Post-CMP removal using compositions and method of use
An amine-free composition and process for cleaning post-chemical mechanical polishing (CMP) residue and contaminants from a microelectronic device having said residue and contaminants thereon. The amine-free composition preferably includes at least one oxidizing agent, at least one complexing agent, at least one basic compound, and water and has a pH in the range from about 2.5 to about 11.5. The composition achieves highly efficacious cleaning of the post-CMP residue and contaminant material from the surface of the microelectronic device without compromising the low-k dielectric material or the copper interconnect material.
1. A composition comprising at least one oxidizing agent in an amount ranging from about 0.1 wt % to about 1 wt %, at least one complexing agent in an amount ranging from about 1 wt % to about 25 wt %, at least one basic compound in an amount ranging from about 0.01 wt % to about 5 wt %, at least one buffering agent in an amount ranging from about 0.1 wt % to about 5 wt %, and water in an amount ranging from about 66.5 wt % to about 95 wt %, wherein
the composition is substantially devoid of amines, quaternary bases, and fluoride-containing sources, and is free of abrasive material;
a pH of the composition is in a range of from about 10.5 to about 12;
the at least one complexing agent comprises a species selected from the group consisting of ascorbic acid, citric acid, benzoic acid, mandelic acid, maleic anhydride, aspartic acid, glutamic acid, glyoxylic acid, phenylacetic acid, quinic acid, terephthalic acid, trimellitic acid, trimesic acid, glyceric acid, propionic acid, acrylic acid, adipic acid, itaconic acid, glucuronic acid, lysine, histidine, phenylalanine, cysteine, leucine, serine, 8-hydroxyquinoline, 2,4-pentanedione, benzetetracarboxylic acid, pyruvic acid, sulfanilic acid, 2-hydroxyphosphonocarboxylic acid (HPAA), pyrocatechol, pyrogallol, (1,2-cyclohexylenedinitrilo)tetraacetic acid (CDTA), 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTCA), phosphonic acid, hydroxyethylidene diphosphonic acid (HEDP), nitrilo-tris(methylenephosphonic acid), p-toluenesulfonic acid, sulfosalicylic acid and derivatives thereof, and any combination thereof; and
wherein the composition at least partially removes residue and contaminants formed on the surface of the microelectronic device during a chemical mechanical polishing process step when in contact with the surface of the microelectronic device, the composition removing the residue and contaminants from the surface of the microelectronic device without damaging low-k dielectric materials, interconnect materials and via materials.
2. The composition of claim 1 , wherein the at least one complexing agent comprises sulfosalicylic acid or derivatives thereof.
3. The composition of claim 1 , wherein the at least one basic compound comprise a species selected from the group consisting of KOH, CsOH, ammonium hydroxide, and combinations thereof.
4. The composition of claim 1 , wherein the at least one basic compound comprises KOH.
5. The composition of claim 1 , wherein the at least one complexing agent further comprises a species selected from the group consisting of lactic acid, maleic acid, malic acid, citric acid, fumaric acid, succinic acid, oxalic acid, malonic acid, phthalic acid, glutaric acid, glycolic acid, pyromellitic acid, tartaric acid, gluconic acid, formic acid, acetic acid, glycine, β-alanine, gallic acid, tannic acid, ethylenediamine tetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylidene diphosphonic acid (HEDP),-p-toluenesulfonic acid, and any combination thereof.
6. The composition of claim 1 , wherein the at least one oxidizing agent comprises a species selected from the group consisting of ozone, nitric acid, bubbled air, cyclohexylaminosulfonic acid, hydrogen peroxide, FeCl 3 , oxone (2KHSO 5 .KHSO 4 . K 2 SO 4 ), ammonium peroxomonosulfate, ammonium chlorite, ammonium chlorate, ammonium iodate, ammonium perborate, ammonium perchlorate, ammonium periodate, ammonium persulfate, ammonium hypochlorite, sodium perborate, sodium persulfate, sodium hypochlorite, potassium iodate, potassium permanganate, potassium persulfate, potassium persulfate, potassium hypochlorite, tetramethylammonium chlorite, tetramethylammonium chlorate, tetramethylammonium iodate, tetramethylammonium perborate, tetramethylammonium perchlorate, tetramethylammonium periodate, tetramethylammonium persulfate, tetrabutylammonium peroxomonosulfate, peroxomonosulfuric acid, ferric nitrate, N-methylmorpholine-N-oxide, trimethylamine-N-oxide, triethylamine-N-oxide, pyridine-N-oxide, N-ethylmorpholine-N-oxide, N-methylpyrrolidine-N-oxide, N-ethylpyrrolidine-N-oxide, urea hydrogen peroxide, peracetic acid, periodic acid, potassium dichromate, potassium chlorate, 2-nitrophenol, 1,4-benzoquinone, peroxybenzoic acid, peroxyphthalic acid salts, vanadium oxides, ammonium metavanadate, ammonium tungstate, sodium nitrate, potassium nitrate, ammonium nitrate, strontium nitrate, sulfuric acid, and combinations thereof.
7. The composition of claim 1 , wherein the at least one oxidizing agent comprises a species selected from the group consisting of hydrogen peroxide, N-methylmorpholine-N-oxide, urea hydrogen peroxide, and combinations thereof.
8. The composition of claim 1 , wherein the at least one buffering agent comprises a species selected from the group consisting of dipotassium phosphate, potassium carbonate, boric acid, lysine, proline, β-alanine, ethylenediamine tetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), dimethyl glyoxime, dibasic phosphate (K 2 HPO 4 ), tribasic phosphate (K 3 PO 4 ), mixtures of dibasic and tribasic phosphate, mixures of dibasic and tribasic carbonate, hydroxyethylidene diphosphonic acid, and combinations thereof.
9. The composition of claim 1 , wherein the at least one buffering agent comprises a species selected from the group consisting of dibasic phosphate (K 2 HPO 4 ), tribasic phosphate (K 3 PO 4 ), mixtures of dibasic and tribasic phosphate, HEDP, and combinations thereof.
10. The composition of claim 1 , further comprising at least one solvating agent comprising a species selected from the group consisting of 2-pyrrolidinone, 1-(2-hydroxyethyl)-2-pyrrolidinone, glycerol, 1,4-butanediol, tetramethylene sulfone (sulfolane), dimethyl sulfone, ethylene glycol, propylene glycol, dipropylene glycol, 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 monobutyl ether, ethylene 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, and combinations thereof.
11. The composition of claim 1 , further comprising at least one solvating agent selected from the group consisting of sulfolane, 1-(2-hydroxyethyl)-2-pyrrolidinone, and combinations thereof.
12. The composition of claim 10 , wherein the amount of at least one solvating agent is about 5 wt % to about 20 wt %, based on the total weight of the composition.
13. The composition of claim 1 , further comprising at least one surfactant selected from the group consisting of dodecylbenzenesulfonic acid (DDBSA), polyethylene glycols, polypropylene glycols, polyethylene or polypropylene glycol ethers, block copolymers based on ethylene oxide and propylene oxide, polyoxyethylene (40) nonylphenylether (branched), dinonylphenyl polyoxyethylene, nonylphenol alkoxylates, polyethylene glycol sorbitan monooleate, sorbitan monooleate, ethoxylated fluorosurfactants, polyoxyethylene (16) tallow ethylmonium ethosulfate, ammonium polyacrylate, fluorosurfactants, polyacrylates, and combinations thereof.
14. The composition of claim 13 , wherein the amount of the at least one surfactant is about 0.001 wt % to about 1 wt %, based on the total weight of the composition.
15. The composition of claim 1 , wherein the composition comprises urea hydrogen peroxide, KOH, KH 2 PO 4 , 5-sulfosalicylic acid, at least one solvating agent, and water.
16. A method comprising: contacting a microelectronic device with a cleaning composition after a chemical mechanical polishing process step, the microelectronic device having residue and contaminants thereon resulting from the chemical mechanical polishing process step,
wherein the microelectronic device is contacted with the cleaning composition for sufficient time to at least partially clean said residue and contaminants from the microelectronic device, and wherein
the composition comprises at least one oxidizing agent in an amount ranging from about 0.1 wt % to about 1 wt %, at least one complexing agent in an amount ranging from about 1 wt % to about 25 wt %, at least one basic compound in an amount ranging from about 0.01 wt % to about 5 wt %, at least one buffering agent in an amount ranging from about 0.1 wt % to about 5 wt %, and water in an amount ranging from about 66.5 wt % to about 95 wt %,
the composition is substantially devoid of amines, quaternary bases, and fluoride-containing sources, and is free of abrasive,
a pH of the composition is in a range of from about 10.5 to about 12, and
the at least one complexing agent comprises a species selected from the group consisting of ascorbic acid, citric acid, benzoic acid, mandelic acid, maleic anhydride, aspartic acid, glutamic acid, glyoxylic acid, phenylacetic acid, quinic acid, terephthalic acid, trimellitic acid, trimesic acid, glyceric acid, propionic acid, acrylic acid, adipic acid, itaconic acid, glucuronic acid, lysine, histidine, phenylalanine, cysteine, leucine, serine, 8-hydroxyquinoline, 2,4-pentanedione, benzetetracarboxylic acid, pyruvic acid, tannic acid, sulfanilic acid, 2-hydroxyphosphonocarboxylic acid (HPAA), pyrocatechol, pyrogallol, (1,2-cyclohexylenedinitrilo)tetraacetic acid (CDTA), 2-phosphonobutane-1,2,4-tricarboxylic acid) (PBTCA), phosphonic acid, hydroxyethylidene diphosphonic acid (HEDP), nitrilo-tris(methylenephosphonic acid, p-toluenesulfonic acid, sulfosalicylic acid and derivatives thereof, and any combination thereof.
17. The method of claim 16 , wherein said residue and contaminants comprise post-CMP residue and contaminants.
18. The method of claim 16 , wherein the at least one basic compound comprise a species selected from the group consisting of KOH, CsOH, ammonium hydroxide, and combinations thereof.
19. The method of claim 16 , wherein the at least one oxidizing agent comprises a species selected from the group consisting of ozone, nitric acid, bubbled air, cyclohexylaminosulfonic acid, hydrogen peroxide, FeCl 3 , oxone (2KHSO 5 .KHSO 4 .K 2 SO 4 ), ammonium peroxomonosulfate, ammonium chlorite, ammonium chlorate, ammonium iodate, ammonium perborate, ammonium perchlorate, ammonium periodate, ammonium persulfate, ammonium hypochlorite, sodium perborate, sodium persulfate, sodium hypochlorite, potassium iodate, potassium permanganate, potassium persulfate, potassium persulfate, potassium hypochlorite, tetramethylammonium chlorite, tetramethylammonium chlorate, tetramethylammonium iodate, tetramethylammonium perborate, tetramethylammonium perchlorate, tetramethylammonium periodate, tetramethylammonium persulfate, tetrabutylammonium peroxomonosulfate, peroxomonosulfuric acid, ferric nitrate, N-methylmorpholine-N-oxide, trimethylamine-N-oxide, triethylamine-N-oxide, pyridine-N-oxide, N-ethylmorpholine-N-oxide, N-methylpyrrolidine-N-oxide, N-ethylpyrrolidine-N-oxide, urea hydrogen peroxide, peracetic acid, periodic acid, potassium dichromate, potassium chlorate, 2 -nitrophenol, 1,4-benzoquinone, peroxybenzoic acid, peroxyphthalic acid salts, vanadium oxides, ammonium metavanadate, ammonium tungstate, sodium nitrate, potassium nitrate, ammonium nitrate, strontium nitrate, sulfuric acid, and combinations thereof.
20. The composition of claim 1 , wherein non-aqueous components are present in the composition in an amount less than about 20 wt %.
21. The composition of claim 1 , wherein the composition has a copper etch rate of less than 5 Åmin −1 and a BTA removal efficiency greater than 20%.