KR20090060104A - Fluoride-free photoresist stripper or residue removing cleaning compositions containing conjugate oligomeric or polymeric material of alpha-hydroxycarbonyl compound/amine or ammonia reaction - Google Patents

Abstract

A fluoride-free microelectronic cleaning composition and a method for cleaning photoresist, contaminant, and etching residue from a microelectronic substrate are provided to improve corrosion resistance, especially, corrosion resistance to copper, and cleaning efficiency. A fluoride-free microelectronic cleaning composition comprises at least one kind of browned or yellowed oligomeric or polymeric conjugate with an alpha-hydroxycarbonyl compound and amine or ammonium compound; at least one kind of amine; and at least one kind of water-miscible organic solvent, or water and at least one kind of water-miscible organic solvent. The alpha-hydroxycarbonyl compound is the compound represented by R1CH(OH)COR2, wherein R1 and R2 are independently selected from the group consisting of an aliphatic group and a cyclic group.

Description

FLUORIDE-FREE PHOTORESIST STRIPPER OR RESIDUE REMOVING CLEANING COMPOSITIONS CONTAINING CONJUGATE OLIGOMERIC OR POLYMERIC MATERIAL OF ALPHA-HYDROXYCARBONYL COMPOUND / AMINE OR AMMONIA REACTION}

The present invention relates to a composition useful for removing photoresist, contaminants, or plasma or etch residues from a microelectronic device, which composition provides excellent copper corrosion inhibition or corrosion resistance while maintaining cleanliness. In particular, the present invention relates to oligomeric or polymeric materials of alpha-hydroxycarbonyl compounds, in particular both "browned" or "yellowed" oligomeric or polymeric conjugate materials of alpha-hydroxycarbonyl compounds, and in particular, Provided are organic solvent based or semi-aqueous based, fluoride-free cleaning compositions in which both "browned" or "yellowed" oligomeric or polymeric conjugate materials of monosaccharides are present. The invention also provides a method of cleaning a microelectronic substrate and device using the composition.

The semiconductor device includes coating an inorganic substrate with a photoresist; Developing after exposure to light to pattern the photoresist film; Etching the exposed portion of the inorganic substrate using the patterned photoresist film as a mask to form a fine circuit; And removing the patterned photoresist film from the inorganic substrate. Alternatively, after forming the microcircuits in the same manner as above, the patterned photoresist film is ashed and then the remaining resist residues are removed from the inorganic substrate.

Many alkaline substrate cleaning compositions have been proposed for removing photoresist and residues from microelectronic devices. However, one significant problem encountered when cleaning such microelectronic devices has been the propensity of the cleaning composition to corrode metals, especially copper, in such microelectronic devices. However, as currently available stripping agents, alkaline stripping solutions generally cause various types of metal corrosion, such as corrosion of metal lines, whiskers, galvanic corrosion, pitting, notching. This is at least partly observed due to the reaction of the metal with the alkaline stripping agent.

Conventional methods used to avoid such corrosion problems used intermediate rinses using non-alkaline organic solvents such as, for example, isopropyl alcohol. However, such methods are expensive and have undesirable consequences for safety, chemical hygiene, and the environment.

U. S. Patent 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. Aqueous compositions typically comprise (a) one or more metal ion-free bases in an amount sufficient to bring the pH to about 10-13; (b) about 0.01% to about 5% by weight (expressed as SiO ₂ %), a water soluble silicate free silicate; (c) about 0.01% to about 10% by weight of one or more metal chelating agents; And (d) optionally other components.

However, none of the compositions disclosed in the prior art effectively removes all organic impurities and metal-containing residues remaining after a typical etching process. Silicon-containing residues in particular are difficult to remove using such formulations. Therefore, there is a need for a peeling composition that cleans the semiconductor wafer substrate by removing inorganic and organic impurities from the semiconductor wafer substrate without damaging the integrated circuit. Such compositions must not partially corrode metal features comprising integrated circuits, and avoid the expense and adverse consequences caused by intermediate rinsing. therefore,

(1) is essentially compatible with all metals (Al, Cu, Mo, etc.) used in semiconductor devices, ie, essentially does not corrode the metals;

(2) no intermediate rinse is required;

(3) suitable for cleaning Si-rich residues;

(4) There is a need for fluoride-containing microelectronic cleaning compositions that do not essentially damage the ILD.

Summary of the Invention

According to the invention, (a) at least one "browned" or "yellowed" alpha-hydroxycarbonyl conjugate which is an oligomer or polymer conjugate of an alpha-hydroxycarbonyl compound with an amine or ammonium compound, (b) A fluoride-free microelectronic cleaning composition or formulation, based on a neutral to organic solvent or semi-aqueous, comprising at least one amine and (c) at least one organic solvent, or at least one organic solvent and water. to provide. Alpha-hydroxycarbonyl compounds are of the general formula R ¹ CH (OH) COR ² , wherein R ¹ and R ² are independently selected from H, aliphatic groups, or cyclic groups, aliphatic groups or cyclic The group may contain one or more substituents. Such substituents include aromatic groups, heteroaromatic groups, hydroxyl groups (-OH groups), ether groups (-COC), amide groups (-C (O) NH), sulfoxide groups (-CS (O) -C) , 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 (-C (O)), It is not limited to this. In alpha-hydroxycarbonyl compounds 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 , where n is an integer 0 To 20, preferably 1 to 10, and more preferably 1 to 6). Some examples of suitable alpha-hydroxycarbonyl compounds include 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 monosaccharides including, in particular, glucose, fructose, or galactose, which are adapted to the general formula above. The reaction of the amine with the alpha-hydroxycarbonyl compound is known to proceed first through the nucleophilic addition of the amine on carbonyl carbon and then through the Maillard reaction [Yaylayan, VA; Harty-Majors, S .; Ismail, AA; J. Agric. Food Chem. 1999, 47, 2335-2340. The Mayal reaction is actually a complex series, the details of which are described in Dills, WL; Am. J. Clin. Nutr. 1993, 58, 779S-787S.

The pH of the composition can be any pH, acidic to basic pH. In one embodiment of the composition of the present invention, the composition also comprises (d) at least one metal-free base, in an amount sufficient to bring the pH of the final composition to at least 7, preferably from about 9.5 to about 10.8. It may contain. The composition of the present invention may also comprise one or more (e) polyhydric alcohols, (f) metal chelating agents, and (g) surfactants. Browned or yellowed oligomers or polymer conjugates of alpha-hydroxycarbonyl compounds used in the compositions of the present invention have an absorbance peak at about 300 to about 330 nm, wherein the absorbance peak is at a wavelength of about 500 to about 800 nm. To be oligomeric or polymeric conjugates. The term "browning" or "yellowing" should be understood to include color and hue, such as a combination of brown and yellow, such as pale orange and dark orange. These browned or yellowed oligomeric or polymeric conjugates are known from the known "" Maillard Reaction " -LC Maillard, Compt . Rend . 154, 66 (1912); Ann , Chim . 9, 5, 258 (1916). Yellowed conjugates, which are oligomeric or polymeric conjugates of alpha-hydroxycarbonyl compounds with amines or ammonium compounds, used in the compositions of the present invention, are generally the same as the yalal reaction, generally at lower temperatures or shorter reactions. It can be formed over time and even by reacting the reactants together at room temperature for a suitable time. The browned conjugate, which is an oligomer or polymer conjugate of an alpha-hydroxycarbonyl compound and an amine or ammonium compound, used in the compositions of the present invention has an absorbance peak at about 300 to about 330 nm, wherein the absorbance peak is about 600 to about While starting at a wavelength of 800 nm, the "yellowed" conjugates of alpha-hydroxycarbonyl compounds, oligomeric or polymeric conjugates that are the reaction products of alpha-hydroxycarbonyl compounds with amines or ammonium, have absorbance at about 300 to about 330 nm. Although having a peak, the absorbance peak starts at about 500 to about 580 nm. The conjugate is first formed and then added to the composition of the present invention, or heated to a temperature of at least 70 ° C., for example, for a time sufficient to allow a mayal reaction between the alpha-hydroxycarbonyl compound and the amine or ammonium compound to occur. The oligomer generated can be formed.

The cleaning composition of the present invention is placed in contact with the semiconductor device for a period of time at a temperature sufficient to clean unwanted contaminants and / or residues from the substrate surface. The composition of the present invention enhances corrosion resistance, in particular copper corrosion resistance, and improves cleaning rate.

The cleaning compositions of the present invention comprise (a) at least one "browned" or "yellowed" alpha-hydroxycarbonyl conjugate, which is an oligomer or polymer conjugate of an alpha-hydroxycarbonyl compound with an amine or ammonium compound, and (b) at least one amine, and (c) at least one organic solvent, or at least one organic solvent and water, comprising an organic solvent based or semi-aqueous based, fluoride-free detergent. The formulation may also contain any other ingredients, (d) at least one metal-free, in an amount sufficient to cause the pH of the final composition to be at least 7, preferably at a pH of about 9.5 to about 10.8, if an alkaline cleaning composition is desired. Ionic bases, and one or more (e) polyhydric alcohols, and (f) metal chelating agents and (g) surfactants.

The "browned" or "yellowed" alpha-hydroxycarbonyl conjugates used in the compositions of the present invention are oligomers or polymer conjugates of alpha-hydroxycarbonyl compounds with amine or ammonium compounds, from about 300 to about 330 nm. Have an absorbance peak at which the absorbance peak begins at a wavelength of about 500 to about 800 nm. Such browned and yellowed oligomers or polymer conjugates are prepared according to known methods such as, for example, the "Myyal reaction" mentioned above. However, any suitable means of obtaining a "browned" alpha-hydroxycarbonyl conjugate can be used. In addition, such "browned" alpha-hydroxycarbonyl conjugates can be used in the form of black molasses. Based on the reaction of one molecule of the alpha-hydroxycarbonyl compound and one mol of the amine or ammonia compound, at a stoichiometric ratio of from about 1: 1 to about 16: 1 of the alpha-hydroxycarbonyl compound to the amine or ammonia compound The reaction of the alpha-hydroxycarbonyl compound with the amine or ammonia containing compound can be carried out. However, when a smaller amount of the amine or ammonia compound reacting with the alpha-hydroxycarbonyl compound is present, the above ratio is preferably 1: 1 because the copper corrosion inhibiting ability of the reaction product is lowered. Although the reaction may be carried out over a wide range of times and temperatures, the alpha-hydroxycarbonyl compound may be carried out at room temperature for at least several hours or at least several days, or for a period of at least about 15 minutes, such as for a period of at least about 3 hours. The reaction is preferably carried out by heating the amine or ammonia compound to about 70 ° C. or higher. As long as the resulting oligomer or polymer conjugate reaction product has an absorbance peak at " browned " or " yellowed " product, i.e., from about 300 to about 330 nm, the absorbance peak begins at about 500 to about 800 nm. Suitable times and temperatures of may be used. In general, the browned and yellowed alpha-hydroxycarbonyl conjugates preferably used in the present invention are characterized by having a low bandgap of about 0.5 eV or less.

Browned or yellowed alpha-hydroxycarbonyl conjugates can be obtained from the reaction of any suitable alpha-hydroxycarbonyl compound with an amine or ammonia compound. Suitable alpha-hydroxycarbonyl compounds are CH ₃ COCH ₂ OH, which is 1-hydroxy-2-propanone, and HOCH ₂ COCH ₂ OH, which is 1,3-dihydroxyacetone, and arabinose, lysos, ribose, Deoxyribose, xylose, ribulose, xylose, allose, altrose, galactose, glucose, gulose, idos, mannose, fructose, psychos, sorbose, tagatose, mannoseheptulose, seldo All monosaccharides including but not limited to heptulose, octolos, 2-keto-3-deoxy-manno-octonate and sialos. Fructose is particularly preferred. Disaccharides cannot be used in the present invention.

Compounds containing any suitable amine or ammonia can be reacted with alpha-hydroxycarbonyl of the present invention to produce browned or yellowed oligomers or polymer conjugates of alpha-hydroxycarbonyl compounds with amine or ammonium compounds. have. Among the suitable amines are amines, diamines, triamines, alkanolamines, amino acids, in particular primary and secondary amines and alkanolamines. Especially useful are alkanolamines of the formula NH ₂ (CH ₂ ) _n OH, wherein n is an integer from 1 to about 10, preferably from 1 to about 4, and in particular 2. Ammonia is suitably the same as the amine described above. Suitable amine compounds include, but are not limited to, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diethylenetriamine, aminoacetic acid. Monoethanolamine is particularly preferred. Preferred browned alpha-hydroxycarbonyl compounds are obtained from the reaction of fructose with monoethanolamine.

The composition will also include one or more amine components. The amine component may be an excess of free amine left in the product resulting from the reaction to form a browned or yellowed oligomer or polymer conjugate of the alpha-hydroxycarbonyl compound, or the browned or yellowed of the alpha-hydroxycarbonyl compound Amines added to compositions other than the prepared oligomers or polymer conjugates. Among the suitable amines are amines, diamines, triamines, alkanolamines, amino acids, in particular primary and secondary amines and alkanolamines. Especially useful are alkanolamines of the formula NH ₂ (CH ₂ ) _n OH, wherein n is an integer from 1 to about 10, preferably from 1 to about 4, and in particular 2. Ammonia is suitably the same as the amine described above. Suitable amine compounds include, but are not limited to, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diethylenetriamine, aminoacetic acid. Monoethanolamine is particularly preferred.

The formulations of the present invention may be organic solvent based or organic solvent and water based. That is, the formulation may optionally contain one or more polar water miscible organic solvents. 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 polar organic solvents include polar organic solvents such as sulfolane (tetrahydrothiophene-1,1-dioxide), 3-methylsulfolane, n-propyl sulfone, dimethyl sulfoxide (DMSO), methyl sulfone, n-butyl sulfone, 3-methylsulfolane, amides such as 1- (2-hydroxyethyl) -2-pyrrolidone (HEP), dimethylpiperidone (DMPD), N-methyl-2-pyrroli Don (NMP), dimethylacetamide (DMAc), and dimethylformamide (DMF), alkylene glycol mono and dialkyl ethers such as ethylene glycol monotyl ether (carbitol®), mixtures thereof, but It is not limited. Particularly preferred as polar organic solvents are N-methylpyrrolidone, sulfolane, ethylene glycol monotyl ether, DMSO and mixtures thereof. The organic solvent is a water miscible organic solvent, which will generally be present in an amount of about 35 to about 98 weight percent, preferably about 40 to about 90 weight percent, and even more preferably about 45 to about 85 weight percent. In addition to one or more organic solvents, water may also optionally be present in the composition. If water is present with the organic solvent, it will be present in an amount of greater than about 0 to about 20 weight percent, preferably about 3 to about 15 weight percent, and more preferably about 5 to about 10 weight percent.

The "browned" or "yellowed" oligomeric or polymeric alpha-hydroxycarbonyl compounds are generally from about 0.1 to about 20 weight percent, preferably from about 1 to about 10 weight percent, and more preferably in the cleaning compositions of the present invention. Preferably in an amount of about 3 to about 7 weight percent. The amine will be present in the composition in an amount of about 1 to about 15 weight percent, preferably about 3 to about 12 weight percent, and more preferably about 5 to about 10 weight percent. The organic solvent is a water miscible organic solvent, which will generally be present in an amount of about 35 to about 98 weight percent, preferably about 40 to about 90 weight percent, and even more preferably about 45 to about 85 weight percent. When water is present with the organic solvent, it will be present in an amount of greater than about 0 to about 20 weight percent, preferably about 3 to about 15 weight percent, and more preferably about 5 to about 10 weight percent. All percentages are based on the total weight of the cleaning composition.

The pH of the cleaning composition may be acidic or alkaline, but will preferably be at least pH 7, preferably at pH from about 7 to about 10.8, more preferably at pH from about 9.5 to about 10.8. If it is necessary to adjust the pH of the composition, a metal free base may optionally be added to the cleaning composition. Any metal free base can be used. Among the suitable metal-free bases that can be used in the present cleaning compositions are quaternary ammonium hydroxides, such as tetraalkyl ammonium hydroxides (typically hydroxy- and alkoxy-containing alkyl groups include 1 to 4 carbon atoms in the alkyl or alkoxy group). ) May be present. Most preferred of these alkaline substances are tetramethyl ammonium hydroxide and trimethyl-2-hydroxyethyl ammonium hydroxide (choline). Examples of other available quaternary ammonium hydroxides include trimethyl-3-hydroxypropyl ammonium hydroxide, trimethyl-3-hydroxybutyl ammonium hydroxide, trimethyl-4-hydroxybutyl ammonium hydroxide, triethyl-2-hydroxyethyl hydroxide Ammonium, tripropyl-2-hydroxyethyl ammonium hydroxide, tributyl-2-hydroxyethyl ammonium hydroxide, dimethylethyl-2-hydroxyethyl ammonium hydroxide, dimethyldi (2-hydroxyethyl) ammonium hydroxide, monomethyltri (2-hydroxyethyl) ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, monomethyl-triethyl ammonium hydroxide, monomethyltripropyl ammonium hydroxide, monomethyltributyl ammonium hydroxide, monoethyltrimethyl Ammonium Hydroxide, Monoethyltributyl Ammonium Hydroxide, Dimethyldiethyl Ammonium Hydroxide, Dimethyldibutyl Hydroxide Ammonium and the like and mixtures thereof. Other bases which may serve in the present invention include ammonium hydroxide, organic amines, in particular alkanolamines such as 2-aminoethanol, 1-amino-2-propanol, 1-amino-3-propanol, 2- (2 -Aminoethoxy) ethanol, 2- (2-aminoethylamino) ethanol, 2- (2-aminoethylamino) ethylamine, and the like, and other organic strong 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 hydroxyamine. The amount of base used in the composition will be that amount which will bring the composition to the desired pH, which is generally about 0 to about 15 weight percent, preferably about 0.5 to about 5 weight percent, and more preferably about 1 to about 2 weight percent It will be the amount of.

The formulations of the present invention may also optionally 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. If present, the amount of polyhydric alcohol present in the composition may range from about 0 to about 10 weight percent, preferably from about 0 to about 7 weight percent, and more preferably from about 0 to about 5 weight percent.

The formulations of the present invention may also contain any ingredients such as surfactants that are not detrimental to the efficacy of the cleaning composition. The compositions of the present invention may also contain any suitable water soluble amphoteric, non-ionic, cationic or anionic surfactant. When the surfactant is added, the surface tension of the formulation is lowered, and the wettability of the surface to be cleaned will be improved, thereby improving the cleaning action of the composition. Amphoteric surfactants useful in the compositions of the present invention include betaines and sulfobetaes, such as alkyl betaines, amidoalkyl betaines, alkyl sulfobetaines, and amidoalkyl sulfobetaines; Aminocarboxylic acid derivatives such as ampoglycinate, ampopropionate, ampodiglycinate, and ampodipropionate; Iminodiacids such as alkoxyalkyl imino-acids or alkoxyalkyl imino-acids; Amine oxides such as alkyl amine oxides and alkylamido alkylamine oxides; Fluoroalkyl sulfonates and fluorinated alkyl amphoteric surfactants; And mixtures thereof. Preferably, the amphoteric surfactant is cocoamidopropyl betaine, cocoamidopropyl dimethyl betaine, cocoamidopropyl hydroxy sultaine, caprylamide dipropionate, cocoamidodipropionate, coco ampopropionate , Cocoampohydroxyethyl propionate, isodecyloxypropylimino dipropionic acid, laurylimino dipropionate, cocoamidopropylamine oxide and cocoamine oxide and fluorinated alkyl amphoteric surfactants. Non-ionic surfactants useful in the compositions of the invention include acetylene diols, ethoxylated acetylene diols, fluorinated alkyl alkoxylates, fluorinated alkylesters, fluorinated polyoxyethylene alkanols, aliphatic acid esters of polyhydric alcohols, poly Oxyethylene monoalkyl ethers, polyoxyethylene diols, siloxane type surfactants, and alkylene glycol monoalkyl ethers. Preferably, the non-ionic surfactant is acetylene diol, or ethoxylated acetylene diol. Anionic surfactants useful in the compositions of the present invention include mono and diesters of orthophosphoic acid, such as carboxylates, N-acylcarcosinates, sulfonates, sulfates, and decyl phosphates. Preferably, the anionic surfactant is a metal free surfactant. Cationic surfactants useful in the compositions of the present invention include amine ethoxylates, dialkyldimethylammonium salts, dialkylmorpholinium salts, alkylbenzyldimethylammonium salts, alkyltrimethylammonium salts, and alkylpyridinium salts. Preferably, the cationic surfactant is a halogen free surfactant. When used in the compositions of the present invention, the surfactant will generally be present in an amount of greater than about 0 to about 1 weight percent, preferably about 0.05 to about 0.2 weight percent.

The formulations of the present invention may also be formulated with one or more metal compatible chelating agents to increase the ability of the formulation to retain metals in solution and to increase the solubility of metallic residues on the wafer substrate. Typical examples of metal chelating agents useful for this purpose are the following organic acids and their isomers and salts: (ethylenedinitrile) tetraacetic acid (EDTA), butylenediaminetetraacetic acid, cyclohexane-1,2-diaminetetra Acetic acid (CyDTA), diethylenetriaminepentaacetic acid (DETPA), ethylenediaminetetrapropionic acid, (hydroxyethyl) ethylenediaminetriacetic acid (HEDTA), N, N, N ', N'-ethylenediaminetetra (methylenephosphaic acid ) (EDTMP), triethylenetetraaminehexaacetic acid (TTHA), 1,3-diamino-2-hydroxypropane-N, N, N ', N'-tetraacetic acid (DHPTA), methyliminodiacetic acid, propylene Diaminetetraacetic acid, nitrolotriacetic acid (NTA), citric acid, tartaric acid, gluconic acid, sugar acid, glycerin acid, oxalic acid, phthalic acid, maleic acid, mandelic acid, malonic acid, lactic acid, salicylic acid, catechol, gallic acid, propyl gallate , Tired , 8-hydroxyquinoline, and cysteine. As the metal chelating agent, aminocarboxylic acids such as cyclohexane-1,2-diaminetetraacetic acid (CyDTA) are preferred. The one or more metal chelating agents may be present in the formulation in an amount greater than about 0 to about 1 weight percent, preferably about 0.05 to about 0.2 weight percent.

The cleaning composition of the present invention may be used to microcontain photoresist or plasma or etch residues by contacting the microelectronic device with the cleaning composition of the invention for a suitable time at a temperature suitable to remove the photoresist or plasma or etch residues from the microelectronic device. It is used to remove from the electronic device.

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

The following are examples of "browned" or "yellowed" alpha-hydroxycarbonyl conjugated oligomers or polymers useful in the compositions of the present invention.

Browned component 1: 100 g of a mixture of 50:50 weight of fructose and water was reacted with 50 g of monoethanolamine at a temperature of 70 ° C. for about 3 hours.

Browned component 2: 100 g of a 50:50 weight mixture of fructose and water was reacted with 16 g monoethanolamine at a temperature of 70 ° C. for about 3 hours.

Browned component 3: 100 g of a 50:50 weight mixture of fructose and water was reacted with 5 g of monoethanolamine at a temperature of 70 ° C. for about 3 hours.

Browned component 4: 100 g of a mixture of 50:50 weight of fructose and water was reacted with 1 g of monoethanolamine at a temperature of 70 ° C. for about 3 hours.

Browned component 5: 50 g of fructose was dissolved in 10 g of water and the mixture was heated to 80 ° C., then 20.8 g of monoisopropanolamine was added, the solution was allowed to heat itself and the water was released during boiling activity. .

Browned component 6: 50 g of fructose was dissolved in 10 g of water, the mixture was heated to 80 ° C., then 29.2 g of diethanolamine was added, allowed to heat in solution and allowed to release water upon boiling activity. .

Browned component 7: 50 g of fructose was dissolved in 10 g of water, the mixture was heated to 80 ° C., then 41.9 g of triethanolamine was added, heated to solution and allowed to release water upon boiling. .

Browned component 8: 50 g of fructose was dissolved in 10 g of water, the mixture was heated to 80 ° C., then 26.5 g of diethylenetriamine was added, the solution was allowed to heat itself and the water was released during boiling activity. All.

Browned component 9: 50 g of fructose is dissolved in 10 g of water, the mixture is heated to 80 ° C., then 20.8 g of aminoacetic acid (glycine) is added, the solution is allowed to heat itself and the water is released during boiling activity. It was.

Browned component 10: 50 g of glucose was dissolved in 10 g of water, the mixture was heated to 80 ° C., then 17.0 g of monoethanolamine was added, heated to solution itself and allowed to release water upon boiling activity. .

Browned component 11: 50 g of galactose was dissolved in 10 g of water, the mixture was heated to 80 ° C., then 20.8 g of monoethanolamine was added, heated to solution itself and allowed to release water upon boiling activity. .

50 g of a browned component 12:50:50 mixture of 1-hydroxy-2-propanone and water was reacted with 8 g of monoethanolamine at 70 ° C. for about 1 hour.

Browned component 13: 50 g of a mixture of 50:50 dihydroxyacetone and water at 70 ° C

                Was reacted with 8 g of monoethanolamine for about 1 hour.

Yellowed component 14: 50 g of a mixture of 50:50 weight of fructose and water was allowed to stand overnight at room temperature of about 20 ° C., followed by 16 g of monoethanolamine at a temperature of 70 ° C. for about 3 hours.

Yellowed component 15: 50 g of a mixture of 50:50 weight of fructose and water was allowed to stand overnight at room temperature of about 20 ° C., followed by 50 g of monoethanolamine at about 70 ° C. for about 1 week.

Further oligomeric components of the invention are those listed in Compositions A through T in Table 1. The oligomer components of the composition were each prepared in situ by the reaction of fructose with monoethanol, which were present as components in the cleaning composition itself and heated to a temperature of 70 ° C. for 15 minutes to form a conjugate. Was produced.

Inhibition of copper corrosion of the compositions of the invention and the comparative compositions was tested in the following manner. The copper blanket wafer was placed in a 150 ml beaker containing the test composition at about 70 ° C. The composition was stirred for 15 minutes at about 200 rpm and the Cu surface was dropped from the stir bar.

The compositions and test results are shown in Table 1.

Table 1

Table 1 (continued)

Table 1 (continued)

In the reaction with amines, several compounds were tested to identify the need for alpha-hydroxycarbonyl compounds that adequately inhibit copper corrosion. Different types of carbonyl compounds were tested; Ketones (acetone, H ₃ CCOCH ₃ ), diketone (2,3-pentanedione, H ₃ CCOCOCH ₂ CH ₃ ), aldehydes (formaldehyde, HCOH), two different alpha-hydroxycarbonyl compounds (1- Hydroxy-2-propanone, CH ₃ COCH ₂ OH and 1,3-dihydroxyacetone, HOCH ₂ COCH ₂ OH). When used with monoethanolamine, it can be seen from Table 2 that acetone and formaldehyde show no benefit. In contrast, when using the alpha-hydroxycarbonyl compounds 1-hydroxy-2-propanone and 1,3-dihydroxyacetone, the Cu etch rate was about 20 times lower than the etching of monoethanolamine. Even when diketone phosphorus 2,3-pentanedione was used, it was shown that corrosion can be moderately inhibited. This is reasonably explained by the keto-enol tautomerization phenomenon, which provides alpha-hydroxycarbonyl compounds at several chemical equilibrium concentrations, well known in the field of organic chemistry [John, M; Organic Chemistry 1997, WW Norton & Company, Inc., 500 Fifth Avenue, New York, NY 10110. Other data that clearly illustrate the need for alpha-hydroxycarbonyl compounds are the results with beta-hydroxycarbonyl compounds that are 4-hydroxy-4-methyl 2-pentanone. This compound showed no improvement in copper compatibility, which strongly explains the need for an alpha-hydroxycarbonyl compound. Table 2 lists the copper corrosion rates (ms / min) in DMSO, NMP, or mixtures thereof for the compounds tested at 70 ° C. In all compositions monoethanolamine was used as the amine reacted with the listed compounds at 70 ° C. for about 3 hours.

TABLE 2

Reaction products Cu etching rate in DMSO (m / min) Cu etching rate in NMP (Å / min) Blanks: monoethanolamine (MEA) > 100 > 100 Monoethanolamine + acetone 192.3 Monoethanolamine + formaldehyde 19.3 (2: 1 NMP: DMSO mixture was used) Monoethanolamine + glyoxal 33.3 (2: 1 NMP: DMSO mixture was used) Monoethanolamine + 1-hydroxy-2-propanone 1.1 1.5 Monoethanolamine + 1,2-dihydroxyacetone 4.7 1.0 Monoethanolamine + 2,3-pentanedione 10.4 5.1 Monoethanolamine + 4-hydroxy-4-methyl2-pentanone 267.1

The compositions of the present invention are similar to microelectronic cleaning compositions, containing known fluorides, provided that there is no significant copper corrosion encountered when using cleaning compositions containing known fluorides, photoresist or plasma, or etching. It provides for cleaning the residue from the microelectronic device. Preferred cleaning compositions of the invention include compositions of oligomers of fructose and monoethanolamine, free monoethanolamine, N-methyl pyrrolidinone, water, sorbitol and carbitol, such as composition M in Table 1.

Although the present invention has been described herein with reference to specific embodiments thereof, it will be appreciated that changes, modifications, and variations may be made without departing from the spirit and scope of the inventive concepts disclosed herein. Accordingly, the present invention is intended to embrace all such changes, modifications and variations that fall within the spirit and scope of the appended claims.

Claims (23)

(a) at least one "browned" or "yellowed" oligomer or polymer conjugate of an 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 compound of claim 1, wherein 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 groups and cyclic groups Composition. The compound of claim 2, wherein the alpha-hydroxycarbonyl compound is a compound of the formula R ¹ CH (OH) COR ² , wherein R ¹ and R ² are H, CH ₃ , and (CH ₂ ) _n CH ₃ And n is an integer from 0 to 20, wherein the oligomer or polymer conjugate of the alpha-hydroxycarbonyl compound and the amine or ammonium compound has an absorbance peak at about 300 to about 330 nm, wherein The absorbance peak begins at about 500 to about 800 nm. 4. The method of claim 3, wherein the alpha-hydroxycarbonyl compound is selected from arabinose, lysose, ribose, deoxyribose, xylose, ribulose, xylose, allose, altrose, galactose, glucose, gulose, ear canal. Selected from the group consisting of mannose, mannose, fructose, cyclose, sorbose, tagatose, mannoseptulose, seldoheptulose, octolos, 2-keto-3-deoxy-manno-octonate and sialos The composition is a monosaccharide. The composition of claim 1, wherein the oligomer or polymer conjugate of the alpha-hydroxycarbonyl compound and the amine or ammonium compound is a conjugate of fructose and monoethanolamine. The composition of claim 5, wherein the oligomer or polymer conjugate of fructose and monoethanolamine has an absorbance peak at about 300 to about 330 nm, wherein the absorbance peak begins at about 500 to about 800 nm. The composition of claim 6, wherein the conjugate is prepared by heating the fructose and the monoethanolamine together at a temperature of at least 70 ° C. for at least 3 hours. 8. The composition of claim 7, further comprising a polyhydric alcohol. The composition of claim 8 wherein the polyhydric alcohol is sorbitol. The composition of claim 1 wherein the pH of the composition is between about 7 pH and about 10.8 pH. The composition of claim 1 comprising 0.1 to about 20 weight percent oligomer or polymer conjugate component, about 1 to about 15 weight percent amine component, and about 35 to about 98 weight percent organic solvent or organic solvent and water. . The composition of claim 1, further comprising one or more components selected from the group consisting of surfactants, metal ion-free bases, polar water miscible organic solvents, polyhydric alcohols, and metal chelating agents. The composition of claim 5 further comprising one or more components selected from the group consisting of surfactants, metal-free bases, polyhydric alcohols, and metal chelating agents. The composition of claim 1 comprising an oligomer of fructose and monoethanolamine, free monoethanolamine, N-methyl pyrrolidinone, water, sorbitol and carbitol. The composition of claim 1, wherein the conjugate has a bandgap of about 0.5 eV or less. 6. The composition of claim 5, wherein the browned conjugate has a bandgap of about 0.5 eV or less. Contacting the microelectronic substrate with the cleaning composition at a temperature and time sufficient to remove photoresist, contaminants, or etching or ashing residues, wherein the cleaning composition comprises (a) an alpha-hydroxycarbonyl compound; At least one "browned" or "yellowed" oligomer or polymer conjugate with an amine or ammonium compound, (b) at least one amine, and (c) at least one water-miscible organic solvent, or at least one A method of cleaning a photoresist, contaminant, or etch or ashing residue from a microelectronic substrate, which is a fluoride-free microelectronic cleaning composition comprising a water-miscible organic solvent and water. The compound of claim 17, wherein 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 groups and cyclic groups Way. The compound of claim 18, wherein the alpha-hydroxycarbonyl compound is a compound of the formula R ¹ CH (OH) COR ² , wherein R ¹ and R ² are H, CH ₃ , and (CH ₂ ) _n CH ₃ And n is an integer from 0 to 20, wherein the oligomer or polymer conjugate of the alpha-hydroxycarbonyl compound and the amine or ammonium compound has an absorbance peak at about 300 to about 330 nm, wherein The absorbance peak begins at about 500 to about 800 nm. 18. The method of claim 17, wherein the oligomer or polymer conjugate of the alpha-hydroxycarbonyl compound and the 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 oligomers of fructose and monoethanolamine, free monoethanolamine, N-methyl pyrrolidinone, water, sorbitol and carbitol. The method of claim 17, wherein the conjugate has a bandgap of about 0.5 eV or less.