Abstract:
The compositions and methods for the removal of residues and contaminants from metal or dielectric surfaces comprises at least one alkyl diphosphonic acid, at least one second acidic substance at a mole ratio of about 1:1 to about 10:1 in water, and pH is adjusted to from about 6 to about 10 with a metal ion free base, and a surfactant. Particularly, a composition and method of cleaning residues after chemical mechanical polishing of a copper or aluminum surface of the semiconductor substrates.

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     The present application is continuation-in-part of application Ser. No. 12/888,569 filed Sep. 23, 2010, and claims priorities from U.S. Provisional Appl. No. 61/254,669, filed Oct. 24, 2009, and are incorporated herein by reference in its entirety. 
    
    
     FIELD OF THE INVENTION 
     The present invention relates to compositions and methods for removal of chemical residues from metal or dielectric surfaces or for chemical mechanical polishing of a copper or aluminum surface including an aqueous solution comprising an alkyl disphosphonic acid compound applied for a time sufficient to remove the chemical residues. 
     BACKGROUND OF THE INVENTION 
     U.S. Pat. Nos. 6,143,705, 6,310,019, 6,440,856, 6,514,352, 6,514,921, 6,534,458, 6,541,434, 6,716,803, 7,250,391, 7,265,005, 7,312,186, and 7,541,322 discuss various compositions and methods of cleaning semiconductor substrates containing phosphonic acids. 
     U.S. Pat. Nos. 6,395,693 and 6,541,434 describe a method and composition for cleaning contaminants from the surface of a semiconductor wafer after the semiconductor wafer has been chemically-mechanically polished, the method comprising contacting the surface of the semiconductor wafer having abrasive particle and metal ion contaminants with a composition comprising carboxylic acid is present in an amount of about 2 wt. % or less, said amine-containing compound is present in an amount of about 0.1 wt. % or less, and said phosphonic acid is present in an amount of about, 2 wt. % or less. The cleaning composition desirably has a pH of about 4-6. Preferably, the cleaning composition has a pH of about 4.5-5.5. The weight ratio of phosphonic acid to carboxylic acid is 1:1. 
     U.S Patent Application No. 20010051597 discusses an aqueous solution of a citric acid concentration of more than 1 vol %, and the chelating, agent is added into the aqueous solution containing the citric acid by 10 ppm or more. The weight ratio of phosphonic acid to carboxylic acid, such is 1:1000 (i.e 10 ppm of phosphonic acid to 1% citric acid) 
     Phosphonic acid, in particular 1-hydroxyethane 1,1-diphosphonic acid (commonly termed HEDPA) has been in commercial use for many years as a corrosion inhibitor and as a complex agent. It is well understood when HEDPA is used in quantities less than 30 parts to million parts water, it acts as corrosion inhibitor. Above 150 parts to million parts water, it acts as a chelating agent. In the range 30-150 parts HEDPA to one million parts water there is a dead zone; the HEDPA does not perform. 
     It is known that HEDPA combined with a surfactant produces a synergistic result. The surfactant not only functions as a dispersant but also improves the residue dissolving performance of the HEDPA when the HEDPA is used in strength above 150 parts to million parts water. 
     SUMMARY OF THE INVENTION 
     The present invention relates to composition and method for cleaning semiconductor substrates. The invention has particular application as a residues and particles remover in semiconductor manufacturing processes and the like. 
     One embodiment encompassed is a cleaning solution that contains, an alkyl diphosphonic acid (component a) of the basic structure; 
                                
wherein R1 and R2 are either the same or different and select from the group consisting of hydrogen (H), hydroxide (OH), chloride (Cl), alkyl or aryl having between 1 to about 8 carbon atoms and alkyl or aryl amine. Some compositions contain a second acidic compound (component b), a buffering amount of one or more basic compounds (component c) to adjust pH from about 6 to about 1.0, optionally from 0% by weight and up to 5% by weight of a surfactant (component d), and a balance of water (component e).
 
     The compositions encompassed may have a mole ratio of alkyl diphosphonic acid to a second acidic compound, or compounds, of about 1:1 to about 10:1. 
     The cleaning solution comprises from about 1% to about 50% by weight of the alkyl disphosphonic acid. 
     Preferred alkyl disphosphonic acids are 1 hydroxyethane 1,1 diphosphonic acid, methylene disphosphonic acid, hydroxymethylene diphosphonic acid, dichloromethylene disphosphonic acid, hydroxycyclohexylmethylene disphosphonic acid, 1-hydroxy-3-aminopropane, 1,1 diphosphonic acid, 1-hydroxy-4-aminobutane 1,1 diphosphonic acid, and the like. 
     Where the composition contains a second acid, that second acid may, for example, be phosphonic acid, sulfonic acid, methanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, xylenesulfonic acid, toluenesulfonic acid, phosphono formic acid, sulfamic acid, 2-amino ethane sulfonic acid, fluoro boric acid, phosphoric acid, hydrofluoric acid, aminotris(methylenephosphonic acid), N carboxymethylaminomethanephosphonic acid, carboxylic acid or mixtures thereof. 
     The composition may also contain an organic carboxylic acid. Where the composition contains an organic carboxylic acid, that acid may be aspartic acid, adipic acid, oxalic acid, lactic acid, citric acid, formic acid, tartaric acid, propionic acid, benzoic acid, ascorbic acid, gluconic acid, malic acid, malonic acid, succinic acid, gallic acid, butyric acid, trifluoracetic acid, hydroxy acetic acid, iminodiacetic acid and the like. 
     It is also contemplated that the compositions may include buffering basic compounds, such as potassium hydroxide, sodium hydroxide and metal ion free base. Where the compositions contain such a compound or mixture of compounds. 
     The metal ion free basic compound or mixture may be at least one basic compounds consisting of hydroxylamine freebase or a hydroxylamine derivative, tetraalkylammonium hydroxide, TMAH pentahydrate, BTMAH (benzyltetramethylammonium hydroxide), TBAH, choline, or THEMAH (Tris(2-hydroxyethyl)methylammonium hydroxide)), monoethanolamine, 2-(2-hydroxylethylamino)ethanol, 2-(2-aminoethoxy)ethanol, N,N,N-tris(2-hydroxyethyl)-ammonia, isopropanolamine, 3-amino-1-propanol, 2-amino-1-propanol, 2-(N-methylamino)ethanol, 2-(2-aminoethylamino)ethanol, tris(hydroxymethyl)aminoethane, or mixtures thereof. 
     A preferred pH range is from about 6 to about 10. 
     Surfactants may also be used in the compositions encompassed herein. Preferred surfactants include nonionic, anionic, cationic, and/or amphoteric, polyaspartic acid, polyacrylic acid or its water-soluble salts, or hydrolyzed poly-maleic anhydride or its water soluble salts and the like. 
     In some applications the compositions may be diluted with DI water at dilution ratios, for example, of up to 1:10, up to 1:50, up to 1:100, up to 1:150, up to 1:250, and up to about 1:500 or any ratios therein. 
     One method of using the compositions described herein involves providing a substrate having a surface comprising copper-containing conductor and a low-k dielectric material and one or more of etching residue, planarization residue, and copper oxide disposed on the surface, which generated from a damascene or dual damascene manufacturing processes or thereof; contacting the surface of the substrate with an effective amount of solution comprising alley diphosphonic acid of the basic structure: 
                                
wherein R1 and R2 are either the same or different and select from the group consisting of hydrogen (H), hydroxide (OH), chloride (Cl), alkyl or aryl having between 1 to about 8 carbon atoms and alkyl or aryl amine, adding a second acidic compound and a buffering amount of basic compounds to adjust pH from about 6 to about 10, optionally including from 0% by weight and up to 5% by weight of a surfactant, with a balance of water. This composition is contacted with a substrate for a time and at a temperature sufficient to remove the resist, residues, and/or copper oxide. The preferred temperature for the method is from about ambient to about 70° C., more preferably about 50° C., and the preferred contact time is between about 10 seconds and about 10 minutes. The compositions described herein may be used in a cleaning process following a chemical mechanical planarization step during the semiconductor fabrication process, as well as other appropriate cleaning processes known to one of skill in the art.
 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     The present invention relates to the provision of an improved cleaning solution which is a blend of alkyl diphosphonic acid and a second acidic substance at a mole ratio of about 1:1 to about 10:1 in water. 
     The alkyl diphosphonic acid of the basic structure: 
                                
wherein R 1  and R 2  are either the same or different and select from the group consisting of hydrogen (H), hydroxide (OH), chloride (Cl), alkyl or aryl having between 1 to about 8 carbon atoms and alkyl or aryl amine.
 
     Non limiting examples of the alkyl diphosphonic acids are as follow: 
     
       
         
               
               
               
               
             
           
               
                   
               
               
                 Name 
                 R1 
                 R2 
                 Structure 
               
               
                   
               
             
             
               
                 -hydroxyethane 1,  1-diphosphonic  acid 
                 OH 
                 CH 3   
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 methylene  diphosphonic  acid (MDP) 
                 H 
                 H 
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 Hydroxymethylene  diphosphonic acid (HMDP) 
                 OH 
                 H 
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 Dichloromethylene  diphosphonic acid (Cl 2 MDP) 
                 Cl 
                 Cl 
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 Hydroxycyclo- hexylmethylene diphosphonic acid  (HCMDP) 
                 OH 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 1-hydroxy- 3 aminopropane  1,1-diphosphonic  acid (APD) 
                 OH 
                 —CH 2 CH 2 NH 2   
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 1-hydroxy-4- aminobutane  1,1 diphosphonic  acid 
                 OH 
                 —CH 2 CH 2 CH 2 NH 2   
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
             
          
         
       
     
     In accordance with the invention, from 1 mole to 10 moles of alkyl diphosphonic acid are mixed with one mole of second acidic substances. 
     Suitable alkyl diphosphonic acids include, but not limited to, 1 hydroxy ethane 1,1 diphosphonic acid, methylene disphosphonic acid, hydroxymethylene diphosphonic acid, dichloromethylene disphosphonic acid, hydroxycyclohexylmethylene disphosphonic acid, 1-hydroxy-3-aminopropane 1,1 diphosphonic acid, 1-hydroxy-4-aminobutane 1,1 diphosphonic acid, and the like. 
     Suitable second acidic substances include phosphonic acid, sulfonic acid, methanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, xylenesulfonic acid, toluenesulfonic acid, phosphono formic acid, sulfamic acid, 2-amino ethane sulfonic acid, fluoro boric acid, phosphoric acid, hydrofluoric acid, aminotris(methylenephosphonic acid), N carboxymethylaminomethanephosphonic acid, carboxylic acid, or mixtures thereof. 
     Non limiting examples of suitable carboxylic acid include aspartic acid, adipic acid, oxalic acid, lactic acid, citric acid, formic acid, tartaric acid, propionic acid, benzoic acid, ascorbic acid, gluconic acid, malic acid, malonic acid, succinic acid, gallic acid, butyric acid, trifluoracetic acid, hydroxy acetic acid, iminodiacetic acid and the like. 
     The mixture or blend is adjusted to a pH of about 6 to about 10 with a buffering amount of basic compounds, such as potassium hydroxide, sodium hydroxide and metal ion free basic compounds consisting of an ammonium compound, such as e.g. ammonium hydroxide, tetraalkylammonium hydroxide, TMAH pentahydrate, BTMAH (benzyltetramethylammonium hydroxide), TBAH, choline, or THEMAH (Tris(2-hydroxyethyl)methylammonium hydroxide)), hydroxylamine freebase, a hydroxylamine derivative, such as e.g N,N diethylhydroxylamine, an, alkanolamine component including but not limited to hydrazine, ethylenediamine, monoethanolamine, N,N diethylamino ethanol, 2-(2-hydroxylethylamino)ethanol, 2-(2-aminoethoxy)ethanol, N,N,N-tris(2-hydroxyethyl)-ammonia, isopropanolamine, 3-amino-1-propanol, 2-amino-1-propanol, 2-(N-methylamino)ethanol, 2-(2-aminoethylamino)ethanol, tris(hydroxymethyl)aminoethane, or mixtures thereof. 
     In one embodiment, the cleaning solution comprises from about 1% to about 50% by weight of at least one alkyl disphosphonic acid. 
     In another embodiment, the at least one alkyl diphosphonic acid may be present in solution in the amount from about 25% to about 50% by weight. 
     In another embodiment, at least two alkyl diphosphonic acids may be present in solution. 
     In another embodiment, at least one or more second acidic compound may be present in solution. 
     In another embodiment, the at least one or more second acidic compound may be present in solution in the amount from about 0.05% to about 50% by weight. 
     In another embodiment, the preferred second acidic compound is sulfamic acid. 
     The basic buffering agent may be present in an amount up to about 25% by weight. 
     Preferably the pH is from about 6 to about 10. 
     EXAMPLES 
     Example 1 
     The following is a list of blends prepared for the purpose of conducting tests: 
     
       
         
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
               
               
                   
                   
                 Mol 
                   
                 Solute 
                 Solute 
                   
               
               
                 Composition 
                 1000 Gram quantities 
                 Wt 
                 Mole 
                 Mole 
                 Gram 
                 Wt % 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 1 
                 1-hydroxy ethanediphosphonic acid 
                 206 
                 6 
                 0.69 
                 142.1 
                 14.21%  
               
               
                   
                 Dodecylbenzene sulfonic acid 
                 326.5 
                 1 
                 0.115 
                 37.55 
                 3.75% 
               
               
                   
                 25% TMAH adjust to pH 6 
                   
                   
                   
                 — 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 2 
                 1-hydroxy ethanediphosphonic acid 
                 206 
                 6 
                 0.69 
                 142.1 
                 14.21%  
               
               
                   
                 phosphono formic acid 
                 128 
                 1 
                 0.115 
                 14.72 
                 1.47% 
               
               
                   
                 25% TMAH adjust to pH 7 
                   
                   
                   
                 — 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 3 
                 1-hydroxy ethanediphosphonic acid 
                 206 
                 6 
                 0.69 
                 142.1 
                 14.21%  
               
               
                   
                 Oxalic Acid 
                 90 
                 1 
                 0.115 
                 10.35 
                 1.04% 
               
               
                   
                 65% (Tris(2-hydroxyethyl)methylammonium 
                   
                   
                   
                 — 
               
               
                   
                 hydroxide)) adjust to pH 9 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 4 
                 1-hydroxy ethanediphosphonic acid 
                 206 
                 6 
                 0.69 
                 142.1 
                 14.21%  
               
               
                   
                 Sulfamic acid 
                 97 
                 1 
                 0.115 
                 11.16 
                 1.12% 
               
               
                   
                 45% Choline Hydroxide adjust to pH 9 
                   
                   
                   
                 — 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 5 
                 1-hydroxy ethanediphosphonic acid 
                 206 
                 6 
                 0.69 
                 142.1 
                 14.21%  
               
               
                   
                 Hydroxy acetic acid 
                 76 
                 1 
                 0.115 
                 8.74 
                 0.87% 
               
               
                   
                 N,N diethylhydroxylamine/monoethanol amine (1:1 wt 
                   
                   
                   
                 — 
               
               
                   
                 ratio) adjust pH to 7 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 6 
                 1-hydroxy ethanediphosphonic acid 
                 206 
                 6 
                 0.69 
                 142.1 
                 14.21%  
               
               
                   
                 Fluoro boric acid 
                 87.8 
                 1 
                 0.115 
                 10.1 
                 1.01% 
               
               
                   
                 Ethylenene diamine adjust pH to 10 
                   
                   
                   
                 — 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 7 
                 1-hydroxy ethanediphosphonic acid 
                 206 
                 6 
                 0.69 
                 142.1 
                 14.21%  
               
               
                   
                 2-amino ethane sulfonic acid 
                 14.5 
                 1 
                 0.115 
                 1.668 
                 0.17% 
               
               
                   
                 25% TMAH adjust to 7 
                   
                   
                   
                 — 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 8 
                 1-hydroxy ethanediphosphonic acid 
                 206 
                 6 
                 0.3 
                 61.8 
                 6.18% 
               
               
                   
                 hydroxy methylenephosphonic acid 
                 112 
                   
                 0.3 
                 33.6 
                 3.36% 
               
               
                   
                 Dodecylbenzene sulfonic acid 
                 326.5 
                 1 
                 0.1 
                 32.65 
                 3.27% 
               
               
                   
                 N,N diethylamino ethanol adjust pH to 7 
                   
                   
                   
                 — 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 9 
                 1-hydroxy-3 aminopropane 1,1-diphosphonic acid 
                 235 
                 6 
                 1.2 
                 282 
                 28.20%  
               
               
                   
                 Hydroxyacetic acid 
                 76 
                 1 
                 0.2 
                 15.2 
                 1.52% 
               
               
                   
                 tris(hydroxymethyl)aminoethane adjust pH to 9 
                   
                   
                   
                 — 
               
               
                   
                 Water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 10 
                 methylene disphosphonic acid 
                 176 
                 6 
                 0.69 
                 121.4 
                 12.10%  
               
               
                   
                 2-amino ethane sulfonic acid 
                 125 
                 1 
                 0.115 
                 14.4 
                 1.40% 
               
               
                   
                 28% ammonium hydroxide adjust pH to 7 
                   
                   
                   
                 — 
               
               
                   
                 Water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 11 
                 1-hydroxy ethanediphosphonic acid 
                 206 
                 6 
                 0.69 
                 142.1 
                 14.21%  
               
               
                   
                 Citric acid 
                 192 
                 1 
                 0.115 
                 22.08 
                 2.21% 
               
               
                   
                 65% (Tris(2-hydroxyethyl)methylammonium 
                   
                   
                   
                 — 
               
               
                   
                 hydroxide)) adjust to pH 9 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 12 
                 hydroxy methylenephosphonic acid 
                 112 
                 6 
                 0.6 
                 67.2 
                 6.72% 
               
               
                   
                 Dodecylbenzene sulfonic acid 
                 326.5 
                 1 
                 0.1 
                 32.65 
                 3.27% 
               
               
                   
                 25% TMAH adjust pH to 10 
                   
                   
                   
                 — 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 13 
                 1-hydroxy ethanediphosphonic acid 
                 206 
                 6 
                 0.69 
                 142.1 
                 14.21%  
               
               
                   
                 Hydroxy acetic acid 
                 76 
                 1 
                 0.115 
                 8.74 
                 0.87% 
               
               
                   
                 Potassium hydroxide adjust pH to 7 
                   
                   
                   
                 — 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 14 
                 1-hydroxy ethanediphosphonic acid 
                 206 
                 10 
                 1.15 
                 236.9 
                 23.69%  
               
               
                   
                 Sulfamic acid 
                 97 
                 1 
                 0.115 
                 11.16 
                 1.12% 
               
               
                   
                 Potassium Hydroxide adjust to pH 7 
                   
                   
                   
                 — 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 15 
                 1-hydroxy ethanediphosphonic acid 
                 206 
                 3 
                 0.345 
                 71.07 
                 7.11% 
               
               
                   
                 Hydroxy acetic acid 
                 76 
                 1 
                 0.115 
                 8.74 
                 0.87% 
               
               
                   
                 Potassium Hydroxide adjust pH to 7 
                   
                   
                   
                 — 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 16 
                 1-hydroxy ethanediphosphonic acid 
                 206 
                 3 
                 0.345 
                 71.07 
                 7.11% 
               
               
                   
                 Fluoro boric acid 
                 87.8 
                 1 
                 0.115 
                 10.1 
                 1.01% 
               
               
                   
                 Potassium hydroxide adjust pH to 10 
                   
                   
                   
                 — 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 17 
                 1-hydroxy ethanediphosphonic acid 
                 206 
                 1 
                 0.115 
                 23.69 
                 2.37% 
               
               
                   
                 2-amino ethane sulfonic acid 
                 14.5 
                 1 
                 0.115 
                 1.668 
                 0.17% 
               
               
                   
                 25% TMAH adjust to 7 
                   
                   
                   
                 — 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 18 
                 1-hydroxy ethanediphosphonic acid 
                 206 
                 4 
                 0.4 
                 82.4 
                 8.24% 
               
               
                   
                 hydroxy methylenephosphonic acid 
                 112 
                 4 
                 0.4 
                 44.8 
                 4.48% 
               
               
                   
                 Dodecylbenzene sulfonic acid 
                 326.5 
                 1 
                 0.1 
                 32.65 
                 3.27% 
               
               
                   
                 65% (Tris(2-hydroxyethyl)methylammonium 
                   
                   
                   
                 — 
               
               
                   
                 hydroxide)) adjust to pH 9 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 19 
                 1-hydroxy ethanediphosphonic acid 
                 206 
                 8 
                 0.92 
                 189.5 
                 18.95%  
               
               
                   
                 phosphono formic acid 
                 128 
                 1 
                 0.115 
                 14.72 
                 1.47% 
               
               
                   
                 25% TMAH adjust to pH 7 
                   
                   
                   
                 — 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 20 
                 1-hydroxy ethanediphosphonic acid 
                 206 
                 8 
                 0.92 
                 189.5 
                 18.95%  
               
               
                   
                 Oxalic Acid 
                 90 
                 1 
                 0.115 
                 10.35 
                 1.04% 
               
               
                   
                 65% (Tris(2-hydroxyethyl)methylammonium 
                   
                   
                   
                 — 
               
               
                   
                 hydroxide)) adjust to pH 9 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 21 
                 hydroxy methylenediphosphonic acid 
                 192 
                 1 
                 0.1 
                 19.2 
                 1.92% 
               
               
                   
                 Dodecylbenzene sulfonic acid 
                 326.5 
                 1 
                 0.1 
                 32.65 
                 3.27% 
               
               
                   
                 25% TMAH adjust pH to 10 
                   
                   
                   
                 — 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 22 
                 1-hydroxy ethanediphosphonic acid 
                 206 
                 6 
                 0.69 
                 142.1 
                 14.21%  
               
               
                   
                 Sulfamic acid 
                 97 
                 1 
                 0.115 
                 11.16 
                 1.12% 
               
               
                   
                 45% Choline Hydroxide adjust to pH 9 
                   
                   
                   
                 — 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 23 
                 1-hydroxy ethanediphosphonic acid 
                 206 
                 1 
                 0.50 
                 103 
                 10.3% 
               
               
                   
                 Sulfamic acid 
                 97 
                 1 
                 0.50 
                 48.5 
                 4.85% 
               
               
                   
                 45% Choline Hydroxide adjust to pH 9 
                   
                   
                   
                 — 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 24 
                 1-hydroxy ethanediphosphonic acid 
                 206 
                 10 
                 1.15 
                 236.9 
                 23.69%  
               
               
                   
                 Sulfamic acid 
                 97 
                 1 
                 0.115 
                 11.16 
                 1.12% 
               
               
                   
                 Potassium Hydroxide adjust to pH 7 
                   
                   
                   
                 — 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 25 
                 1-hydroxy ethanediphosphonic acid 
                 206 
                 10 
                 0.03 
                 6.18 
                 6.18% 
               
               
                   
                 Sulfamic acid 
                 97 
                 1 
                 0.003 
                 0.29 
                 0.29% 
               
               
                   
                 Potassium Hydroxide adjust to pH 7 
                   
                   
                   
                 — 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 26 
                 1-hydroxy-3 aminopropane 1,1-diphosphonic acid 
                 235 
                 6 
                 1.2 
                 282 
                 28.20%  
               
               
                   
                 Sulfamic acid 
                 97 
                 1 
                 0.2 
                 19.4 
                 1.94% 
               
               
                   
                 tris(hydroxymethyl)aminoethane adjust pH to 9 
                   
                   
                   
                 — 
               
               
                   
                 Water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 27 
                 1-hydroxy-3 aminopropane 1,1-diphosphonic acid 
                 235 
                 10 
                 1.2 
                 282 
                 28.20%  
               
               
                   
                 Sulfamic acid 
                 97 
                 1 
                 0.12 
                 11.64 
                 1.16% 
               
               
                   
                 tris(hydroxymethyl)aminoethane adjust pH to 9 
                   
                   
                   
                 — 
               
               
                   
                 Water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 28 
                 1-hydroxy-3 aminopropane 1,1-diphosphonic acid 
                 235 
                 1 
                 1.2 
                 282 
                 28.20%  
               
               
                   
                 Sulfamic acid 
                 97 
                 1 
                 1.2 
                 116.4 
                 11.64%  
               
               
                   
                 tris(hydroxymethyl)aminoethane adjust pH to 9 
                   
                   
                   
                 — 
               
               
                   
                 Water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                   
               
             
          
         
       
     
     This example illustrates the significance of the mole ratio of alkyl phosphonic acid to second acidic component in the cleaning composition of the present invention in reducing slurry particle remnants and metal ion remnants on the surface of a substrate. 
     Silicon oxide wafers were immersed for 30 seconds with copper-contaminated slurry. The oxide wafers were then washed with each of the above listed compositions and followed by rinsing in DI water. There was a complete and relatively fast dissolution of the remnants. Each of the blends removed the slurry particle remnants and metal ion from the surface of the substrates without attacking the exposed metal surfaces. 
     Example 2 
     The procedure was repeated with 5 parts of Composition 9 in 100 parts of D.I water (1:20 water dilution). Effectively, this solution contains 1.343% of 1-hydroxy-3 aminopropane 1,1-diphosphonic acid and 0.122% of hydroxyacetic acid. It still maintains a 6:1 mole ratio of alky diphosphonic to second acidic compound. The same results were obtained by the use of this mixture. 
     Example 3 
     The procedure was repeated with 1 parts of Composition 5 in 100 parts of D.I water (1:100 wafer dilutions). Effectively, this solution contains 0.141% of 1-hydroxy ethanediphosphonic acid and 0.009% of hydroxyacetic acid. It still maintains 6:1 mole ratio of alky diphosphonic to second acidic compound. The same results were obtained by the use of this mixture. 
     Example 4 
     The procedure was repeated with 1 parts of Composition 15 in 100 parts of D.I water (1:100 water dilutions). Effectively, this solution contains 0.0711% of 1-hydroxy ethanediphosphonic acid and 0.009% of hydroxyacetic acid. It still maintains 3:1 mole ratio of alky diphosphonic to second acidic compound. The same results were obtained by the use of this mixture. 
     Example 5 
     The procedure was repeated with 5 parts of Composition 14 in 100 parts of D.I water (1:20 water dilution). Effectively, this solution contains 1.185% of 1-hydroxy ethanediphosphonic acid and 0.056% of sulfamic acid. It still maintains a 10:1 mole ratio of alky diphosphonic to second acidic compound. The same results were obtained by the use of this mixture. 
     Example 6 
                                                                       Trade name/       Wt           Ingredients   product name   Supplier   (Grams)   %                                1-hydroxy ethane-   DEQUEST 2010   Thermphos   580   13.0%       diphosphonic acid       CAS#2809-21-4       Hydroxy acetic acid   Glycolic Acid   Du Pont   60   1.3%       Hydroxylamine       San Fu   600   13.4%       Freebase (50%)       Triethanolamine   TEA85   Dow   470   10.5%       (85%)       water           2760   61.7%       Total           4470   100.0%                    
The pH of the above solution is 7.24-7.26. The solution can be used as is or further diluted with water if necessary.
 
     Example 7 
                                                                       Trade name/       Wt           Ingredients   product name   Supplier   (Grams)   %                                1-hydroxy ethane-   DEQUEST 2010   Thermphos   530   11.2%       diphosphonic acid       CAS#2809-21-4       Amino tris   DEQUEST 2000   Thermphos   90   1.9%       (methylene       phosphonic       acid) in water       CAS#6419-19-8       N,N Diethyl-       Arkema   310   6.6%       hydroxylamine 85%       CAS#3710-84-7       Monoethanolamine   MEA   Dow   310   6.6%       water           3480   73.7%       Total           4420   100.0%                    
The solution is 7.7. The solution can be used as is or further diluted with water if desired.
 
     Examples 8 
     
       
         
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
               
               
                   
                   
                 Mol 
                   
                 Solute 
                 Solute 
                   
               
               
                 Composition 
                 1000 Gram quantities 
                 Wt 
                 Mol 
                 Mole 
                 Gram 
                 Wt % 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 1 
                 1-hydroxy ethanediphosphonic acid 
                 206 
                 6 
                 1.26 
                 259.6 
                 25.96% 
               
               
                   
                 Oxalic Acid 
                 90 
                 1 
                 0.21 
                 18.9 
                 1.89% 
               
               
                   
                 65% (Tris(2-hydroxyethyl)methylammonium 
                   
                   
                   
                 — 
               
               
                   
                 hydroxide)) adjust to pH 9 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 2 
                 1-hydroxy ethanediphosphonic acid 
                 206 
                 6 
                 1.5 
                 309 
                 30.90% 
               
               
                   
                 Hydroxy acetic acid 
                 76 
                 1 
                 0.25 
                 19 
                 1.90% 
               
               
                   
                 N,N diethylhydroxylamine/monoethanol amine 
                   
                   
                   
                 — 
               
               
                   
                 (1:1 wt ratio) adjust pH to 7 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 3 
                 1-hydroxy-3 aminopropane 1,1-diphosphonic 
                 235 
                 6 
                 1.2 
                 282 
                 28.20% 
               
               
                   
                 acid 
               
               
                   
                 Hydroxyacetic acid 
                 76 
                 1 
                 0.2 
                 15.2 
                 1.52% 
               
               
                   
                 tris(hydroxymethyl)aminoethane adjust pH to 9 
                   
                   
                   
                 — 
               
               
                   
                 Water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 4 
                 1-hydroxy ethanediphosphonic acid 
                 206 
                 6 
                 1.32 
                 271.9 
                 27.19% 
               
               
                   
                 Citric acid 
                 192 
                 1 
                 0.22 
                 42.24 
                 4.22% 
               
               
                   
                 65% (Tris(2-hydroxyethyl)methylammonium 
                   
                   
                   
                 — 
               
               
                   
                 hydroxide)) adjust to pH 9 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 5 
                 1-hydroxy ethanediphosphonic acid 
                 206 
                 6 
                 1.8 
                 370.8 
                 37.08% 
               
               
                   
                 Hydroxy acetic acid 
                 76 
                 1 
                 0.3 
                 22.8 
                 2.28% 
               
               
                   
                 Potassium hydroxide adjust pH to 7 
                   
                   
                   
                 — 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 6 
                 1-hydroxyethanediphosphonic acid 
                 206 
                 3 
                 1.5 
                 309 
                 30.90% 
               
               
                   
                 Hydroxy acetic acid 
                 76 
                 1 
                 0.5 
                 38 
                 3.80% 
               
               
                   
                 Potassium Hydroxide adjust pH to 7 
                   
                   
                   
                 — 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 7 
                 1-hydroxy ethanediphosphonic acid 
                 206 
                 8 
                 1.6 
                 329.6 
                 32.96% 
               
               
                   
                 Oxalic Acid 
                 90 
                 1 
                 0.2 
                 18 
                 1.80% 
               
               
                   
                 65% (Tris(2-hydroxyethyl)methylammonium 
                   
                   
                   
                 — 
               
               
                   
                 hydroxide)) adjust to pH 9 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 8 
                 1-hydroxy ethanediphosphonic acid 
                 206 
                 1 
                 1.26 
                 259.6 
                 25.96% 
               
               
                   
                 Oxalic Acid 
                 90 
                 1 
                 1.26 
                 113.4 
                 11.34% 
               
               
                   
                 65% (Tris(2-hydroxyethyl)methylammonium 
                   
                   
                   
                 — 
               
               
                   
                 hydroxide)) adjust to pH 9 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                 9 
                 hydroxy methylene diphosphonic acid 
                 192 
                 1 
                 1.5 
                 288 
                 28.8 
               
               
                   
                 Dodecylbenzene sulfonic acid 
                 326.5 
                 1 
                 1.5 
                 489.75 
                 49 
               
               
                   
                 25% TMAH adjust pH to 6 
                   
                   
                   
                 — 
               
               
                   
                 water 
                   
                   
                   
                 Bal 
               
               
                   
                 Total 
                   
                   
                   
                 1000 
               
               
                   
               
             
          
         
       
     
     It will be obvious to any skill in the art that the effectiveness of removing particle and metal ion contaminant will depend on the seriousness of the problem. A higher concentration of the blended composition will produce faster results. 
     The composition of the invention does not sequest and there is no dead or non-performance zone of cleaning. 
     The alky diphosphonic acid acts as a chelating agent throughout a large concentration range, starting with a few parts to million parts water. 
     In another embodiment, the composition contains a surfactant which enhance the cleaning performance of the composition over the composition with alkyl diphosphonic acid alone. 
     Preferably a surfactant is admixed with the blend to both keep it from re-precipitating and to enhance the cleaning ability of the composition. There are several types of surfactants available. Readily available and relatively inexpensive surfactants include anionic, cationic, non-ionic, amphoteric, polyaspartic acid, polyacrylic acid, water-soluble salts of polyacrylic acid, hydrolyzed poly-maleic anhydride, or water-soluble salts of polyacrylic acid. 
     While the invention has been described and illustrated herein by reference to various specific materials, procedures and examples, it is understood that the invention is not restricted to the particular combinations of materials and procedures selected for that purpose. Numerous variations of such details can be implied as will be appreciated by those skilled in the art. It is intended that me specification and examples considered as exemplary, only, with the true scope and spirit of the invention being indicated by the following claims. All references, patents, patent applications referred to in this application are herein being incorporated by reference in their entirety.