阅读说明：本技术 多胺的季铵碱 (Quaternary ammonium bases of polyamines ) 是由 D·H·钱皮恩 D·C·刘易斯 J·乌里亚特 周晖 K·张 C·政 于 2019-07-29 设计创作，主要内容包括：本发明提供一种季铵碱溶液,其包含多胺与有机环氧烷的反应产物。该季铵碱溶液可以用于多种应用,例如用于从金属或电介质表面除去化学残留物。(The present invention provides a quaternary ammonium base solution comprising the reaction product of a polyamine and an organic alkylene oxide. The quaternary ammonium base solutions can be used in a variety of applications, such as for removing chemical residues from metal or dielectric surfaces.)

1. A quaternary ammonium base solution comprising the reaction product of (i) a polyamine and (ii) an organic alkylene oxide,

(i) the polyamine has the formula:

wherein each R₁Independently hydrogen, alkyl, cycloalkyl, aryl, alkoxyalkyl, hydroxylated alkyl, hydroxylated alkoxyalkyl, or two R₁The groups may combine to form a cyclic amine, provided that said R₁The groups are selected from combinations that form at least one tertiary nitrogen; x is 0 or an integer of at least 1; r' is a group having 2 to 10An alkyl group of carbon atoms, an aryl group, an alkylaryl group or an unsaturated hydrocarbon group having 2 to 10 carbon atoms, or a group containing O or N in combination with C and H and which may form a ring structure;

(ii) the organic alkylene oxide has the formula:

wherein each R is independently hydrogen, an alkyl group having 1 to 6 carbon atoms, an unsaturated alkyl group, an aryl group, an aralkyl group, or one or more R groups may form a ring structure containing 3 to 12 carbon atoms, and optionally the R groups may contain one or more oxygen atoms.

2. A quaternary ammonium base solution according to claim 1, wherein the polyamine is bis (3-dimethylaminopropyl) ether.

3. A quaternary ammonium base solution according to claim 1, wherein the polyamine is bis (2-morpholinoethyl) ether.

4. A quaternary ammonium base solution according to claim 1, wherein the polyamine is bis (2-dimethylaminoethyl) amine.

5. A quaternary ammonium base solution according to claim 1, wherein the polyamine is N, N-tris (3-dimethylaminopropyl) amine.

6. The quaternary ammonium hydroxide solution according to claim 1, wherein the polyamine is N, N', N "-pentamethyldiethylenetriamine.

7. The quaternary ammonium hydroxide solution according to claim 1, wherein the polyamine is N, N', N "-pentamethyldipropylenetriamine.

8. A quaternary ammonium base solution according to claim 1, wherein the organic alkylene oxide is ethylene oxide.

9. A quaternary ammonium base solution according to claim 1, wherein the organic alkylene oxide is propylene oxide.

10. The quaternary ammonium base solution according to claim 1, wherein the quaternary ammonium compound comprises 1 mol% or more of a quaternary ammonium compound having at least two quaternary ammonium groups relative to the total number of moles of the quaternary ammonium compound.

11. A quaternary ammonium compound solution according to claim 1, further comprising water.

12. The quaternary ammonium compound solution according to claim 1, further comprising a miscible organic solvent.

13. A composition for removing chemical residues from metal surfaces or dielectric surfaces comprising the quaternary ammonium base solution of claim 1.

14. A method for removing chemical residues from a metal surface or a dielectric surface comprising contacting the metal surface or dielectric surface with the composition of claim 1.

15. A method of forming a quaternary ammonium base solution comprising: (i) contacting a polyamine comprising at least one primary or secondary amine group in situ with an organic alkylene oxide to convert the polyamine comprising primary or secondary amine groups to a polyamine comprising tertiary amine groups, and (ii) further reacting the polyamine comprising tertiary amine groups with the organic alkylene oxide to form a quaternary ammonium base.

16. The method of claim 15, wherein the polyamine comprising a primary or secondary amine group is N, N' -bis (2-aminoethyl) piperazine.

17. The quaternary ammonium base solution of claim 15, wherein the polyamine comprising a primary or secondary amine group is N, N' -bis (3-aminopropyl) piperazine.

18. The quaternary ammonium base solution of claim 15, wherein the polyamine containing a primary or secondary amine group is bis (2-dimethylaminoethyl) ether.

19. A quaternary ammonium base solution formed by the method of claim 15.

Technical Field

The present invention generally relates to a quaternary ammonium base solution comprising the reaction product of a polyamine and an organic alkylene oxide. The quaternary ammonium base solution can be used in a variety of applications including, but not limited to, etching, cleaning, polishing, and patterning of metal and dielectric surfaces.

Background

The fabrication of integrated circuits and other electronic devices, such as photovoltaic cells, introduces a variety of processing steps that may include many toxic, flammable, explosive, and/or environmentally unfriendly chemicals. Many of these chemicals are also widely used for metal or non-metal surfaces in a variety of other applications including aircraft exterior cleaning, metal part machining, and engine maintenance.

Aluminum hydroxides such as tetramethylammonium hydroxide have traditionally been used for etching, cleaning, polishing, and patterning, as described in:

U.S. patent 7,825,079, which discloses a composition comprising tetramethylammonium hydroxide and a chelating agent for removing photoresist or post etch residue;

U.S. patent 7,671,001, which discloses a composition comprising tetramethylammonium hydroxide and a metal corrosion inhibitor for cleaning semiconductor wafer substrates:

us patent 7,498,295, which discloses a composition comprising tetramethylammonium hydroxide, a chelating agent and a corrosion inhibitor for use after chemical mechanical planarization (planarization) of a semiconductor substrate; and

WO2006/056298, which discloses a composition comprising tetramethylammonium hydroxide, dimethyl sulfoxide, ethylene glycol and water for cleaning microelectronic substrates.

While tetramethylammonium hydroxide is known to be very effective, it has been found to be highly toxic to the nervous system. Therefore, safer alternatives to this chemical are always sought. One such replacement that has recently been used is choline hydroxide, as described in:

U.S. patent 8,765,653, which discloses a composition comprising a copolymer of acrylamido-methyl-propane sulfonate, acrylic acid-2-acrylamido-2-methylpropane sulfonic acid copolymer and mixtures thereof, a non-acetylidene surfactant, and choline hydroxide for removing residues from semiconductor manufacturing processes; and

us patent 7,135,445, which discloses a composition comprising bis-or tris-choline hydroxide, a solvent and a corrosion inhibitor, for cleaning solder flux and resist material from microcircuits.

Although choline hydroxide has several advantages over tetramethylammonium hydroxide, such as low toxicity, relatively low cost, ease of manufacture, and biodegradability, it has serious odor problems during use and can decompose to produce colored solutions and precipitates. Accordingly, it would be desirable to develop new compositions that are as effective as prior art compositions containing tetramethylammonium hydroxide or choline hydroxide, but that do not exhibit the toxicity, odor, or color problems described above.

Disclosure of Invention

The present invention relates to a quaternary ammonium base solution comprising the reaction product of (i) a polyamine and (ii) an organic alkylene oxide.

The quaternary ammonium bases of the present invention can be used in a variety of applications, such as in compositions used to remove chemical residues from metal surfaces or dielectric surfaces.

Detailed Description

If appearing herein, the term "comprising" and derivatives thereof is not intended to exclude the presence of any additional component, step or procedure, whether or not the same is disclosed herein. For the avoidance of any doubt, all compositions claimed herein through use of the term "comprising" may include any additional additive, adjuvant or compound, unless indicated to the contrary. Conversely, if appearing herein, the term "consisting essentially of … …" excludes any other components, steps, or procedures from any subsequently stated range, except for those that are not essential to operability, and if used, the term "consisting of … …" excludes any components, steps, or procedures not expressly described or recited. Unless otherwise specified, the term "or" means the members of the list individually as well as in any combination.

The articles "a" and "an" are used herein to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article. For example, "a polyamine" means one polyamine or more than one polyamine. The phrases "in one embodiment," "according to one embodiment," and the like generally mean that a particular feature, structure, or characteristic described after the phrase is included in at least one embodiment of the invention, and may be included in more than one embodiment of the invention. Importantly, such expressions do not necessarily refer to the same embodiment. If the specification states a component or feature "may", "can", or "may" be included or have a certain characteristic, that particular component or feature does not necessarily have to be included or have that characteristic.

As used herein, the term "about" may allow for a variable degree within a value or range, for example, may be within 10%, within 5%, or within 1% of the value or limit of the range.

The recitation of values by ranges is intended to be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a range of 1 to 6 should be considered to have explicitly disclosed sub-ranges such as 1 to 3, or 2 to 4, or 3 to 6, etc., as well as individual numbers within that range, such as 1,2,3, 4, 5, and 6. This applies regardless of the breadth of the range.

In the methods and processes described herein, the steps may be performed in any order, except when time or order of operation is explicitly recited. Further, the specified steps can be performed concurrently unless the explicit claim language dictates that they are performed separately.

The term "substantially free" refers to a composition or mixture wherein a particular compound is present in an amount that does not materially affect the composition or mixture. For example, "substantially free of choline hydroxide" means that choline hydroxide may be included in the composition or mixture in an amount that does not substantially affect the odor or color of the composition or mixture. It is within the ability of one skilled in the art, having the benefit of this disclosure, to determine whether the amount of a compound has a substantial effect on the composition. In some embodiments, substantially free may be less than 2 wt%, or less than 1 wt%, or less than 0.5 wt%, or less than 0.1 wt%, or less than 0.05 wt%, or even less than 0.01 wt%, based on the total weight of the composition. In some embodiments, substantially free means that the particular compound is not present in any amount (i.e., 0.0 wt%) in the corresponding composition.

As used herein, the term "alkyl" refers to a branched or unbranched saturated hydrocarbon group having 1-30 carbon atoms, such as methyl ("Me"), ethyl ("Et"), n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. In some aspects, the alkyl groups herein can contain 1 to 12 carbon atoms. The term "lower alkyl" refers to an alkyl group having 1 to 7 carbon atoms, or in some aspects 1 to 4 carbon atoms. The term "higher alkyl" refers to alkyl groups having more than 7 carbon atoms.

The term "organic alkylene oxide" refers to a compound having the formula:

wherein each R is the same or different and is hydrogen, an alkyl group having 1 to 6 carbon atoms, an unsaturated alkyl group, an aryl group, or an aralkyl group, or one or more R groups form a ring structure containing 3 to 12 carbon atoms, and in some embodiments the R groups may contain one or more oxygen atoms. Examples of alkylene oxides (a sub-class of organic alkylene oxides) that may be used include, but are not limited to, formaldehyde, ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, and hexylene oxide.

The term "alkoxyalkyl" refers to an-O-alkyl substituted alkyl group.

The term "aryl" refers to C₆-C₁₄Monocyclic or polycyclic aromatic ring systems including, but not limited to, phenyl, naphthyl, phenanthryl, anthracyl, indenyl, azulenyl, biphenyl, biphenylene, and fluorenyl.

The term "aralkyl" refers to an aryl-substituted alkyl group.

The term "cycloalkyl" refers to saturated cycloalkyl groups having 3 to 12 carbon atoms, such as cyclopropyl, cyclohexyl, and cyclooctyl, which may have suitable substituents on the ring.

The terms "optional" or "optionally" mean that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not. For example, the expression "optionally substituted alkyl" means that the alkyl may or may not be substituted, and the description includes both unsubstituted alkyls and alkyls with substitution.

The term "polyamine" refers to a compound having two or more amine groups per molecule, wherein at least one amine group is a tertiary amine group or is converted in situ to such an amine group. For example, N' -tetrakis (2-hydroxyethyl) ethylenediamine can be prepared in situ by reacting ethylenediamine with ethylene oxide, and then can be further ethoxylated (i.e., reacted with an organic alkylene oxide) to form a quaternary ammonium base.

As noted above, ammonium hydroxide is commonly used in the electronics and metal processing industries in processes such as etching, cleaning, polishing, and patterning of metal and dielectric surfaces. Although the effect of these ammonium compounds is believed to be due to the presence of hydroxide ions acting at the metal or dielectric surface, the design of the organic ammonium ions can significantly affect the performance of these hydroxides. Applicants have surprisingly found that many quaternary ammonium bases exhibit high reactivity on metal or dielectric surfaces. In addition, the quaternary ammonium bases of the present invention are relatively non-toxic and substantially odor-free, and can be readily designed to provide a wide variety of alternatives of reactivity when specific reaction rates are required during wet processing steps or when specific types or mixtures of metal or dielectric surfaces are encountered. The quaternary ammonium bases of the present invention may also be used to develop, etch, or remove unwanted organic or other residues from organic photoresists.

Accordingly, in a first embodiment, there is provided a quaternary ammonium base solution comprising the reaction product of a polyamine and an organic alkylene oxide.

Various polyamines can be used as long as they have at least one tertiary amine group capable of forming a quaternary ammonium group (or can form a tertiary amine in situ). In one embodiment, the quaternary ammonium hydroxide can be derived from a non-hydroxylated polyamine, a hydroxylated polyamine, or a mixture thereof.

In one embodiment, the non-hydroxylated polyamine may be a compound having the formula:

wherein each R₁Identical or different and is hydrogen, alkyl, cycloalkyl, aryl, alkoxyalkyl, hydroxylated alkyl or hydroxylated alkoxyalkyl, in such combination forming at least one tertiary nitrogen; x is 0 or an integer of at least 1, such as 1 to 10, or 1 to 3; and each R' is the same or different and is an alkyl, aryl, alkaryl, unsaturated hydrocarbon group having at least 2, such as 2 to 10 carbon atoms or 2 to 5 carbon atoms, or may contain O or N in combination with C and H and further may form a ringAnd (5) structure. In some embodiments, R₁Two of the groups may combine to form cyclic amines, for example morpholine and piperidine and alkyl derivatives, such as N-alkyl morpholine and N-alkyl piperidine and imidazoline. In some embodiments, the R' group may form a ring or heterocyclic or aromatic ring, such as morpholine, piperazine, piperidine, imidazoline, or phenylene.

In another embodiment, the hydroxylated polyamine may be a compound having the formula:

or a compound having the formula:

wherein each R₁Identical or different and is hydrogen, alkyl, cycloalkyl, aryl, alkoxyalkyl, hydroxylated alkyl or hydroxylated alkoxyalkyl, in such combination forming at least one tertiary nitrogen; x is 0 or an integer of at least 1, such as 1 to 10, or 1 to 3; and n is an integer of at least 2, such as 2 to 10, or 2 to 5. In some embodiments, R₁Two of the groups may combine to form cyclic amines, for example morpholine and piperidine and alkyl derivatives, such as N-alkyl morpholine and N-alkyl piperidine and imidazoline.

Examples of the above-mentioned polyamine may include, but are not limited to, N, N, N ', N' -tetramethylethylenediamine, N, N, N ', N' -tetraethylethylenediamine, N, N, N ', N' -pentamethyldiethylenetriamine, N, N, N ', N' -tetramethylpropane-1, 3-diamine, N, N, N ', N' -pentamethyldipropylenetriamine, N, N, N ', N' -tetramethylpropane-1, 3-diamine, N, N, N ', N' -tetramethylbutane-1, 4-diamine, N, N, N ', N' -tetramethylhexane-1, 6-diamine, N, N, N ', N' -tetrakis (2-hydroxyethyl) ethylenediamine, 1,4,7,10, 10-hexamethyltriethylenetetramine, N, N, N ', N' -tetrakis (2-hydroxypropyl) ethylenediamine, bis (N, N-dimethylaminoethyl) ether and bis (2-dimethylaminoethyl) ether, bis (3-dimethylaminopropyl) ether, bis (2-morpholinoethyl) ether, triethylenediamine, methyltriethylenediamine, ethyltriethylenediamine, dimethyltriethylenediamine, N, N, N-tris (3-dimethylaminopropyl) amine, bis (2-dimethylaminoethyl) amine, N, N '-bis (2-aminoethyl) piperazine, N, N' -bis (3-aminopropyl) piperazine, and mixtures thereof.

In one embodiment, the organic alkylene oxide is a compound having the formula:

wherein R is₂And R₃Identical or different and are hydrogen, alkyl having 1 to 12 carbon atoms, unsaturated hydrocarbon radicals, aryl having 6 to 18 carbon atoms, aralkyl having 6 to 18 carbon atoms, or R₂And R₃The groups may form a ring structure containing 3 to 12 carbon atoms. In some embodiments, R₂And R₃The group may further contain one or more oxygen atoms. Examples of organic alkylene oxides may include, but are not limited to, ethylene oxide, propylene oxide, 1, 2-butylene oxide, 1, 2-pentylene oxide, styrene oxide, diene dioxides such as butadiene oxide, and mixtures thereof. Examples of other organic alkylene oxide compounds are cyclohexene oxide, glycidol, allyl glycidyl ether, phenyl glycidyl ether, alkyl glycidyl ether, styrene oxide, bicyclo [2.2.1]Oxepane and bicyclo [2.2.2]And epoxy octane.

The reaction of an organic alkylene oxide (e.g., alkylene oxide group) with a basic nitrogen atom to form a quaternary ammonium moiety is well known to those skilled in the art and need not be described in detail. Thus, in one embodiment, the polyamine is reacted with an organic alkylene oxide in the presence of water. The polyamine may be mixed with water and the system may then be pressurized. The organic alkylene oxide may then be added in a molar ratio of at least about 1:1 to the polyamine. In some embodiments, the organic alkylene oxide can be reacted with an amine in the presence of at least a stoichiometric amount of water to form a quaternary ammonium base, and in the presence of an organic solvent. In some embodiments, the molar ratio may be from about 1:1 to about 3N:1 of the organic alkylene oxide to the polyamine, or from about 1:1 to about 1.5N:1 of the organic alkylene oxide to the polyamine, where N is the number of amine groups in the starting compound. For example, for a triamine such as Pentamethyldiethylenetriamine (PMDETA), 3 moles of the organic alkylene oxide having one alkylene oxide per molecule would be N moles of the organic alkylene oxide relative to PMDETA. In some embodiments, the amount of organic alkylene oxide and additional amount of alkylene oxide to polyamine used to convert any primary or secondary amine to a tertiary amine is an organic alkylene oxide to polyamine of from 1:1 to about 3N:1, or from about 1:1 to about 1.5N:1, where N is the number of amine groups in the starting compound. The reaction can be carried out at a temperature of less than about 70 deg.C, for example, from about 40 deg.C to about 50 deg.C, with continuous stirring, and its completion can be marked by a pressure drop to about atmospheric pressure, or the quaternary ammonium content can be determined by potentiometric titration using a strong acid such as HCl.

The quaternary ammonium base solution can contain any suitable concentration of quaternized amine nitrogens. Thus, in one embodiment, the concentration of quaternized amine in the quaternary ammonium base solution can be from about 1 weight percent to about 80 weight percent based on the total amount of the quaternary ammonium base solution. In other embodiments, the concentration of quaternized amine nitrogens in the quaternary ammonium base solution can be from about 10 wt% to about 70 wt%, or from about 35 wt% to about 65 wt%, or from about 40 wt% to about 60 wt%, or from about 45 wt% to about 55 wt%, based on the total amount of the quaternary ammonium base solution.

In another embodiment, the product of the invention (i.e., quaternary ammonium base solution) may comprise quaternary ammonium bases having at least about 1% total quaternary molecule (quat molecule) containing more than one quaternary ammonium base group. In other embodiments, the products of the invention may comprise quaternary ammonium bases having at least about 2.5% total quaternary molecules containing more than one quaternary ammonium base group, or having at least about 5% of the total quaternary ammonium molecule containing more than one quaternary ammonium base group, or having at least about 10% of the total quaternary ammonium molecule containing more than one quaternary ammonium base group, or having at least about 15% of the total quaternary ammonium molecule containing more than one quaternary ammonium base group, or having at least about 20% of the total quaternary ammonium molecule containing more than one quaternary ammonium base group, or having at least about 25% of the total amount of quaternary molecules containing more than one quaternary ammonium base group, or having at least about 30% of the total amount of quaternary molecules containing more than one quaternary ammonium base group, or having at least about 35% of the total quaternary ammonium molecule containing more than one quaternary ammonium base group, or having at least about 40% of the total quaternary ammonium molecule containing more than one quaternary ammonium base group.

The quaternary ammonium base solutions of the present invention can be used in a variety of applications. Thus, in a second aspect, there is provided a composition for removing chemical residues from a metal or dielectric surface comprising a quaternary ammonium base solution of the invention. In some embodiments, the composition may comprise at least about 0.1 wt.%, or at least about 0.5 wt.%, or at least about 1 wt.%, or at least about 2 wt.%, or at least about 5 wt.%, or at least about 7 wt.%, or at least about 10 wt.% of the quaternary ammonium base solution of the present invention, wherein the wt.% is based on the total weight of the composition. In other embodiments, the composition may comprise less than about 20 wt.%, or less than about 15 wt.%, or less than about 10 wt.% of the quaternary ammonium base solution of the present invention, wherein the wt.% is based on the total weight of the composition.

In some embodiments, the composition may be substantially free of choline hydroxide, tetramethylammonium hydroxide, or both. In other embodiments, the composition may be substantially free of at least one or all of the following etchants.

In addition to the quaternary ammonium base solutions of the present invention, the compositions can further comprise solvents, chelating agents, oxidizing agents, metal corrosion inhibitors, etchants, low dielectric constant passivating agents, silicon-containing compounds, surfactants, and combinations thereof.

The solvent may include, but is not limited to, water, at least one water miscible organic solvent, or a combination thereof. For example, the solvent may include at least one selected from the group consisting of: water, methanol, ethanol, isopropanol, butanol, pentanol, hexanol, 2-ethyl-1-hexanol, heptanol, octanol, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, butylene carbonate, ethylene carbonate, propylene carbonate, butyrolactone, butyrolactam, choline bicarbonate, dipropylene glycol, dimethyl sulfoxide, sulfolane, tetrahydrofuran, tetrahydrofurfuryl alcohol (THFA), 1, 2-butanediol, 1, 4-butanediol, tetramethylurea, N' -dimethylimidazolidinone (dimethylethyleneurea), diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether (DPGME), Tripropylene glycol methyl ether (TPGME), dipropylene glycol dimethyl ether, dipropylene glycol ethyl ether, propylene glycol N-propyl ether, dipropylene glycol N-propyl ether (DPGPE), tripropylene glycol N-propyl ether, propylene glycol N-butyl ether, dipropylene glycol N-butyl ether, tripropylene glycol N-butyl ether, propylene glycol phenyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, 2, 3-dihydrodecafluoropentane, ethyl perfluorobutyl ether, methyl perfluorobutyl ether, alkyl carbonate, 4-methyl-2-pentanol, N-methylpyrrolidone (NMP), hexamethylphosphoramide, N' -Dimethylacetamide (DMAC), N-Dimethylformamide (DMF), and combinations thereof. In some embodiments, the solvent comprises water, and in other embodiments, deionized water. The solvent may be present in an amount of about 20 wt% to about 99.9 wt%, or about 30 wt% to about 98 wt%, or even about 50 wt% to about 95 wt%, wherein the wt% is based on the total weight of the composition.

The chelating agent may include, but is not limited to, β -diketonate compounds such as acetylacetonates, 1,1, 1-trifluoro-2, 4-pentanedione, and 1,1,1,5,5, 5-hexafluoro-2, 4-pentanedione; amines and amino acids such as glycine, serine, proline, leucine, alanine, asparagine, aspartic acid, glutamine, valine, and lysine; a polyprotic acid selected from: iminodiacetic acid (IDA), malonic acid, oxalic acid, succinic acid, boric acid, nitrilotriacetic acid, malic acid, citric acid, acetic acid, maleic acid, ethylenediaminetetraacetic acid (EDTA), EDTA-2NH₃(ethylenediaminetetraacetic acid diammonium salt), (1, 2-cyclohexylidenedinitrilo) tetraacetic acid (CDTA), diethylenetriaminepentaacetic acid (DTPA), 2-phosphonobutane-1, 2, 4-tricarboxylic acid (PBTCA), ethylenediaminedisuccinic acid, and propylenediaminetetraacetic acid; a phosphonic acid; phosphonic acid derivatives such as hydroxyethylidene diphosphonic acid (HEDP), 1-hydroxyethane-1, 1-diphosphonic acid, phosphinic acidNitro-tris (methylenephosphonic acid) (NTMP), aminotri (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) (EDTMPA); ethylene diamine; 2, 4-pentanedione; benzalkonium chloride; 1-imidazole; tetraglyme; pentamethyldiethylenetriamine (PMDETA); 1,3, 5-triazine-2, 4, 6-trithiol trisodium salt solution; 1,3, 5-triazine-2, 4, 6-trithiol triammonium salt solution; sodium diethyldithiocarbamate; disubstituted dithiocarbamates, and combinations thereof. The chelating agent may be present in an amount of about 0.01 wt% to about 1 wt%, wherein the wt% is based on the total weight of the composition.

The oxidizing agent may include, but is not limited to, hydrogen peroxide (H)₂O₂)、FeCl₃、FeF₃、Fe(NO₃)₃、Sr(NO₃)₂、CoF₃、MnF₃Potassium hydrogen persulfate preparation (2 KHSO)₅·KHSO₄·K₂SO₄) Periodic acid, iodic acid, vanadium (V) oxide, vanadium (IV, V) oxide, ammonium vanadate, polyatomic ammonium salts (e.g. ammonium peroxymonosulfate, ammonium chlorite (NH)₄ClO₂) Ammonium chlorate (NH)₄ClO₃) Ammonium iodate (NH)₄IO₃) Ammonium Nitrate (NH)₄NO₃) Ammonium perborate (NH)₄BO₃) Ammonium perchlorate (NH)₄ClO₄) Ammonium periodate (NH)₄IO₄) Ammonium persulfate ((NH)₄)₂S₂O₈) Ammonium hypochlorite (NH)₄ClO)), ammonium hypobromite, ammonium tungstate ((NH)₄)₁₀H₂(W₂O₇) Polyatomic sodium salt (e.g., sodium persulfate (Na)), sodium salt₂S₂O₈) Sodium hypochlorite (NaClO), sodium perborate, sodium hypobromite (NaBrO)), polyatomic potassium salt (e.g., potassium iodate (KIO)₃) Potassium permanganate (KMnO)₄) Potassium persulfate, nitric acid (HNO)₃) Potassium persulfate (K)₂S₂O₈) Potassium hypochlorite (KClO)), tetramethylammonium polyatomic salt (e.g., tetramethylammonium chlorite ((N (CH)₃)₄)ClO₂) Tetramethylammonium chlorate ((N (CH)₃)₄)ClO₃) Tetramethyl iodic acidAmmonium ((N (CH)₃)₄)IO₃) Tetramethylammonium perborate ((N (CH)₃)₄)BO₃) Tetramethylammonium perchlorate ((N (CH)₃)₄)ClO₄) Tetramethylammonium periodate ((N (CH)₃)₄)IO₄) Tetramethylammonium persulfate ((N (CH)₃)₄)S₂O₈) Tetrabutylammonium polyatomic salts (e.g., tetrabutylammonium peroxymonosulfate), monosulfate peroxide, ferric nitrate (Fe (NO)₃)₃) Urea hydrogen peroxide ((CO (NH)₂)₂)H₂O₂) Peracetic acid (CH)₃(CO) OOH), 1, 4-benzoquinone, toluquinone, dimethyl-1, 4-benzoquinone, chloranil, alloxan, N-methylmorpholine N-oxide, trimethylamine N-oxide, and combinations thereof. When the oxidizing agent is a salt, it may be hydrated or anhydrous. The oxidizing agent may be present in an amount of about 10 wt% to about 40 wt%, wherein the wt% is based on the total weight of the composition.

Metal corrosion inhibitors contemplated herein include, but are not limited to, 5-amino-1, 3, 4-thiadiazo-2-thiol (ATDT), 2-amino-5-ethyl-1, 3, 4-thiadiazo, Benzotriazole (BTA), 1,2, 4-Triazole (TAZ), tolyltriazole, 5-methyl-benzotriazole (mBTA), 5-phenyl-benzotriazole, 5-nitro-benzotriazole, benzotriazole carboxylic acid, 3-amino-5-mercapto-1, 2, 4-triazole, 1-amino-1, 2, 4-triazole, hydroxybenzotriazole, 2- (5-amino-pentyl) -benzotriazole, 1-amino-1, 2, 3-triazole, or mixtures thereof, 1-amino-5-methyl-1, 2, 3-triazole, 3-amino-1, 2, 4-triazole (3-ATA), 3-mercapto-1, 2, 4-triazole, 3-isopropyl-1, 2, 4-triazole, 5-phenylthiol-benzotriazole, halo-benzotriazole (halo ═ F, Cl, Br, or I), naphthotriazole, 2-Mercaptobenzimidazole (MBI), 2-mercaptobenzothiazole, 4-methyl-2-phenylimidazole, 2-mercaptothiazoline, 5-amino-1, 2, 4-triazole (5-ATA), Sodium Dodecyl Sulfate (SDS), 3-amino-5-mercapto-1, 2, 4-triazole, or mixtures thereof, 3, 5-diamino-1, 2, 4-triazole, pentylenetetrazole, 5-phenyl-1H-tetrazole, 5-benzyl-1H-tetrazole, 5-methyltetrazole, 5-mercapto-1-methyl-tetrazole, 1-phenyl-1H-tetrazole-5-thiol, 2-benzylpyridine, succinimide, 2, 4-diamino-6-methyl-1, 3, 5-triazine, thiazole, triazine, methyltetrazole, 1, 3-dimethyl-2-imidazolidinone, 1, 5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, diaminomethyltriazine, imidazolidinethione, 4-methyl-4H-1, 2, 4-triazole-3-thiol, 4-amino-4H-1, 2, 4-triazole, 3-amino-5-methylthio-1H-1, 2, 4-triazole, benzothiazole, imidazole, benzimidazole, 2-aminobenzimidazole, 1-methylimidazole, benzisoxazole (indiazole), adenine, succinimide, adenosine, carbazole, o-sulfonylbenzoylimine, uric acid, and benzoin oxime. Additional corrosion inhibitors include cationic quaternary salts such as benzalkonium chloride, benzyldimethyldodecylammonium chloride, tetradecyltrimethylammonium bromide, dodecyltrimethylammonium bromide, hexadecylpyridinium chloride, benzyldimethylbenzylammonium chloride, hexadecyltrimethylammonium p-toluenesulfonate, hexadecyltrimethylammonium hydroxide, 1-methyl-1 '-tetradecyl-4, 4' -bipyridinium dichloride, alkyltrimethylammonium bromide, aprylammonium hydrochloride, benzethonium hydroxide, benzethonium chloride, benzyldimethylhexadecylammonium chloride, benzyldimethyltetradecylammonium chloride, benzyldodecyldimethylammonium bromide, benzyldodecyldimethylammonium chloride, hexadecylpyridinium chloride, choline p-toluenesulfonate, dimethyldioctadecylammonium bromide, dodecylethyldimethylammonium bromide, dodecyldimethylammonium bromide, dodecyltrimethylammonium chloride, and mixtures thereof, Dodecyl trimethyl ammonium chloride, Decyl Trimethyl Ammonium Chloride (DTAC), ethylhexadecyl dimethyl ammonium bromide, Girard's reagent, hexadecyl (2-hydroxyethyl) dimethyl ammonium dihydrogen phosphate, hexadecyl pyridinium bromide, hexadecyl trimethyl ammonium chloride, methylbenzyl ammonium chloride, N ', N ' -polyoxyethylene (10) -N-tallow-1, 3-diaminopropane liquid, oxfenammonium bromide, tetraheptyl ammonium bromide, tetra (decyl) ammonium bromide, tonozo ammonium bromide, tridodecyl ammonium chloride, trimethyloctadecyl ammonium bromide, 1-methyl-3-N-octyl tetrafluoroborate imidazolium, 1-decyl-3-methyltetrafluoroborate imidazolium, 1-decyl-3-methylimidazolium chloride, Tridodecyl methyl ammonium bromide, dimethyl distearyl ammonium chloride, hexadecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide and hexamethonium chloride. Other corrosion inhibitors include nonionic surfactants such as polyethylene glycol, polypropylene glycol, ethylene oxide/propylene oxide block copolymers such as polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monolaurate, polyoxypropylene/polyoxyethylene block copolymers, anionic surfactants such as dodecylbenzene sulfonic acid, sodium dodecylbenzene sulfonate, dodecylphosphonic acid (DDPA), bis (2-ethylhexyl) phosphate, benzylphosphonic acid, diphenylphosphinic acid, 1, 2-ethylenediphosphonic acid, phenylphosphonic acid, cinnamic acid, and combinations thereof. The metal corrosion inhibitor may be present in an amount of about 0.01 wt.% to about 2 wt.%, wherein the wt.% is based on the total weight of the composition.

Etchants may include, but are not limited to, HF, ammonium fluoride, tetrafluoroboric acid, hexafluorosilicic acid, other compounds containing B-F or Si-F bonds, tetrabutylammonium tetrafluoroborate (TBA-BF)₄) Tetraalkylammonium fluoride (NR)_aR_bR_cR_dF) Strong bases such as tetraalkylammonium hydroxides (NR)_aR_bR_cR_dOH) wherein R_a、R_b、R_cAnd R_dMay be identical to or different from each other and may be chosen from hydrogen, linear or branched C₁-C₆Alkyl (e.g. methyl, ethyl, propyl, butyl, pentyl, hexyl), C₁-C₆Alkoxy groups (e.g., hydroxyethyl, hydroxypropyl), substituted or unsubstituted aryl groups (e.g., benzyl), weak bases, and combinations thereof. In some embodiments, the fluoride source comprises tetrafluoroboric acid, hexafluorosilicic acid, H₂ZrF₆、H₂TiF₆、HPF₆Ammonium fluoride, tetramethylammonium hydroxide, ammonium hexafluorosilicate, ammonium hexafluorotitanate, or a combination of ammonium fluoride and tetramethylammonium fluoride. Alternatively or additionally to the fluoride source, the etchant may include a strong base such as tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), benzyltrimethylammonium hydroxide (BTMAH), potassium hydroxide, ammonium hydroxide, benzyltriethylammonium hydroxide (BTEAH), tetrabutylphosphonium hydroxide (TBPH), (2-hydroxyethyl) trimethylammonium hydroxide (choline hydroxide), (2-hydroxyethyl) triethylammonium hydroxidePropyl ammonium hydroxide, (1-hydroxypropyl) trimethyl ammonium hydroxide, ethyl trimethyl ammonium hydroxide, diethyl dimethyl ammonium hydroxide (DEDMAH), tris (2-hydroxyethyl) methyl ammonium hydroxide (THEMA), 1,3, 3-Tetramethylguanidine (TMG), potassium hydroxide, guanidine carbonate, arginine, and combinations thereof. If choline hydroxide is used, it is known to those skilled in the art that commercial products often contain small amounts of stabilizers to minimize the degradation of choline hydroxide to undesirable by-products. Choline hydroxide stabilizers are known in the art and include, but are not limited to, formaldehyde, hydroxylamine, sulfites, and hydrides. Contemplated weak bases include, but are not limited to, ammonium hydroxide, Monoethanolamine (MEA), Diethanolamine (DEA), Triethanolamine (TEA), ethylenediamine, cysteine, and combinations thereof. The additional etchant may be present in an amount of about 0.01 wt% to about 15 wt%, wherein the wt% is based on the total weight of the composition.

Low dielectric constant passivating agents may include, but are not limited to, boric acid, borates such as ammonium pentaborate, sodium tetraborate, 3-hydroxy-2-naphthoic acid, malonic acid, iminodiacetic acid, and combinations thereof. The low dielectric constant passivating agent can be present in an amount of about 0.01 wt% to about 2 wt%, wherein the wt% is based on the total weight of the composition.

Silicon-containing compounds include, but are not limited to, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, Tetraethoxysilane (TEOS), N-propyltrimethoxysilane, N-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, and combinations thereof. Other silicon-containing compounds that may be used in place of or in addition to the above-described alkoxysilanes include ammonium hexafluorosilicate, sodium silicate, potassium silicate, tetramethylammonium silicate (TMAS), and combinations thereof. The silicon-containing compound may be present in an amount of about 0.001 wt% to about 2 wt%, wherein the wt% is based on the total weight of the composition.

The surfactant that may be added to the aqueous composition may be a fluorinated anionic surfactant that is antioxidant. Contemplated anionic surfactants include, but are not limited to, fluorosurfactants such asUR andFS-62(DuPont Canada Inc.), and ammonium fluoroalkyl sulfonates such as Novec^TM4300(3M Company)。

It will be appreciated that it is common practice to make the composition in a concentrated form, diluted prior to use. For example, the composition may be manufactured in a more concentrated form, and thereafter diluted with at least one solvent prior to and/or during use. The dilution ratio may be from about 0.1 part diluent to 1 part composition concentrate to about 100 parts diluent to 1 part composition concentrate. It is further understood that the concentrated form may be substantially free of oxidizing agent, and that the oxidizing agent may be introduced into the concentrate or diluted composition prior to and/or during use.

The above compositions can be readily formulated by simply adding the components and mixing to homogeneous conditions. In addition, the compositions can be readily formulated as single-pack formulations or as multi-part formulations that are mixed at the time of use or prior to use. The individual parts of the multi-part formulation may be mixed at the tool or in a mixing area/range such as an in-line mixer or in a reservoir upstream of the tool. It is contemplated that the different parts of the multi-part formulation may contain any combination of ingredients/components that when mixed together form the desired composition. The concentrations of the ingredients may vary widely, i.e., be more dilute or more concentrated, in particular compositions, and it will be understood that the compositions may vary and optionally comprise, consist of, or consist essentially of any combination of ingredients in accordance with the present invention.

According to a third aspect, the present invention relates to a method of removing a chemical residue from a metal or dielectric surface by contacting the metal or dielectric surface with the composition of the second aspect. The composition may be applied to the metal or dielectric surface in any suitable manner, such as by spraying the composition onto the surface, by dipping (in a static or dynamic volume of the composition) the surface, by contacting the surface with another material, such as a pad or fibrous absorbent applicator element, onto which the composition has been absorbed, by contacting the surface with a circulating composition, or by any other suitable means, manner or technique whereby the composition comes into removable contact with the surface. The composition may be contacted with the surface at a temperature of from about 20 ℃ to about 100 ℃, or from about 30 ℃ to about 70 ℃ for a sufficient time of from about 0.3 minutes to about 60 minutes, or from about 0.5 minutes to about 30 minutes. Such contact times and temperatures are exemplary and any other suitable time and temperature conditions effective to at least partially remove chemical residues from the surface may be used.

Examples

Example 1: quaternary ammonium base Synthesis procedure

The autoclave was charged with 3.50 lbs of N, N, N ', N' -tetramethylethylenediamine, followed by 8.07 lbs of deionized water. After purging the contents with nitrogen, 2.72 pounds of ethylene oxide were added at a rate to maintain the reaction temperature below 40 ℃. The reaction was allowed to continue for 1 hour, then purged with nitrogen to remove unreacted ethylene oxide. Titration indicated that about 55% of the amine nitrogens were quaternized.

Example 2: quaternary ammonium base Synthesis procedure

In a manner similar to example 1, 5.00 pounds of pentamethyldiethylenetriamine ("PMDETA") were reacted with 3.89 pounds of ethylene oxide in the presence of 11.52 pounds of deionized water at a maximum temperature of 45 ℃. Titration indicated about 61% of the amine nitrogen, or 1.9 nitrogen atoms/molecule, was quaternized. The NMR spectrum indicated that quaternary nitrogen was formed on the nitrogen with two methyl groups in the same molecule, not on the central nitrogen of PMDETA. An excess of two moles/mole of ethylene oxide of PMDETA is chained to a limited extent on the hydroxyethyl groups on the diquat terminal (diquat terminal).

Examples 3A and 3B: quaternary ammonium base Synthesis procedure

3A: in a manner similar to example 1, 9.50 pounds of N, N, N ', N' -tetrakis (2-hydroxyethyl) ethylenediamine was reacted with 3.61 pounds of ethylene oxide in the presence of 10.81 pounds of deionized water at a maximum temperature of 39 ℃. Titration indicated that about 50% of the amine nitrogens were quaternized.

3B: in a manner similar to example 1, 9.03 pounds of N, N' -tetrakis (2-hydroxyethyl) ethylenediamine was reacted with 8.42 pounds of ethylene oxide in the presence of 5.42 pounds of deionized water at a maximum temperature of 47 ℃. Titration showed that about 52% of the amine nitrogens were quaternized.

Example 4: quaternary ammonium base Synthesis procedure

In a manner similar to example 1, 2.40 lbs of bis (2-dimethylaminoethyl) ether was reacted with 1.35 lbs of ethylene oxide in the presence of 5.00 lbs of deionized water at a maximum temperature of 40 ℃. Titration showed that about 85% of the amine nitrogens were quaternized.

Copper and aluminum substrates were exposed for 3 days on examples 1,2, 3A and 3B and an indication of their reactivity was compared to prior art quaternary ammonium bases, as shown below.

^aTris (2-hydroxyethyl) methylammonium hydroxide,^bcholine hydroxide

While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.