JP2009141311A - Fluoride-free photoresist stripper or residue removal cleaning composition containing oligomeric or polymeric material of alpha-hydroxycarbonyl compound / amine or ammonia reaction conjugate - Google Patents

Abstract

A cleaning formulation useful for cleaning microelectronic devices without significant metal corrosion and compatible with ILD.
(A) at least one “yellowing” or “browning” alpha-hydroxycarbonyl compound, which is an oligomeric or polymeric conjugate of an alpha-hydroxycarbonyl compound with an amine or ammonium compound, (b) A cleaning formulation based on a fluoride-free organic solvent comprising at least one free amine and (c) at least one organic solvent or at least one organic solvent and water is provided. Such a formulation comprises (d) at least one metal ion-free base in an amount sufficient to produce a final product having a pH of 7 or greater, preferably a pH of about 9.5 to about 10.8, and (e Other optional ingredients may also be included including :) polyhydric alcohols, (f) metal chelators, and (g) surfactants.
[Selection figure] None

Description

  The present invention relates to a composition useful for removing photoresist, contaminants, or plasma or etch residues from microelectronic devices, which provides good copper corrosion inhibition while maintaining cleaning efficiency. Or bring resistance. In particular, the present invention relates to an oligomeric or polymeric type material of an alpha-hydroxycarbonyl compound in the composition, in particular an oligomeric or polymeric type binding material of a “brown” or “yellowed” alpha-hydroxycarbonyl compound, and In particular, there is provided a fluoride-free cleaning composition based on organic or semi-aqueous solvents in which an oligomeric or polymeric binder of “brown” or “yellowing” monosaccharide is present. The present invention also provides methods for cleaning microelectronic substrates and devices using such compositions.

  A semiconductor device comprises coating an inorganic substrate with a photoresist; patterning a photoresist film by exposure and subsequent development; etching an exposed region of the inorganic substrate using the patterned photoresist film as a mask; It has been manufactured by steps of forming a fine circuit structure; and removing the patterned photoresist film from the inorganic substrate. Alternatively, after forming a fine circuit structure in the same manner as described above, the patterned photoresist film is ashed, and then the remaining resist residue is removed from the inorganic substrate.

  A number of alkali-based cleaning compositions have been proposed for cleaning photoresists and residues from such microelectronic devices. However, one significant problem faced in cleaning such microelectronic devices is the propensity for the cleaning composition to corrode metals, particularly copper, in such microelectronic devices. However, currently available strippers, which are usually alkaline strippers, lead to various types of metal corrosion such as corrosion whiskers, electrolytic corrosion, pitting, metal wire notches, which are at least partially It was observed that this was due to the reaction of the metal with an alkaline release agent.

  Past methods used to avoid this corrosion problem used an intermediate rinse with a non-alkaline organic solvent such as isopropyl alcohol. However, such methods are expensive and have undesirable safety, chemical hygiene and environmental impacts.

US Pat. No. 6,465,403 discloses an aqueous alkaline composition useful in the microelectronics industry for stripping or cleaning semiconductor wafer substrates by removing photoresist residues and other unwanted contaminants. Yes. The aqueous composition typically comprises (a) an amount of one or more metal ion-free bases sufficient to provide a pH of about 10-13; (b) about 0.01 wt% to about about 5 wt% water-soluble metal ion free silicate of (as% SiO ₂ notation); (c) from about 0.01% to about 10 wt% of one or more metal chelating agents and (d) Optionally, other ingredients are included.
US Pat. No. 6,465,403

However, none of the compositions disclosed in the prior art effectively removes all organic contaminants and metal-containing residues remaining after a typical etching process. Silicon-containing residues are particularly difficult to remove using these formulations. Accordingly, there is a need for a stripping composition that cleans semiconductor wafer substrates by removing inorganic and organic contaminants from such substrates without damaging the integrated circuit. Such compositions should not corrode the metal features that partially make up the integrated circuit, and should avoid expense and deleterious effects due to intermediate rinses. Therefore,
(1) Compatible with essentially all metals (Al, Cu, Mo, etc.) used in semiconductor devices;
(2) No need for intermediate rinsing;
(3) good for cleaning of Si-rich residues; and
(4) essentially does not damage the ILD,
There is a demand for cleaning agents.

According to the present invention, (a) at least one “brown” or “yellowing” alpha-hydroxycarbonyl conjugate (b) which is an oligomeric or polymeric conjugate of an alpha-hydroxycarbonyl compound with an amine or ammonium compound. Fluoride-free microelectronic cleaning composition based on an organic or semi-aqueous solvent comprising at least one amine and (c) at least one organic solvent or at least one organic solvent and water Or a formulation is provided. The alpha-hydroxycarbonyl compound is of the general formula R ¹ CH (OH) COR ^{2 wherein} R ¹ and R ² are independently selected from H, an aliphatic group, or a cyclic group; An aliphatic or cyclic group may contain one or more substituents. Such substituents include aromatic groups, heteroaromatic groups, hydroxyl groups (—OH groups), ether groups (—C—O—C), amide groups (—C (O) NH). A sulfoxide group (—C—S (O) —C), an amine (—NR ³ R ⁴ , wherein R ³ and R ⁴ are H or alkyl having 1 to 10 carbon atoms), and a ketone group (— Groups selected from C (O)) are included, but not limited to. In the alpha-hydroxycarbonyl compound of the general formula R ¹ CH (OH) COR ² , R ¹ and R ² are preferably H, CH ₃ and (CH ₂ ) _n CH ₃ (n is 0 to 20, preferably 1). To 10 and more preferably an integer of 1 to 6. Suitable alpha - Examples of hydroxycarbonyl compounds, 1-hydroxy-2-propanone _{(CH 3 COCH 2 OH) CAS} # 119-09-6,1,3- dihydroxyacetone _{(HOCH 2 COCH 2 OH) CAS} # 62147- 49-3 and, in particular, monosaccharides that conform to the above general structure, including but not limited to glucose, fructose or galactose. The reaction of amines with alpha-hydroxycarbonyl compounds is known to proceed first by nucleophilic addition of the amine at the carbon of the carbonyl and then continue via the Maillard reaction (Yaylayan, VA; Harty-Majors, S Ismail, AA; J. Agric. Food Chem. 1999, 47, 2335-2340). The Maillard reaction is actually a complex continuous reaction, details can be found in Dills, W. L; Am. J. Clin. Nutr. 1993, 58, 779S-787S.

  The pH of the composition may be any suitable pH from acidic pH to basic pH. In certain embodiments of the compositions of the present invention, the composition comprises (d) at least 1 in an amount sufficient to bring the final composition to pH 7 or above, preferably from about 9.5 to about 10.8. Certain metal ion-free bases may also be included. The compositions of the present invention may also include one or more (e) polyhydric alcohols, and (f) metal chelators, and (g) surfactants. The oligomer type or polymer type conjugate of the browned or yellowed alpha-hydroxycarbonyl compound used in the composition of the present invention is an oligomer type or polymer type conjugate having an absorption peak at about 300 to 330 nm, and its absorption peak. Starts at a wavelength of about 500 to 800 nm. The terms “yellowing” and “browning” are understood to include colors and shades that are a combination of brown and yellow, such as light and dark orange. These browned or yellowed oligomeric or polymeric conjugates can be formed by the known “Maillard reaction” —LC Maillard, Compt. Rend. 154, 66 (1912); Ann. Chim. 9, 5, 258 (1916). The yellowed conjugate, which is an oligomeric or polymeric conjugate of an alpha-hydroxycarbonyl compound with an amine or ammonium compound used in the composition of the present invention, has the same Maillard reaction, generally at a lower temperature or shorter reaction time. Or even by leaving the reactants together at room temperature for a suitable period of time. The browning conjugate which is an oligomeric or polymeric conjugate of an alpha-hydroxycarbonyl compound with an amine or ammonium compound used in the composition of the present invention has an absorption peak at about 300 to 330 nm, and the absorption peak is about The “yellowing” conjugate, which is an oligomeric or polymeric conjugate of the reaction product of an alpha-hydroxycarbonyl compound with an amine or ammonium compound, begins at a wavelength of 600 to 800 nm, and has an absorption peak at about 300 to 330 nm. However, the absorption peak starts at about 500 to 580 nm. These conjugates may be first formed and then added to the composition of the invention, or an alpha-hydroxycarbonyl compound that forms an oligomer in the composition, for example at a temperature of 70 ° C. or higher, and It may be produced by heating for a time sufficient to cause a Maillard-type reaction with an amine or ammonium compound.

  The cleaning composition of the present invention is contacted with the semiconductor device for a time and at a temperature sufficient to clean unwanted contaminants and / or residues from the substrate surface. The composition of the present invention provides enhanced corrosion resistance, particularly enhanced copper corrosion resistance, and improved cleaning efficiency.

  The cleaning composition of the present invention comprises (a) at least one “brown” or “yellowing” alpha-hydroxycarbonyl conjugate which is an oligomeric or polymeric conjugate of an alpha-hydroxycarbonyl compound with an amine or ammonium compound. And a fluoride-free cleaning formulation based on an organic or semi-aqueous solvent comprising (b) at least one amine and (c) at least one organic solvent or at least one organic solvent and water including. Such a formulation comprises (d) at least 1 in an amount sufficient to bring the final composition to a pH of 7 or higher, preferably from about 9.5 to about 10.8, if an alkaline cleaning composition is desired. Other, including, but not limited to, species-free bases of metal ions, and one or more (e) polyhydric alcohols, and (f) metal chelators, and (g) surfactants. Optional components may also be included.

  The “brown” and “yellowed” alpha-hydroxycarbonyl conjugates used in the compositions of the present invention have an absorption peak at about 300 to 330 nm, the absorption peak starting at a wavelength of about 500 to 800 nm. -An oligomeric or polymeric conjugate of a hydroxycarbonyl compound with an amine or ammonium compound. Such browned or yellowed oligomeric or polymeric conjugates are produced according to known methods such as the “Maillard reaction” described above. However, any suitable means for obtaining a “brown” alpha-hydroxycarbonyl conjugate can be used. Furthermore, such “brown” alpha-hydroxycarbonyl conjugates can be used, for example, in the form of dark molasses. The reaction of an alpha-hydroxycarbonyl compound with an amine or ammonia-containing compound is based on the reaction of 1 mole of alpha-hydroxycarbonyl compound with 1 mole of amine or ammonia compound, with respect to the amine or ammonia compound of the alpha-hydroxycarbonyl compound. Stoichiometric ratios can be performed from about 1: 1 to about 16: 1. However, it is preferred that the ratio be 1: 1 since the lower presence of amine or ammonia compounds that react with the alpha-hydroxycarbonyl compound results in a reduction of the copper corrosion inhibition ability of the reaction product. The reaction can be conducted over a wide range of times and temperatures, but at room temperature for a few hours or a day or more, or the alpha-hydroxycarbonyl compound with the amine or ammonia compound at about 70 ° C. or above for about 15 minutes. Alternatively, the reaction is preferably carried out by heating for more, for example 3 hours or more. The resulting oligomeric or polymeric conjugate reaction product is a “brown” or “yellowing” product, ie having an absorption peak at about 300-330 nm, the peak starting at about 500-800 nm Any suitable time and temperature may be used. In general, the browning and yellowing alpha-hydroxycarbonyl conjugates preferably used in the present invention are characterized by having a low band gap of about 0.5 eV or less.

Browned or yellowed alpha-hydroxycarbonyl conjugates may be obtained from the reaction of any suitable alpha-hydroxycarbonyl compound with an amine or ammonia compound. Suitable alpha-hydroxycarbonyl compounds include 1-hydroxy-2-propanone, CH ₃ COCH ₂ OH and 1,3-dihydroxyacetone, HOCH ₂ COCH ₂ OH, and arabinose, lyxose, ribose, deoxyribose, xylose, ribulose , Xylulose, allose, altrose, galactose, glucose, gulose, idose, mannose, fructose, psicose, sorbose, tagatose, mannoheptulose, sedoheptulose, octulose, 2-keto-3-deoxy-manno-octonate and siarose All monosaccharides are included, but are not limited to these. Particularly preferred is fructose. Disaccharides cannot be used in the present invention.

Any suitable amine or ammonia-containing compound can be reacted with an alpha-hydroxycarbonyl compound of the present invention to produce an oligomeric or polymeric conjugate of the browned or yellowed alpha-hydroxycarbonyl compound with an amine or ammonium compound. . Suitable amines include amines, diamines, triamines, alkanolamines, amino acids, especially primary and secondary amines and alkanolamines. Particularly useful are alkanolamines of the formula NH ₂ (CH ₂ ) nOH, where n is 1 to about 10, preferably 1 to about 4, especially 2. Ammonia is suitable as well as the above amines. Suitable amine compounds include, but are not limited to, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diethylenetriamine, aminoacetic acid. Particularly preferred is monoethanolamine. Preferred browned alpha-hydroxycarbonyl compounds are obtained from the reaction of fructose with monoethanolamine.

The composition also contains at least one amine component. The amine component may be a free excess amine left in the product resulting from a reaction that forms an oligomeric or polymeric conjugate of a browned or yellowed alpha-hydroxycarbonyl compound, or is browned or yellowed It may be an amine added to the composition in addition to the oligomeric or polymeric conjugate of the alpha-hydroxycarbonyl compound. Suitable amines include amines, diamines, triamines, alkanolamines, amino acids, especially primary and secondary amines and alkanolamines. Particularly useful are alkanolamines of the formula NH ₂ (CH ₂ ) nOH, where n is 1 to about 10, preferably 1 to about 4, especially 2. Ammonia is suitable as well as the above amines. Suitable amine compounds include, but are not limited to, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diethylenetriamine, aminoacetic acid. Particularly preferred is monoethanolamine.

The formulations of the present invention can be based on organic solvents or can be based on organic solvents plus water. That is, the formulation will contain at least one polar water-miscible organic solvent. Any suitable polar water-miscible organic solvent can be used in the formulation. Such suitable polar water-miscible organic solvents include, but are not limited to, amides, sulfones, sulfoxides, saturated alcohols, glycol ethers, and the like. Such organic polar solvents include sulfolane (tetrahydrothiophene-1,1-dioxide), 3-methylsulfolane, n-propylsulfone, dimethylsulfoxide (DMSO), methylsulfone, n-butylsulfone, 3-methylsulfolane, etc. Organic polar solvents of 1- (2-hydroxyethyl) -2-pyrrolidone (HEP), dimethylpiperidone (DMPD), N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc) and dimethylformamide (DMF) Although alkylene glycol mono- and dialkyl ethers and mixtures thereof such as ethylene glycol monoethyl ether (Carbitol® ^(TM)) include, but are not limited to. Particularly preferred as organic polar solvents are N-methylpyrrolidone, sulfolane, ethylene glycol monoethyl ether, DMSO and mixtures thereof. The organic solvent is a water miscible organic solvent and is generally present in an amount of about 35 to about 98% by weight, preferably about 40 to about 90% by weight, even more preferably about 45 to about 85% by weight. To do. Water may also be present in the composition, optionally in addition to at least one organic solvent. If water is present with the organic solvent, it will generally be present in the composition of the present invention in an amount greater than about 0 to about 20% by weight, preferably from about 3 to about 15% by weight, more preferably from about 5 to about 5%. It will be present in an amount of about 10% by weight.

  The “brown” or “yellowed” oligomeric or polymeric alpha-hydroxycarbonyl compound is generally about 0.1 to about 20% by weight, preferably about 1 to about 1%, in the cleaning composition of the present invention. It is present in an amount of about 10% by weight, more preferably about 3 to about 7% by weight. The amine is present in the composition in an amount of from about 1% to about 15%, preferably from about 3% to about 12%, more preferably from about 5 to about 10%. The organic solvent is a water miscible organic solvent and is generally present in an amount of about 35 to about 98% by weight, preferably about 40 to about 90% by weight, even more preferably about 45 to about 85% by weight. To do. If water is present with the organic solvent, it is generally from about 0 to about 20% by weight, preferably from about 3 to about 15% by weight, more preferably from about 5 to about 10%, in the composition of the present invention. Present in an amount by weight. All percentages are based on the total weight of the cleaning composition.

  The pH of the cleaning composition is alkaline or acidic, but is preferably 7 or higher, preferably from about pH 7 to about 10.8, more preferably from about 9.5 to about 10.8. If necessary to adjust the pH of the composition, a metal ion-free base can optionally be added to the cleaning composition. Any suitable metal ion-free base can be used. Suitable metal ion-free bases that can be used in the present cleaning compositions include tetraalkylammonium hydroxides (hydroxy- and alkoxy-containing, generally having 1 to 4 carbon atoms in the alkyl or alkoxy group). There may be quaternary ammonium hydroxides (including alkyl groups). Most preferred among these alkaline substances are tetramethylammonium hydroxide and trimethyl-2-hydroxyethylammonium hydroxide (choline). Examples of other quaternary ammonium hydroxides that can be used include: trimethyl-3-hydroxypropylammonium hydroxide, trimethyl-3-hydroxybutylammonium hydroxide, trimethyl-4-hydroxybutylammonium hydroxide, triethyl-2-hydroxy Ethylammonium hydroxide, tripropyl-2-hydroxyethylammonium hydroxide, tributyl-2-hydroxyethylammonium hydroxide, dimethylethyl-2-hydroxyethylammonium hydroxide, dimethyldi (2-hydroxyethyl) ammonium hydroxide, monomethyltri (2-hydroxyethyl) ammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, Rabutylammonium hydroxide, monomethyl-triethylammonium hydroxide, monomethyltripropylammonium hydroxide, monomethyltributylammonium hydroxide, monoethyltrimethylammonium hydroxide, monoethyltributylammonium hydroxide, dimethyldiethylammonium hydroxide, dimethyldibutylammonium hydroxide And mixtures thereof. Other bases that function in the present invention include ammonium hydroxide, organic amines, especially alkanolamines such as 2-aminoethanol, 1-amino-2-propanol, 1-amino-3-propanol, 2- (2-amino Ethoxy) ethanol, 2- (2-aminoethylamino) ethanol, 2- (2-aminoethylamino) ethylamine, and other strong organic bases such as guanidine, 1,3-pentanediamine, 4-aminomethyl -1,8-octanediamine, aminoethylpiperazine, 4- (3-aminopropyl) morpholine, 1,2-diaminocyclohexane, tris (2-aminoethyl) amine, 2-methyl-1,5-pentanediamine and hydroxyl Amines are included. The amount of such base used in the composition is that amount which provides the desired pH to the composition, generally from about 0 to about 15% by weight, preferably from about 0.5 to about 5% by weight, And more preferably in an amount of about 1 to about 2% by weight.

  The formulations of the present invention can optionally also contain any suitable polyhydric alcohol component. Such suitable polyhydric alcohols include, but are not limited to, sorbitol, xylitol, glycerol, ethylene glycol, butane-1,4-diol. Preferably, the polyhydric alcohol used is preferably D-sorbitol. The amount of polyhydric alcohol present in the composition, if present, is greater than about 0 to about 10% by weight, preferably greater than about 0 to about 7% by weight, more preferably greater than about 0 to about 5%. It can be in the range of up to% by weight.

  The formulations of the present invention may also contain optional ingredients that are not detrimental to the effectiveness of the cleaning composition, such as surfactants. The compositions of the present invention may also contain any suitable water-soluble, amphoteric, nonionic, cationic or anionic surfactant. The addition of a surfactant reduces the surface tension of the formulation and improves the wetting of the surface to be cleaned, thus improving the cleaning action of the composition. Amphoteric surfactants useful in the compositions of the present invention include betaines and sulfobetaines such as alkylbetaines, amidoalkylbetaines, alkylsulfobetaines and amidoalkylsulfobetaines; ampho glycinates, amphopropionates, amphodiglycines Amino carboxylic acid derivatives such as sinate and amphodipropionate; iminodiacids such as alkoxyalkyliminodibasic acids; amine oxides such as alkylamine oxides and alkylamidoalkylamine oxides; fluoroalkylsulfonates And fluorinated alkyl amphoteric; and mixtures thereof. Preferably, the amphoteric surfactant is cocoamide propyl betaine, cocoamidopropyl dimethyl betaine, cocoamidopropyl hydroxysultane (sultaine), capryloam hodipropionate, cocoamide dipropionate, cocoamuhopropionate, Cocoafohydroxyethyl propionate, isodecyloxypropyliminodipropionic acid, lauryliminodipropionate, cocoamidopropylamine oxide and cocoamine oxide and fluorinated alkyl amphoteric substances. Nonionic surfactants useful in the compositions of the present invention include acetylenediol, ethoxylated acetylenic diol, fluorinated alkyl alkoxylates, fluorinated alkyl esters, fluorinated polyoxyethylene alkanols, fatty acid esters of polyhydric alcohols, Polyoxyethylene monoalkyl ethers, polyoxyethylene diols, siloxane type surfactants, and alkylene glycol monoalkyl ethers are included. Preferably, the nonionic surfactant is acetylenic diol or ethoxylated acetylenic diol. Anionic surfactants useful in the compositions of the present invention include carboxylate, N-acyl sarcosinate, sulfonate, sulfate, and mono and diesters of orthophosphoric acid such as decyl phosphate. . Preferably, the anionic surfactant is a metal-free surfactant. Cationic surfactants useful in the compositions of the present invention include amine ethoxylates, dialkyl dimethyl ammonium salts, dialkyl morpholinum salts, alkyl benzyl dimethyl ammonium salts, alkyl trimethyl ammonium salts, and alkyl pyridinium salts. included. Preferably, the cationic surfactant is a halogen-free surfactant. Surfactants, when used in the compositions of the present invention, are generally present in an amount greater than about 0 to about 1% by weight, preferably from about 0.05 to about 0.2% by weight.

  The formulations of the present invention can also be formulated with a suitable one or more metal chelating agents to increase the ability of the formulation to retain the metal in solution and enhance dissolution of metallic residues on the wafer substrate. Typical examples of metal chelators useful for this purpose are the following organic acids and their isomers and salts: (ethylenedinitrilo) tetraacetic acid (EDTA), butylenediaminetetraacetic acid, cyclohexane-1, 2-diaminetetraacetic acid (CyDTA), diethylenetriaminepentaacetic acid (DETPA), ethylenediaminetetrapropionic acid, (hydroxyethyl) ethylenediaminetriacetic acid (HEDTA), N, N, N ′, N′-ethylenediaminetetra (methylenephosphonic) acid ( EDTMP), triethylenetetraminehexaacetic acid (TTHA), 1,3-diamino-2-hydroxypropane-N, N, N ′, N′-tetraacetic acid (DHPTA), methyliminodiacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid ( NTA), citric acid, tartaric acid, gum Con acid, saccharic acid, glyceric acid, oxalic acid, phthalic acid, maleic acid, mandelic acid, malonic acid, lactic acid, salicylic acid, catechol, gallic acid, propyl gallate, pyrogallol, 8-hydroxyquinoline, and cysteine. Preferred as the metal chelating agent is an aminocarboxylic acid such as cyclohexane-1,2-diaminetetraacetic acid (CyDTA). The at least one metal chelator may be present in an amount greater than about 0 to about 1% by weight, preferably from about 0.05 to about 0.2% by weight.

  The cleaning composition of the present invention contacts a microelectronic device with the cleaning composition of the present invention for a suitable time and at a suitable temperature to remove photoresist or plasma or etch residues from the microelectronic device. Is used to clean photoresist or plasma or etch residues from microelectronic devices.

  The present invention is illustrated and described by the following illustrative examples, but is not limited thereto.

The following are examples of “brown” or “yellowed” alpha-hydroxycarbonyl-linked oligomers or polymers useful in the compositions of the present invention.
Browning component 1: 100 g of a 50:50 (by weight) mixture of fructose and water was reacted with 50 g of monoethanolamine at a temperature of 70 ° C. for about 3 hours.
Browning component 2: 100 g of a 50:50 (by weight) mixture of fructose and water was reacted with 16 g of monoethanolamine at a temperature of 70 ° C. for about 3 hours.
Browning component 3: 100 g of a 50:50 (by weight) mixture of fructose and water was reacted with 5 g of monoethanolamine at a temperature of 70 ° C. for about 3 hours.
Browning component 4: 100 g of a 50:50 (by weight) mixture of fructose and water was reacted with 1 g of monoethanolamine at a temperature of 70 ° C. for about 3 hours.
Browning component 5: 50 g of fructose was dissolved in 10 g of water, the mixture was heated to 80 ° C., and then 20.8 g of monoisopropanolamine was added. The solution was heated by an exothermic reaction and released water under boiling.
Browning component 6: 50 g of fructose was dissolved in 10 g of water, the mixture was heated to 80 ° C. and then 29.2 g of diethanolamine was added. The solution was heated by an exothermic reaction and released water under boiling.
Browning component 7: 50 g of fructose was dissolved in 10 g of water, the mixture was heated to 80 ° C. and then 41.9 g of triethanolamine was added. The solution was heated by an exothermic reaction and released water under boiling.
Browning component 8: 50 g of fructose was dissolved in 10 g of water, the mixture was heated to 80 ° C., and then 26.5 g of diethylenetriamine was added. The solution was heated by an exothermic reaction and released water under boiling.
Browning component 9: 50 g of fructose was dissolved in 10 g of water, the mixture was heated to 80 ° C., and then 20.8 g of aminoacetic acid (glycine) was added. The solution was heated by an exothermic reaction and released water under boiling.
Browning component 10: 50 g glucose was dissolved in 10 g water, the mixture was heated to 80 ° C. and then 17.0 g monoethanolamine was added. The solution was heated by an exothermic reaction and released water under boiling.
Browning component 11: 50 g of galactose was dissolved in 10 g of water, the mixture was heated to 80 ° C., and then 20.8 g of monoethanolamine was added. The solution was heated by an exothermic reaction and released water under boiling.
Browning component 12: 1 50 g of a 50:50 mixture of 1-hydroxy-2-propanone and water was reacted with 8 g of monoethanolamine at 70 ° C. for about 1 hour.
Browning component 13: 50 g of a 50:50 mixture of dihydroxyacetone and water was reacted with 8 g of monoethanolamine at 70 ° C. for about 1 hour.
Yellowing component 14: 100 g of a 50:50 mixture of fructose and water was reacted with 16 g of monoethanolamine at a temperature of 70 ° C. for about 3 hours and then allowed to stand at room temperature of about 20 ° C. overnight.
Yellowing component 15: 100 g of a 50:50 mixture of fructose and water was reacted with 50 g of monoethanolamine overnight at a temperature of 70 ° C. and then allowed to stand at room temperature of about 20 ° C. for 1 week.

  Further oligomeric components of the present invention are those described in compositions A to T in Table 1. The oligomeric component of these compositions is a reaction in which fructose and monoethanolamine are in the components in the cleaning composition, and the cleaning composition heated to a temperature of 70 ° C. is heated for 15 minutes to form a conjugate. Each was prepared in situ.

  For the compositions of the present invention and comparative compositions, copper corrosion inhibition was tested in the following manner. The copper coated wafer was placed in a 150 ml beaker containing the test composition at about 70 ° C. The composition was stirred at about 200 rpm for 15 minutes with the Cu surface away from the stirrer bar.

The compositions and test results are presented in Table 1.
Table 1

Table 1 (continued)

Table 1 (continued)

Several compounds were tested to confirm that an alpha-hydroxycarbonyl compound was required in the reaction with amines to provide adequate copper corrosion inhibition. Different types of carbonyl compounds were tested; ketones (acetone, H ₃ CCOCH ₃ ), diketones (2,3-pentanedione, H ₃ CCOCOCH ₂ CH ₃ ), aldehydes (formaldehyde, HCOH) and two different alpha-hydroxys Carbonyl compounds (1-hydroxy-2-propanone, CH ₃ COCH ₂ OH, and 1,3-dihydroxyacetone, HOCH ₂ COCH ₂ OH). From Table 2, it can be seen that both acetone and formaldehyde do not show any benefit when used in combination with monoethanolamine. In contrast, using the alpha-hydroxycarbonyl compounds 1-hydroxy-2-propanone and 1,3-dihydroxyacetone, the Cu etch rate is 20 times lower than that of monoethanolamine. It has also been shown that reasonable corrosion inhibition can be obtained by using a diketone, 2,3-pentanedione. This is reasonably explained by the well-known keto-enol tautomerism phenomenon in organic chemistry that results in chemical equilibrium concentrations for alpha-hydroxycarbonyl compounds (Jones, M; Organic Chemistry 1997, WW Norton & Company, Inc., 500 Fifth Avenue, New York, NY 10110). Other data clearly showing the need for alpha-hydroxycarbonyl compounds are the results using 4-hydroxy-4-methyl 2-pentanone, a beta-hydroxycarbonyl compound. This compound did not show improved copper compatibility. This strongly indicates the need for alpha-hydroxycarbonyl compounds. For each test composition, the copper etch rate (７０ / min) at 70 ° C. in DMSO, NMP or mixtures thereof is listed in Table 2. All compositions utilized monoethanolamine as the amine and reacted with the listed compounds at 70 ° C. for about 3 hours.

Table 2

  The composition of the present invention is similar to microelectronic cleaning compositions containing known fluorides, but without the significant copper corrosion encountered with the use of cleaning compositions containing known fluorides. Cleaning resist or plasma or etch residues from microelectronic devices is provided. A preferred cleaning composition of the present invention comprises a composition of fructose and monoethanolamine oligomer, free monoethanolamine, N-methylpyrrolidinone, water, sorbitol and carbitol, as in composition M in Table 1. Including.

  Although the invention has been described with reference to particular embodiments, it will be understood that changes, modifications and variations can be made without departing from the spirit and scope of the inventive concepts disclosed herein. Accordingly, all such changes, modifications, and variations are intended to be included within the spirit and scope of the appended claims.

Claims (23)

  (A) an oligomeric or polymeric conjugate of at least one “brown” or “yellowed” alpha-hydroxycarbonyl compound with an amine or ammonium compound, (b) at least one amine, and (c) A fluoride-free microelectronic cleaning composition comprising at least one water-miscible organic solvent or at least one water-miscible organic solvent and water. The alpha-hydroxycarbonyl compound is a compound of the formula R ¹ CH (OH) COR ² , wherein R ¹ and R ² are independently selected from the group consisting of aliphatic or cyclic groups. Item 2. The composition according to Item 1. The alpha-hydroxycarbonyl compound is a group selected from the group consisting of formula R ¹ CH (OH) COR ² , wherein R ¹ and R ² are H, CH ₃ , (CH ₂ ) nCH ₃ , n Is an integer of 0 to 20, and an oligomeric or polymeric conjugate of an alpha-hydroxycarbonyl compound with an amine or ammonium compound has an absorption peak of about 300 to 330 nm, The composition of claim 2, which begins at about 500 to 800 nm.   Alpha-hydroxycarbonyl compounds are arabinose, lyxose, ribose, deoxyribose, xylose, ribulose, xylulose, allose, altrose, galactose, glucose, growth, idose, mannose, fructose, psicose, sorbose, tagatose, mannoheptulose, 4. The composition of claim 3, which is a monosaccharide selected from the group consisting of cedoheptulose, octulose, 2-keto-3-deoxy-manno-octonate and siarose.   The composition according to claim 1, wherein the oligomeric or polymeric conjugate of an alpha-hydroxycarbonyl compound with an amine or ammonium compound is a conjugate of fructose and monoethanolamine.   6. The composition of claim 5, wherein the fructose and monoethanolamine oligomeric or polymeric conjugate has an absorbance peak of about 300 to 330 nm, the absorbance peak starting at about 500 to 800 nm.   The composition of claim 6 wherein the conjugate is prepared by heating fructose and monoethanolamine together at a temperature of at least 70 ° C for at least 3 hours.   The composition according to claim 7, wherein the composition further comprises a polyhydric alcohol.   The composition according to claim 8, wherein the polyhydric alcohol is sorbitol.   The composition of claim 1, wherein the pH of the composition is from about pH 7 to about pH 10.8.   0.1 to about 20% by weight oligomeric or polymeric conjugate component, about 1 to about 15% by weight amine component, and about 35 to about 98% by weight organic solvent or organic solvent and water. Item 2. The composition according to Item 1.   The composition of claim 1, further comprising one or more components selected from the group consisting of a surfactant, a metal ion-free base, a polar water-miscible organic solvent, a polyhydric alcohol, and a metal chelator. object.   6. The composition of claim 5, further comprising one or more components selected from the group consisting of a surfactant, a metal ion-free base, a polyhydric alcohol, and a metal chelator.   The composition of claim 1 comprising an oligomer of fructose and monoethanolamine, free monoethanolamine, N-methylpyrrolidinone, water, sorbitol and carbitol.   The composition of claim 1, wherein the conjugate has a band gap of about 0.5 eV or less.   6. The composition of claim 5, wherein the browning conjugate has a band gap of about 0.5 eV or less.   A method of cleaning photoresist, contaminants or etching or ashing residues from a microelectronic substrate, the microelectronics substrate being sufficient to remove photoresist, contaminants or etching or ashing residues. Contacting the cleaning composition at a suitable time and temperature, the cleaning composition comprising: (a) an oligomer of at least one “brown” or “yellowed” alpha-hydroxycarbonyl compound with an amine or ammonium compound Type or polymer type conjugates, (b) at least one amine, and (c) at least one water-miscible organic solvent or at least one water-miscible organic solvent and water-free fluoride-containing micro A method, which is a cleaning composition for electronics. The alpha-hydroxycarbonyl compound is a compound of the formula R ¹ CH (OH) COR ² , wherein R ¹ and R ² are independently selected from the group consisting of aliphatic or cyclic groups. Item 18. The method according to Item 17. The alpha-hydroxycarbonyl compound is a group selected from the group consisting of formula R ¹ CH (OH) COR ² , wherein R ¹ and R ² are H, CH ₃ , (CH ₂ ) nCH ₃ , n Is an integer of 0 to 20, and an oligomeric or polymeric conjugate of an alpha-hydroxycarbonyl compound with an amine or ammonium compound has an absorption peak of about 300 to 330 nm, The method of claim 18, wherein the method begins at about 500 to 800 nm.   18. The method of claim 17, wherein the oligomeric or polymeric conjugate of an alpha-hydroxycarbonyl compound with an amine or ammonium compound is a conjugate of fructose and monoethanolamine.   The method of claim 17, wherein the composition further comprises sorbitol.   18. The method of claim 17, wherein the composition comprises fructose and monoethanolamine oligomers, free monoethanolamine, N-methylpyrrolidinone, water, sorbitol and carbitol.   The method of claim 17, wherein the conjugate has a band gap of about 0.5 eV or less.