Unsaturated dicarboxylic acid and ethylene urea containing formulation for cleaning semiconductor and cleaning method

Abstract

A semiconductor wafer cleaning formulation comprising an unsaturated dicarboxylic acid and ethylene urea, and a cleaning method are provided. The formulation comprises an unsaturated dicarboxylic acid and ethylene urea as essential components, and is used for removing residues in semiconductor fabrication. As the unsaturated dicarboxylic acid, maleic acid is particularly preferable. The preferred formulation comprises an unsaturated dicarboxylic acid, ethylene urea, at least one organic carboxylic acid except unsaturated dicarboxylic acid, at least one basic compound except ethylene urea and water. The formulation can optionally comprise at least one selected from the group consisting of an organic solvent, a chelating agent, a surfactant, and phosphonic acid and/or phosphinic acid.

1 . A semiconductor wafer cleaning formulation for use in semiconductor fabrication comprising an unsaturated dicarboxylic acid, and ethylene urea.  
   
   
       2 . The cleaning formulation according to  claim 1 , wherein the formulation is an aqueous solution.  
   
   
       3 . The cleaning formulation according to  claim 2 , comprising 
 1-9% by weight of an unsaturated dicarboxylic acid; and    1-20% by weight of ethylene urea.    
   
   
       4 . The cleaning formulation according to  claim 2 , further comprising 
 at least one organic carboxylic acid except unsaturated dicarboxylic acid, and    at least one basic compound except ethylene urea.    
   
   
       5 . The cleaning formulation according to  claim 4 , comprising 
 1-9% by weight of an unsaturated dicarboxylic acid;    1-20% by weight of ethylene urea;    1-20% by weight of at least one organic carboxylic acid except unsaturated dicarboxylic acid;    0.1-50% by weight of at least one basic compound except ethylene urea; and    20-90% by weight of water.    
   
   
       6 . The cleaning formulation according to  claim 4 , wherein the unsaturated dicarboxylic acid is selected from the group consisting of maleic acid and citraconic acid.  
   
   
       7 . The cleaning formulation according to  claim 4 , wherein the unsaturated dicarboxylic acid is maleic acid.  
   
   
       8 . The cleaning formulation according to  claim 4 , wherein the organic carboxylic acid is selected from the group consisting of: 
 formic acid (FA),    acetic acid (AA), and    propionic acid (PA).    
   
   
       9 . The cleaning formulation according to  claim 4 , wherein the basic compound is selected from the group consisting of: 
 hydroxyethylpiperazine (HEP),    hydroxypropylpiperazine (HPP),    aminoethylpiperazine (AEP),    aminopropylpiperazine (APP),    hydroxyethylmorpholine (HEM),    hydroxypropylmorpholine (HPM),    aminoethylmorpholine (AEM),    aminopropylmorpholine (APM),    triethanolamine (TEA),    pentamethyldiethylenetriamine (PMDETA),    dimethylaminoethoxyethanol (DMAEE),    aminoethoxyethanol (AEE),    trimethylaminoethylethanolamine (TMAEEA),    trimethylaminopropylethanolamine (TMAPEA),    N-(2-cyanoethyl)ethylenediamine (CEEDA),    N-(2-cyanopropyl)ethylenediamine (CPEDA), and    ammonia (NH 3 ).    
   
   
       10 . The cleaning formulation according to  claim 4 , further comprising at least one selected from the group consisting of: 
 an organic solvent,    a chelating agent,    a surfactant, and    phosphonic acid and/or phosphinic acid.    
   
   
       11 . The cleaning formulation according to  claim 10 , wherein 1-20% by weight of the organic solvent, 0.01-5% by weight of the chelating agent, 0.01-0.2% by weight of the surfactant, and 0.5-5% by weight of phosphonic acid and/or phosphinic acid are contained.  
   
   
       12 . The cleaning formulation according to  claim 10 , wherein the organic solvent is selected from the group consisting of: 
 1,4-butanediol (1,4-BD),    1,3-butanediol (1,3-BD),    ethylene glycol (EG),    propylene glycol (PG),    N-methylpyrrolidone (NMP),    γ-butyrolactone (GBL),    propylene glycol monomethylether (PGME), and    propylene glycol monomethylether acetate (PGMEA).    
   
   
       13 . The cleaning formulation according to  claim 10 , wherein the chelating agent is selected from the group consisting of: 
 ascorbic acid,    gluconic acid,    mannitol,    sorbitol, and    boric acid.    
   
   
       14 . The cleaning formulation according to  claim 10 , wherein the surfactant is a C 1-10 alkyl glucoside.  
   
   
       15 . A method for cleaning a semiconductor wafer comprising: 
 cleaning the wafer by using a chemical formulation comprising an unsaturated dicarboxylic acid, and ethylene urea in semiconductor fabrication.    
   
   
       16 . The method according to  claim 15 , wherein the formulation is an aqueous solution.  
   
   
       17 . The method according to  claim 16 , wherein the formulation comprises 
 1-9% by weight of an unsaturated dicarboxylic acid; and    1-20% by weight of ethylene urea.    
   
   
       18 . The method according to  claim 16 , wherein the formulation further comprises: 
 at least one organic carboxylic acid except unsaturated dicarboxylic acid, and    at least one basic compound except ethylene urea.    
   
   
       19 . The method according to  claim 18 , wherein the formulation comprises: 
 1-9% by weight of an unsaturated dicarboxylic acid;    1-20% by weight of ethylene urea;    1-20% by weight of at least one organic carboxylic acid except unsaturated dicarboxylic acid;    0.1-50% by weight of at least one basic compound except ethylene urea; and    20-90% by weight of water.    
   
   
       20 . The method according to  claim 18 , wherein the unsaturated dicarboxylic acid is selected from the group consisting of maleic acid and citraconic acid.  
   
   
       21 . The method according to  claim 18 , wherein the unsaturated dicarboxylic acid is maleic acid.  
   
   
       22 . The method according to  claim 18 , wherein the organic carboxylic acid is selected from the group consisting of: 
 formic acid (FA),    acetic acid (AA), and    propionic acid (PA).    
   
   
       23 . The method according to  claim 18 , wherein the basic compound is selected from the group consisting of: 
 hydroxyethylpiperazine (HEP),    hydroxypropylpiperazine (HPP),    aminoethylpiperazine (AEP),    aminopropylpiperazine (APP),    hydroxyethylmorpholine (HEM),    hydroxypropylmorpholine (HPM),    aminoethylmorpholine (AEM),    aminopropylmorpholine (APM),    triethanolamine (TEA),    pentamethyldiethylenetriamine (PMDETA),    dimethylaminoethoxyethanol (DMAEE),    aminoethoxyethanol (AEE),    trimethylaminoethylethanolamine (TMAEEA),    trimethylaminopropylethanolamine (TMAPEA),    N-(2-cyanoethyl)ethylenediamine (CEEDA),    N-(2-cyanopropyl)ethylenediamine (CPEDA), and    ammonia (NH 3 ).    
   
   
       24 . The method according to  claim 18 , wherein the formulation further comprises at least one selected from the group consisting of: 
 an organic solvent,    a chelating agent,    a surfactant, and    phosphonic acid and/or phosphinic acid.    
   
   
       25 . The method according to  claim 24 , wherein 1-20% by weight of the organic solvent, 0.01-5% by weight of the chelating agent, 0.01-0.2% by weight of the surfactant, and 0.5-5% by weight of phosphonic acid and/or phosphinic acid are contained.  
   
   
       26 . The method according to  claim 24 , wherein the organic solvent is selected from the group consisting of: 
 1,4-butanediol (1,4-BD),    1,3-butanediol (1,3-BD),    ethylene glycol (EG),    propylene glycol (PG),    N-methylpyrrolidone (NMP),    γ-butyrolactone (GBL),    propylene glycol monomethylether (PGME), and    propylene glycol monomethylether acetate (PGMEA).    
   
   
       27 . The method according to  claim 24 , wherein the chelating agent is selected from the group consisting of: 
 ascorbic acid,    gluconic acid,    mannitol,    sorbitol, and    boric acid.    
   
   
       28 . The method according to  claim 24 , wherein the surfactant is a C 1-10 alkyl glucoside.  
   
   
       29 . A method for cleaning a semiconductor wafer comprising: 
 cleaning the wafer by using a chemical formulation comprising an unsaturated dicarboxylic acid, and ethylene urea, in a cleaning process after a following process: 
 (i) making via hole;  
 (ii) making trench;  
 (iii) punching of etch stopper layer; or  
 (iv) CMP (chemical mechanical polishing) process.  
   
   
   
       30 . The method according to  claim 29 , wherein the formulation is an aqueous solution.  
   
   
       31 . The method according to  claim 30 , wherein the formulation comprises 
 1-9% by weight of an unsaturated dicarboxylic acid; and    1-20% by weight of ethylene urea.    
   
   
       32 . The method according to  claim 30 , wherein the formulation further comprises: 
 at least one organic carboxylic acid except unsaturated dicarboxylic acid, and    at least one basic compound except ethylene urea.    
   
   
       33 . The method according to  claim 32 , wherein the formulation comprises: 
 1-9% by weight of an unsaturated dicarboxylic acid;    1-20% by weight of ethylene urea;    1-20% by weight of at least one organic carboxylic acid except unsaturated dicarboxylic acid;    0.1-50% by weight of at least one basic compound except ethylene urea; and    20-90% by weight of water.    
   
   
       34 . The method according to  claim 32 , wherein the unsaturated dicarboxylic acid is selected from the group consisting of maleic acid and citraconic acid.  
   
   
       35 . The method according to  claim 32 , wherein the unsaturated dicarboxylic acid is maleic acid.  
   
   
       36 . The method according to  claim 32 , wherein the organic carboxylic acid is selected from the group consisting of: 
 formic acid (FA),    acetic acid (AA), and    propionic acid (PA).    
   
   
       37 . The method according to  claim 32 , wherein the basic compound is selected from the group consisting of: 
 hydroxyethylpiperazine (HEP),    hydroxypropylpiperazine (HPP),    aminoethylpiperazine (AEP),    aminopropylpiperazine (APP),    hydroxyethylmorpholine (HEM),    hydroxypropylmorpholine (HPM),    aminoethylmorpholine (AEM),    aminopropylmorpholine (APM),    triethanolamine (TEA),    pentamethyldiethylenetriamine (PMDETA),    dimethylaminoethoxyethanol (DMAEE),    aminoethoxyethanol (AEE),    trimethylaminoethylethanolamine (TMAEEA),    trimethylaminopropylethanolamine (TMAPEA),    N-(2-cyanoethyl)ethylenediamine (CEEDA),    N-(2-cyanopropyl)ethylenediamine (CPEDA), and    ammonia (NH 3 ).    
   
   
       38 . The method according to  claim 32 , wherein the formulation further comprises at least one selected from the group consisting of: 
 an organic solvent,    a chelating agent,    a surfactant, and    phosphonic acid and/or phosphinic acid.    
   
   
       39 . The method according to  claim 38 , wherein 1-20% by weight of the organic solvent, 0.01-5% by weight of the chelating agent, 0.01-0.2% by weight of the surfactant, and 0.5-5% by weight of phosphonic acid and/or phosphinic acid are contained.  
   
   
       40 . The method according to  claim 38 , wherein the organic solvent is selected from the group consisting of: 
 1,4-butanediol (1,4-BD),    1,3-butanediol (1,3-BD), ethylene glycol (EG),    propylene glycol (PG),    N-methylpyrrolidone (NMP),    γ-butyrolactone (GBL),    propylene glycol monomethylether (PGME), and    propylene glycol monomethylether acetate (PGMEA).    
   
   
       41 . The method according to  claim 38 , wherein the chelating agent is selected from the group consisting of: 
 ascorbic acid,    gluconic acid,    mannitol,    sorbitol, and    boric acid.    
   
   
       42 . The method according to  claim 38 , wherein the surfactant is a C 1-10 alkyl glucoside.