), silicon, silicates, and/or interlayer dielectric materials, such as deposited silicon oxides and derivatized silicon oxides, e.g., HSQ, MSQ, FOX, TEOS, and spin-on-glass, and/or high-k materials, e.g., hafnium silicate, hafnium oxide, Barium Strontium Titanium (BST), Ta ₂O ₅And TiO ₂Wherein the photoresist and/or residue and the metal, silicon, silicide, interlevel dielectric material, and/or high-k material are both contacted with the cleaning composition. Additionally, the compositions disclosed herein can exhibit a minimum etch rate for certain dielectric materials (e.g., silicon oxide). The compositions and methods disclosed herein are useful for selectively removing residues without significantly attacking one or more of the following: metal, silicon dioxide, interlayer dielectric materials, and/or high-k materials. In one embodiment, the compositions disclosed herein may be suitable for structures containing sensitive low-k films. In certain embodiments, the substrate may contain one or more metals, such as, but not limited to, copper alloys, aluminum alloys, titanium nitride, tantalum nitride, tungsten, and titanium/tungsten, one or more of which are not attacked by the cleaning composition.

The compositions disclosed herein comprise water, oxalic acid, two or more corrosion inhibitors, and optionally, an organic solvent, and other optional components.

Water (W)

The cleaning composition of the present invention is water-based and therefore comprises water. In the present invention, water acts in various ways, for example, to dissolve one or more solid components of the residue, as a carrier for the component, as an aid to remove metal residues, as a viscosity modifier for the composition, and as a diluent. Preferably, the water used in the cleaning composition is Deionized (DI) water.

It is believed that for most applications, water may comprise an amount within a range having a starting point and an ending point selected from the following list of weight percentages: 20. 50, 55, 65, 80, 85, 86, 87, 88, 90, 92, 93, 95, 96, 97, 98, 99, 99.5, for example, from about 20 to about 99.5 wt.%, or from about 20 to about 99 wt.%, or from about 50 to about 99 wt.%, or from about 65 to about 99 wt.%, or from about 80 to about 99 wt.%, or from about 85 to about 98 wt.%, or from about 88 to about 97 wt.%, or from about 88 to about 95 wt.%, or from about 85 to about 95 wt.%, or from about 90 to about 95 wt.%, or from about 88 to about 95 wt.% water. Other preferred embodiments of the present invention may comprise from about 92 to about 99.5 wt.%, or from about 92 to about 99 wt.%, or from about 92 to about 97 wt.%, or from about 92 to about 95 wt.%, or from about 93 to about 99 wt.%, or from about 93 to about 98 wt.%, or from about 93 to about 96 wt.% water. Still other preferred embodiments of the present invention may include water in an amount to achieve the desired weight percentage of the other ingredients.

Oxalic acid

The cleaning composition of the present invention comprises oxalic acid. It is believed that for most applications, the composition may comprise oxalic acid in a range having a start and end point selected from the following list of weight percentages: 0.1, 0.5, 0.8, 1, 1.5, 3,4, 4.5, 6, 7, 8, 10, 12, 15, for example, from about 0.1 to about 15 wt%, or from about 0.5 to about 12 wt%, or from about 0.8 to about 10 wt%, or from about 0.8 to about 8 wt%, or from about 0.8 to about 7 wt%, or from about 1 to about 8 wt%, or from about 1 to about 6 wt%, or from about 0.5 to about 6 wt%, or from about 1 to about 4.5 wt%, or from about 1.5 to about 3 wt%, or from about 0.5 to less than 4 wt% oxalic acid.

Corrosion inhibitors

The composition of the present composition comprises two or more corrosion inhibitors selected from at least two of the following three types of corrosion inhibitors: (a) one or more amino acids; (b) one or more non-phenolic organic acids, non-phenolic organic acid salts or other derivatives of non-phenolic organic acids, and (c) one or more of phenol and phenol derivatives.

Examples of type (a) corrosion inhibitors (i.e., amino acids) include glycine, histidine, lysine, alanine, leucine, threonine, serine, valine, aspartic acid, glutamic acid, arginine. Other amino acids that may be used in the compositions of the present invention include cysteine, asparagine, glutamine, isoleucine, methionine, phenylalanine, proline, tryptophan and tyrosine. Some preferred amino acids include glycine, alanine, valine, leucine, isoleucine, histidine. Some preferred amino acids have a molecular weight of less than 135, or less than 132, or less than 119, or less than 100. In some embodiments, preferred amino acids have an isoelectric pH between 5.9 and 7.9, or between 5.9 and 6.9, or between 5.9 and 6.1, and in some embodiments, both the molecular weight range and the isoelectric point are within a combination of the ranges specified above in any combination.

Examples of corrosion inhibitors of type (b) (i.e., non-phenolic organic acids and non-phenolic organic acid derivatives) that may be used as one or more than one corrosion inhibitor include ascorbic acid and ascorbic acid derivatives or mixtures thereof. Ascorbic acid derivatives that can be used in the compositions of the present invention include 2-O-alkyl ascorbic acid ethers, 3-O-alkyl ascorbic acid ethers, 5-6-O-alkylene-ascorbic acid, 2-O-alkanoyl-ascorbic acid, 3-O-alkanoyl-ascorbic acid and 6-O-alkanoyl-ascorbic acid. Non-phenolic organic acids are acids that do not have a phenol in their structure. In preferred embodiments, these corrosion inhibitors may comprise cyclic structures other than a benzene ring. In some embodiments, these corrosion inhibitors may comprise a heterocyclic ring.

Examples of corrosion inhibitors of type (c) (i.e., phenol derivatives) as corrosion inhibitors useful in the present invention include catechol, tert-butylcatechol, resorcinol, pyrogallol, hydroquinone, 1,2, 4-benzenetriol and 1,3, 5-benzenetriol, gallic acid and gallic acid derivatives, cresol, xylenol, salicyl alcohol, p-hydroxybenzyl alcohol, o-hydroxybenzyl alcohol, p-aminophenol, m-aminophenol, diaminophenol, p-hydroxybenzoic acid, o-hydroxybenzoic acid, 2, 4-dihydroxybenzoic acid, 2, 5-dihydroxybenzoic acid, 3, 4-dihydroxybenzoic acid and 3, 5-dihydroxybenzoic acid. As the phenol derivatives which can be used as the corrosion inhibitor in the present invention, there can be exemplified catechol, tert-butylcatechol, resorcinol, pyrogallol, hydroquinone, resorcinol, catechol, 1,2, 3-benzenetriol, 1,2, 4-benzenetriol and 1,3, 5-benzenetriol, gallic acid and gallic acid derivatives. The phenol derivative useful in the present invention may have at least two hydroxyl groups. The phenol derivatives as corrosion inhibitors useful in the present invention may be gallic acid and gallic acid derivatives. The gallic acid derivatives include methyl gallate, phenyl gallate, 3,4, 5-triacetoxy gallic acid, methyl trimethyl gallate, ethyl gallate and gallic acid anhydride.

In some embodiments, the corrosion inhibitor in the compositions of the present invention comprises: (a) one or more amino acids; and: (b) one or more non-phenolic organic acids or derivatives of non-phenolic organic acids or mixtures thereof or (c) phenol or one or more phenol derivatives and/or mixtures thereof. In some embodiments, the corrosion inhibitor in the compositions of the present invention comprises (a) and (b). In some embodiments, the compositions of the present invention comprise (a) and (c). In other embodiments, the compositions of the present invention comprise (b) and (c). In some embodiments, the corrosion inhibitor in the compositions of the present invention comprises: (a) one or more amino acids; (b) one or more non-phenolic organic acids or derivatives of non-phenolic organic acids or mixtures thereof; and (c) one or more phenol derivatives and/or phenols. In one embodiment, the corrosion inhibitor comprises one or more of gallic acid and gallic acid derivatives or one or more of ascorbic acid and ascorbic acid derivatives. In another embodiment, the composition of the invention comprises one or more gallic acid or gallic acid derivatives and one or more ascorbic acid or ascorbic acid derivatives. In one embodiment, the corrosion inhibitor comprises one or more amino acids and/or one or more ascorbic acid and ascorbic acid derivatives. In another embodiment, the composition of the invention comprises one or more amino acids and one or more gallic acid or gallic acid derivatives. In another embodiment, the composition of the invention comprises one or more gallic acid or gallic acid derivatives, one or more ascorbic acid or ascorbic acid derivatives, and one or more amino acids.

It is believed that the total amount of one or more or two or more or three or more corrosion inhibitors of any number or combination of types of corrosion inhibitors (a), (b), and (c) in the cleaning compositions of the present invention can be within a range having a starting point and an ending point selected from the following list of weight percentages: 0.1, 0.2, 0.5, 1, 1.5, 2,3, 4,5, 6, 7, 8, 10, 12, 15, 18, 20, for example, from about 0.1 to about 15 wt.%, or from about 0.1 to about 10 wt.%, or from about 0.1 to about 8 wt.%, or from about 0.5 to about 15 wt.%, or from about 0.5 to about 10 wt.%, or from about 5 to about 12 wt.%, or from about 1 to about 8 wt.%, or from about 1 to about 6 wt.%, or from about 1 to about 5 wt.% of the composition.

In other embodiments, one or more corrosion inhibitors (alone or in combination with the other types of corrosion inhibitors described above) comprising an amino acid (corrosion inhibitor of type (a)) in the composition, if present, can be within a range having a starting point and an ending point selected from the following list of weight percentages: for example, 0.1, 0.2, 0.5, 1, 1.5, 2,3, 4,5, 6, 7, 8, 10, 12, 15, 18, 20, for example, about 0.1 to about 15 wt%, or about 1 to about 10 wt%, or about 1 to about 8 wt%, or about 1 to about 7 wt%, or about 1 to about 6 wt%, or about 2 to about 5 wt% of the composition.

In other embodiments, the one or more corrosion inhibitors (alone or in combination with other types of corrosion inhibitors described above) comprising the non-phenolic organic acid and/or the derivative of the non-phenolic organic acid or mixtures thereof (corrosion inhibitor of type (b)), if present, in the composition may be within a range having a starting point and an ending point selected from the following list of weight percentages: 0.1, 0.2, 0.5, 1, 1.5, 2,3, 4,5, 6, 7, 8, 10, 12, 15, 18, 20, for example from about 1 to about 15 wt%, or from about 1 to about 10 wt%, or from about 1 to about 8 wt%, or from about 1 to about 7 wt%, or from about 1 to about 6 wt%, or from about 2 to about 5 wt% of the composition.

One or more phenols and/or phenol derivatives or mixtures thereof (corrosion inhibitors of type (c)) if present (alone or in combination with other types of corrosion inhibitors described above) in the composition may be in a range having a starting point and an ending point selected from the following list of weight percentages: 0.1, 0.2, 0.5, 1, 1.5, 2,3, 4,5, 6, 7, 8, 10, 12, 15, 18, 20, for example, a positive amount of about 0.1 to about 15 wt%, or about 0.1 to about 10 wt%, or about 0.1 to about 8 wt%, or about 0.1 to about 7 wt%, or about 0.1 to about 5 wt%, or about 0.1 to about 2 wt%, or about 0.2 to about 2 wt%, or less than 3 wt% of the composition.

In some embodiments, wherein the composition comprises one or more phenols and/or phenol derivatives or mixtures thereof and one or more non-phenolic organic acids and/or non-phenolic organic acid derivatives or mixtures thereof, each in an amount of any combination as described in the preceding three paragraphs, for example, from about 1 to about 8% of one or more non-phenolic organic acid and/or non-phenolic organic acid derivatives or mixtures thereof, and from about 0.1 to about 5% of one or more than one phenol and/or phenol derivatives or mixtures thereof; or from about 0.5 to about 5% of one or more non-phenolic organic acids and/or derivatives of non-phenolic organic acids or mixtures thereof, and from about 0.1 to about 2% of one or more than one phenol and/or phenol derivatives or mixtures thereof. In other embodiments, wherein the composition comprises any two or three of (a), (b), and (c); (a) is one or more than one amino acid, (b) is one or more non-phenolic organic acids and/or derivatives of non-phenolic organic acids or mixtures thereof, and (c) is one or more phenols and/or phenol derivatives or mixtures thereof, the amount of (a) and/or (b) and/or (c) can be any combination of the amounts in the preceding three paragraphs with respect to the corrosion inhibitor, e.g., (a) about 1% or about 10% of one or more than one amino acid; (b) from about 1 to about 10% of one or more non-phenolic organic acids and/or derivatives of non-phenolic organic acids or mixtures thereof, and (c) from about 0.1 to about 10% of one or more than one phenol and/or phenol derivatives or mixtures thereof; or, (a) from about 1 to about 8% of one or more than one amino acid; (b) from about 1 to about 8% of one or more non-phenolic organic acids and/or derivatives of non-phenolic organic acids or mixtures thereof, and (c) from about 0.1 to about 5% of one or more than one phenol and/or phenol derivatives or mixtures thereof. In yet another example, the compositions of the present invention may comprise (a) from about 1 to about 5% of one or more than one amino acid; (b) from about 0.5 to about 5% of one or more non-phenolic organic acids and/or derivatives of non-phenolic organic acids or mixtures thereof, and (c) from about 0.1 to about 5% of one or more phenols and/or phenol derivatives or mixtures thereof.

pH

In certain embodiments, the cleaning composition has a pH within a range defined by any combination of the following endpoints: 0.1, 0.5, 0.8, 1, 1.2, 1.5, 2, 2.5, 2.8, 3,4,5, 6, 7, for example, from about 0.1 to about 7, or from about 0.5 to about 5, or from about 0.5 to about 4, or from about 0.5 to about 3, or from about 0.5 to about 2.8, or from about 0.5 to about 2.5, or from about 0.8 to about 2. In some embodiments, the pH is less than 4. In other embodiments, the pH is less than 3. In certain embodiments, a composition for removing highly inorganic etch residues and oxide scum (e.g., alumina scum) may require a pH of 0.5 to 3. The pH of the composition can be measured directly using a commercially available pH meter.

Additional organic acids (optional)

The compositions of the present invention may comprise additional organic acids (other than the types of corrosion inhibitors listed above) including glycolic acid, lactic acid, hydroxybutyric acid, glyceric acid, malic acid, tartaric acid, formic acid, citric acid, malonic acid, succinic acid, glutaric acid, maleic acid. Alternatively, the compositions of the present invention may be substantially free or free of any or all of the additional organic acids listed in the preceding sentence in any combination, or substantially free or free of all of the additional organic acids. In the latter case, the composition of the invention may be free or substantially free of glycolic acid, lactic acid, hydroxybutyric acid, glyceric acid, malic acid, tartaric acid, formic acid, citric acid, malonic acid, succinic acid, glutaric acid and maleic acid. Alternatively, as non-limiting examples without any combination of one or more acids: the composition of the present invention may be substantially free or free of formic acid, or citric acid, or formic acid and citric acid. Alternatively, if present, the additional organic acid may be present in an amount of about 0.1 to 10 weight percent.

Water miscible solvent (optional)

The etching composition of the invention may comprise a water miscible solvent. Examples of water-miscible organic solvents that may be used are N-methylpyrrolidone (NMP), 1-methoxy-2-propyl acetate (PGMEA), ethylene glycol, propylene glycol, butyl diglycol, 1, 4-butanediol, tripropylene glycol methyl ether, propylene glycol propyl ether, ethylene glycol N-butyl ether (e.g. commercially available under the trade name Dowanol DB), hexyloxypropylamine, poly (oxyethylene) diamine, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, glycerol, alcohols, sulfoxides or mixtures thereof. Preferred solvents are alcohols, glycols or mixtures thereof.

In some embodiments of the invention, the water-miscible organic solvent may comprise a glycol ether. Examples of the glycol ether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monobenzyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, polyethylene glycol monomethyl ether, diethylene glycol methyl ether, triethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol diisopropyl ether, tripropylene glycol monomethyl ether, 1-methoxy-2-butanol, 2-methoxy-1-butanol, 2-methoxy-2-methylbutanol, 1-dimethoxyethane, and 2- (2-butoxyethoxy) ethanol.

It is believed that for most applications, the amount of water-miscible organic solvent in the composition may be in a range having a starting point and an ending point selected from the following list of weight percentages: 0.1, 0.5, 1, 5, 7, 12, 15, 25, 30, 35, 40, 50, 65, 75, 80, 85. Examples of such solvent ranges include from about 0.5 to about 80 wt% of the composition; or about 0.5 to about 65 wt%; or about 1 to about 50 wt%; or about 0.1 to about 30 wt%, 0.5 to about 25 wt%; or about 0.5 to about 15 wt%; or about 1 to about 7 wt%; or from about 0.1 to about 12%. When a solvent is present in the composition of the invention, the total amount of water and solvent is preferably greater than 70 wt%, or greater than 75 wt%, or greater than 80 wt%, or greater than 85 wt%, or greater than 90 wt%, and/or preferably less than 97 wt%, or less than 96 wt%, or less than 95 wt%, or less than 94 wt% of the total composition.

The solvent (if present) can support the cleaning action and protect the wafer surface.

In some embodiments, the compositions of the present invention are free or substantially free of any or all of the above-listed water-miscible organic solvents, in any combination, or all of the water-miscible organic solvents added to the composition.

Metal chelating agents (optional)

Another optional ingredient that may be used in the cleaning composition is a metal chelating agent, which generally functions to increase the ability of the composition to retain metals in solution and enhance dissolution of metallic residues. Typical examples of chelating agents which can be used for this purpose are the following organic acids and isomers and salts thereof: (ethylenediamine) tetraacetic acid (EDTA), butanediamine tetraacetic acid, (1, 2-cyclohexanediamine) tetraacetic acid (CyDTA), diethylenetriaminepentaacetic acid (DETPA), ethylenediaminetetrapropionic acid, (hydroxyethyl) ethylenediaminetriacetic acid (HEDTA), N '-ethylenediaminetetra (methylenephosphonic) acid (EDTMP), triethylenetetraminehexaacetic acid (TTHA), 1, 3-diamino-2-hydroxypropyl-N, N' -tetraacetic acid (DHPTA), methyliminodiacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid (NTA), gluconic acid, saccharic acid, phthalic acid, mandelic acid, salicylic acid, and 8-hydroxyquinoline. Preferred chelating agents are aminocarboxylic acids, such as EDTA, CyDTA, and aminophosphonic acids, such as EDTMP.

It is believed that for most applications, the chelating agent, if present, is present in the composition in an amount of from about 0.01 to about 10 wt%, or from about 0.1 to about 5 wt%, or from about 0.5 to about 5 wt% of the composition.

In some embodiments, the compositions of the present invention are free or substantially free (in any combination) of any or all of the metal chelating agents listed above, or all of the metal chelating agents added to the composition.

Additional Corrosion inhibitors (optional)

Examples of additional corrosion inhibitors include triazole compounds.

Exemplary triazole compounds include benzotriazole, o-tolyltriazole, m-tolyltriazole, p-tolyltriazole, carboxybenzotriazole, 1-hydroxybenzotriazole, nitrobenzotriazole and dihydroxypropylbenzotriazole.

In some other embodiments, the additional corrosion inhibitor is a triazole and is at least one of benzotriazole, o-tolyltriazole, m-tolyltriazole, and p-tolyltriazole.

It is believed that for most applications, the additional corrosion inhibitor or inhibitors, if present, will comprise from about 0.1 to about 15 wt%, or from about 0.1 to about 10 wt%, or from about 0.5 to about 5 wt%, or from about 0.1 to about 1 wt%, or from about 0.5 to about 5 wt% of the composition.

In some embodiments, the compositions of the present invention are free or substantially free of any or all of the additional corrosion inhibitors listed above, including any or all triazole compounds, added to the composition.

Other ingredients optionally included or excluded

In other embodiments, the composition may comprise, or be substantially free of, or free of, any or all of: surfactants, chemical modifiers, dyes, biocides.

In some embodiments, the compositions of the present invention may be free or substantially free of at least one or more than one or all of any combination of the following, or, if already present in the composition, any additional of the following: all nitrogen-containing compounds other than amino acids, sulfur-containing compounds, bromine-containing compounds, chlorine-containing compounds, iodine-containing compounds, fluorine-containing compounds, halogen-containing compounds, phosphorus-containing compounds, ammonium salts, metal-containing compounds, hydroxylamines or hydroxylamine derivatives (including N, N-Diethylhydroxylamine (DEHA), isopropylhydroxylamine or salts of hydroxylamines, such as hydroxylammonium chloride, ammonium hydroxylammonium sulfate), sodium-containing compounds, calcium-containing compounds, alkyl thiols, organosilanes, halide-containing compounds, oxidizing agents, peroxides, amines, alkanolamines, buffer substances, polymers, inorganic acids, quaternary ammonium compounds, substituted and unsubstituted ammonium hydroxides, amides, aminoalcohols, metal hydroxides, and strong bases.

Materials removed with the compositions described herein include ashed photoresist and processing residues known in the art under the names sidewall polymers, masks, spacer etch residues, ashing residues, and the like. In certain preferred embodiments, the photoresist is exposed, developed, etched, and ashed prior to contacting with the composition described herein. The compositions disclosed herein are compatible with low-k films such as hsq (fox), MSQ, SiLK, and the like. The formulations are also effective in stripping ashed photoresist, including both positive and negative photoresist, and plasma etch residues, such as organic residues, organometallic residues, inorganic residues, metal oxides or photoresist complexes, at low temperatures with very low erosion of tungsten, aluminum, copper, titanium containing substrates. In addition, the composition is compatible with a variety of high dielectric constant materials. For many of the listed metals, such as aluminum, copper or aluminum and copper alloys, or tungsten, etc., the compositions and methods of the present invention can provide etch rates of less than about 10 angstroms/minute, or less than about 8 angstroms/minute, or less than about 6 angstroms/minute, or less than about 5 angstroms/minute, or less than about 4 angstroms/minute, or less than about 3 angstroms/minute, which can be provided at processing temperatures below 60 ℃ or below 45 ℃. For tungsten, the etch rate provided by the compositions and methods of the present invention can be less than about 1 angstrom/minute or less than 0.5 angstrom/minute, which can be provided at processing temperatures below 60 ℃ or below 45 ℃.

During the manufacturing process, a photoresist layer is coated on the substrate. Using a photolithographic process, a pattern is defined on the photoresist layer. The patterned photoresist layer is thus plasma etched, thereby transferring the pattern to the substrate. Etching residues are generated in the etching stage. The patterned substrate is subsequently ashed to form a residue. The primary residue to be cleaned when the substrate is ashed may be an etchant residue.

The methods described herein can be performed by contacting a substrate with the composition (either by dipping or spraying one at a time, or by bringing a plurality of substrates into a bath sized to hold a plurality of substrates having organic or metal-organic polymers, inorganic salts, oxides, hydroxides, or composites or combinations thereof present as a film or residue). The actual conditions, such as temperature, time, etc., depend on the nature and thickness of the material to be removed. Typically, the substrate is contacted or immersed in a container containing the cleaning composition of the present invention at a temperature of from about 20 ℃ to about 80 ℃, or from about 20 ℃ to about 60 ℃, or from about 20 ℃ to about 40 ℃. Typical time periods for exposure of the substrate to the composition can be, for example, from 0.1 to 90 minutes, or from 1 to 60 minutes, or from 1 to 30 minutes. After contact with the composition, the substrate may be rinsed and then dried. Drying is typically carried out under an inert atmosphere and may include spinning. In certain embodiments, a deionized water rinse or a rinse containing deionized water and other additives may be performed before, during, and/or after contacting the substrate with the compositions described herein.