Substrate surface cleaning liquid medium and cleaning method

Abstract

A substrate surface cleaning liquid medium and a cleaning method using the cleaning liquid medium are capable of removing finely particulate contaminants more efficiently than conventional techniques from substrates for devices in the production of semiconductor devices, display devices, etc., which cleaning liquid medium contains the following ingredients (A), (B), (C), and (D), has a pH of 9 or higher, and a content of ingredient (C) of 0.01 to 4% by weight: (A) an ethylene oxide addition type surfactant which has an optionally substituted hydrocarbon group and a polyoxyethylene group in the same molecular structure and in which the ratio of the number of carbon atoms contained in the hydrocarbon group (m) to the number of oxyethylene groups in the polyoxyethylene group (n), m/n, is m/n≦1.5, (B) an alkali ingredient, (C) hydrogen peroxide, and (D) water.

1 - 15 . (canceled)  
   
   
       16 . A semiconductor substrate surface cleaning liquid medium consisting essentially of the ingredients (A), (B), (C), and (D), wherein 
 (A) is an ethylene oxide addition type surfactant which has an optionally substituted hydrocarbon group and a polyoxyethylene group in the same molecular structure and in which the ratio of the number of carbon atoms contained in the hydrocarbon group (m) to the number of oxyethylene groups in the polyoxyethylene group (n) is 1.5 or less, wherein ethylene oxide addition type surfactant is selected from the group consisting of at least one polyoxyalkylene alkyl ether, at least one polyoxalkylene fatty acid ester, at least one polyoxyalkylene alkyl amine, at least one polyoxylalkylene alkly ether sulfate, and combinations thereof;    (B) is an alkali ingredient;    (C) is hydrogen peroxide; and    (D) is water;    wherein the substrate surface cleaning liquid medium has a pH of from about 10.5 to 11.5, an ingredient (A) content ranging from 0.0001% to 0.01% by weight, and an ingredient (C) content ranging from 0.01 to 4% by weight.    
   
   
       17 . The semiconductor substrate surface cleaning liquid medium of  claim 16 , wherein m/n is 0.5≦m/n≦1.5.  
   
   
       18 . The semiconductor substrate surface cleaning liquid medium of  claim 16 , wherein ingredient (B) is represented by the following general formula:  
       (R 1 ) 4 N + OH −   (1)  
     wherein R 1  represents a hydrogen atom or an alkyl group which may have one or more substituents selected from the group consisting of a hydroxy group, an alkoxy group and a halogen atom, provided that the four R 1 s may be the same or different.  
   
   
       19 . The semiconductor substrate surface cleaning liquid medium of  claim 18 , wherein ingredient (B) is ammonium hydroxide.  
   
   
       20 . The semiconductor substrate surface cleaning liquid medium of  claim 16 , wherein the number of moles of oxyethylene groups added (n) in ingredient (A) is 10≦n≦50.  
   
   
       21 . The semiconductor substrate surface cleaning liquid medium of  claim 16 , wherein ingredient (A) is a polyoxyethylene alkyl ether.  
   
   
       22 . The semiconductor substrate surface cleaning liquid medium of  claim 16 , wherein the ratio of the content of ingredient (A), a, to the content of ingredient (C), c, is 1/3000≦a/c≦1/20.  
   
   
       23 . The semiconductor substrate surface cleaning liquid medium of  claim 18 , further comprising a complexing agent.  
   
   
       24 . The semiconductor substrate surface cleaning liquid medium of  claim 16  which, when used for cleaning a semiconductor substrate surface, attains a percentage removal of particles of 94% or higher after the cleaning with respect to the removal of particles having a particle diameter of 0.06 μm or larger present on the semiconductor substrate surface, and which, when used for cleaning a semiconductor substrate surface having a silicon thermal oxide film thereon, etches the silicon thermal oxide film to a depth of 1 nm or less.  
   
   
       25 . The semiconductor substrate surface cleaning liquid medium of  claim 24 , wherein the percentage removal of particles is 94% or higher when the semiconductor substrate surface cleaning liquid medium in contact with the semiconductor substrate surface has a temperature of 60° C. or lower.  
   
   
       26 . A semiconductor substrate surface cleaning liquid medium consisting essentially of the ingredients (A), (B), (C), (D), and (E) wherein: 
 (A) is an ethylene oxide addition type surfactant which has an optionally substituted hydrocarbon group and a polyoxyethylene group in the same molecular structure and in which the ratio of the number of carbon atoms contained in the hydrocarbon group (m) to the number of oxyethylene groups in the polyoxyethylene group (n) is 1.5 or less, wherein ethylene oxide addition type surfactant is selected from the group consisting of at least one polyoxyalkylene alkyl ether, at least one polyoxalkylene fatty acid ester, at least one polyoxyalkylene alkyl amine, at least one polyoxylalkylene alkly ether sulfate, and combinations thereof;    (B) is an alkali ingredient;    (C) is hydrogen peroxide;    (D) is water; and    (E) is a complexing agent;    wherein the substrate surface cleaning liquid medium has a pH ranging from about 10.5 to 11.5 and an ingredient (C) content ranging from 0.01 to 4% by weight.    
   
   
       27 . The semiconductor substrate surface cleaning liquid medium of  claim 26 , wherein m/n is 0.5≦m/n≦1.5.  
   
   
       28 . The semiconductor substrate surface cleaning liquid medium of  claim 26 , wherein ingredient (B) is represented by the following general formula:  
       (R 1 ) 4 N = OH −   (1)  
     wherein R 1  represents a hydrogen atom or an alkyl group which may have one or more substituents selected from the group consisting of a hydroxy group, an alkoxy group and a halogen atom, provided that the four R 1 s may be the same or different, provided that (R 1 ) 4 N + OH −  is not ammonium hydroxide.  
   
   
       29 . The semiconductor substrate surface cleaning liquid medium of  claim 26 , wherein the number of moles of oxyethylene groups added (n) in ingredient (A) is 10≦n≦50.  
   
   
       30 . The semiconductor substrate surface cleaning liquid medium of  claim 26 , wherein ingredient (A) is a polyoxyethylene alkyl ether.  
   
   
       31 . The semiconductor substrate surface cleaning liquid medium of  claim 26 , wherein the content of ingredient (A) ranges from 0.0001 to 0.5% by weight.  
   
   
       32 . The semiconductor-substrate surface cleaning liquid medium of  claim 26 , wherein the ratio of the content of ingredient (A), a, to the content of ingredient (C), c, is 1/3000≦a/c≦1/20.  
   
   
       33 . The semiconductor substrate surface cleaning liquid medium as claimed in  claim 16 , wherein the content of ingredient (A) is from 0.0003 to 0.1% by weight.  
   
   
       34 . The semiconductor substrate surface cleaning liquid medium of  claim 26 , wherein the complexing agent is ethylenediaminedi-o-hydroxyphenylacetic acid.  
   
   
       35 . The semiconductor substrate surface cleaning liquid medium of  claim 16 , wherein the pH is about 10.5.  
   
   
       36 . The semiconductor substrate surface cleaning liquid medium of  claim 26 , wherein the pH is about 10.5