Separation-material composition for photo-resist and manufacturing method of semiconductor device

Abstract

One example of a separation-material composition for a photo-resist according to the present invention comprises 5.0 weight % of sulfamic acid, 34.7 weight % of H 2 O, 0.3 weight % of ammonium 1-hydrogen difluoride, 30 weight % of N,N-dimethylacetamide and 30 weight % of diethylene glycol mono-n-buthyl ether. Another example of a separation-material composition for a photo-resist according to the present invention comprises 1-hydroxyethylidene-1, 3.0 weight % of 1-diphosphonic acid, 0.12 weight % of ammonium fluoride, 48.38 weight % of H 2 O and 48.5 weight % of diethylene glycol mono-n-buthyl ether. The separation-material composition for the photo-resist is mainly used for a medicinal liquid washing liquid/scientific liquid in order to remove the photo-resist residuals and the by-product polymer after an ashing process of a photo-resist mask. It can propose a separation-material composition for a photo-resist such that the photo-resist residuals and the by-product polymer are easily removed after a dry etching process and at the same time the low dielectric-constant insulation film is avoided from erosion and oxidization.

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       8 . A manufacturing method of a semiconductor device comprising: 
 a process for forming a photo-resist mask having a photo-resist pattern on an under-layer and for processing said under-layer subsequently by using said photo-resist mask, and 
 a washing process for washing processing said processed under-layer by using a separation-material composition for a photo-resist such that at least one of said photo-resist mask residuals and the by-product polymer is separated and removed,  
 wherein a separation-material composition for a photo-resist which includes at least sulfamic acid (NH 2 SO 3 H) and water is used as said separation-material composition for the photo-resist.  
   
   
   
       9 . A manufacturing method of a semiconductor device comprising: 
 a process for forming a photo-resist mask having a photo-resist pattern on an under-layer and for processing said under-layer subsequently by using said photo-resist mask, and 
 an ashing process for ashing processing so as to remove said photo-resist mask, and  
 a washing process for washing processing said processed under-layer by using a separation-material composition for a photo-resist such that at least one of said photo-resist mask residuals and the by-product polymer residuals is separated and removed,  
 wherein a separation-material composition for a photo-resist which includes at least sulfamic acid (NH 2 SO 3 H) and water is used as said separation-material composition for the photo-resist.  
   
   
   
       10 . A manufacturing method of a semiconductor device according to  claim 8  or  9 , wherein in the process for processing said under-layer, an insulation film is film-made as said under-layer on a semiconductor substrate and a photo-resist mask having a photo-resist pattern of a wiring groove or a connecting aperture as said photo-resist mask is subsequently formed on said insulation film, and said insulation film is dry-etching processed, such that a wiring groove or a connecting aperture having a predetermined pattern is formed.  
   
   
       11 . A manufacturing method of a semiconductor device according to  claim 10 , wherein a silicon oxide film is film-made as said insulation film.  
   
   
       12 . A manufacturing method of a semiconductor device according to  claim 10 , wherein a low dielectric-constant insulation film or a stacked insulation film having a low dielectric-constant insulation film is film-made as said insulation film.  
   
   
       13 . A manufacturing method of a semiconductor device according to  claim 8  or  9 , wherein in the process for processing said under-layer, an etching-stopper layer having a metal diffusion prohibiting effect is film-made as said under-layer on a lower layer wiring, a photo-resist mask having a photo-resist pattern of a connecting aperture is subsequently formed as said photo-resist mask on the etching-stopper layer, and a connecting aperture which reaches the lower layer wiring is formed on the etching-stopper layer by subsequently dry-etching the etching-stopper layer.  
   
   
       14 . A manufacturing method of a semiconductor device according to  claim 13 , wherein a silicon nitride film or a silicon carbide film is film-made as said etching-stopper layer having the metal diffusion prohibiting effect.  
   
   
       15 . A manufacturing method of a semiconductor device according to  claim 8  or  9 , wherein in the process for processing said under-layer, a metal film is film-made as the under-layer, a photo-resist mask having a photo-resist pattern of a wiring is subsequently formed as said photo-resist mask on said metal film, and a wiring having a predetermined pattern is subsequently formed by dry-etching said metal film.  
   
   
       16 . A manufacturing method of a semiconductor device according to  claim 15 , wherein an aluminum film or an aluminum-alloy film is film-made as said metal film.  
   
   
       17 . A manufacturing method of a semiconductor device comprising: 
 a process for film-making a hard mask forming layer on an under-layer;    a process for forming a photo-resist mask having a photo-resist pattern on said hard mask forming layer, for subsequently etching said hard mask forming layer by using said photo-resist mask and for forming a hard mask transferred with said photo-resist pattern;    a process for subsequently processing said under-layer by using said hard mask; and    a washing process for washing processing said processed under-layer by using a separation-material composition for a photo-resist such that at least one of said photo-resist mask residuals and the by-product polymer is separated and removed;    wherein a separation-material composition for a photo-resist which includes at least sulfamic acid (NH 2 SO 3 H) and water is used as said separation-material composition for the photo-resist.    
   
   
       18 . A manufacturing method of a semiconductor device according to one of claims  8 ,  9  and  17 , wherein in said washing process, a photo-resist separation-material composition for a photo-resist which includes water-soluble organic solvent additively to sulfamic acid and water is used as said separation-material composition for the photo-resist.  
   
   
       19 . A manufacturing method of a semiconductor device according to  claim 17 , wherein in said washing process, a photo-resist separation-material composition which further includes salt formed by hydroacid fluoride and a base which does not include a metal additively to said sulfamic acid, water and a water-soluble organic solvent is used as said separation-material composition for the photo-resist.  
   
   
       20 . A manufacturing method of a semiconductor device according to  claim 19 , wherein said salt formed by hydroacid fluoride and a base which does not include a metal has a molar ratio in a range from 1:0.1 or more to 1:10 or less between said hydroacid fluoride and said base which does not include a metal.  
   
   
       21 . A separation-material composition for a photo-resist which is used when a photo-resist mask having a photo-resist pattern is formed on an under-layer, said under-layer is subsequently processed by using said photo-resist mask and said photo-resist mask is removed thereafter, wherein the separation-material composition for the photo-resist is a water solution including at least phosphonic acid (H 2 PHO 3 ) and a water-soluble organic solvent.  
   
   
       22 . A separation-material composition for a photo-resist according to  claim 21 , wherein the content of said phosphonic acid is in a range from 0.1 weight % or more to 30 weight % or less and the content of said organic solvent is in a range from 30 weight % or more to 95 weight % or less.  
   
   
       23 . A separation-material composition for a photo-resist according to  claim 21  or  22 , further including salt formed by hydroacid fluoride and a base which does not include a metal additively to said water solution including the phosphonic acid (H 2 PHO 3 ) and the water-soluble organic solvent.  
   
   
       24 . A separation-material composition for a photo-resist according to  claim 23 , wherein said salt formed by hydroacid fluoride and a base which does not include a metal has a molar ratio in a range from 1:0.1 or more to 1:10 or less between said hydroacid fluoride and said base which does not include a metal.  
   
   
       25 . A separation-material composition for a photo-resist according to  claim 24 , wherein the content of the salt formed by hydroacid fluoride and a base which does not include a metal is in a range from 0.01 weight % or more to 10 weight % or less.  
   
   
       26 . A separation-material composition for a photo-resist according to one of claims  25 , wherein the pH of said water solution including the phosphonic acid (H 2 PHO 3 ) and the water-soluble organic solvent is selected to be less than or equal to 8.  
   
   
       27 . A manufacturing method of a semiconductor device comprising: 
 a process for forming a photo-resist mask having a photo-resist pattern on an under-layer and for processing said under-layer subsequently by using said photo-resist mask, and 
 a washing process for washing processing said processed under-layer by using a separation-material composition for a photo-resist such that at least one of said photo-resist mask residuals and the by-product polymer is separated and removed,  
 wherein a separation-material composition for a photo-resist which is a water solution including at least phosphonic acid (H 2 PHO 3 ) and a water-soluble organic solvent is used as said separation-material composition for the photo-resist.  
   
   
   
       28 . A manufacturing method of a semiconductor device comprising: 
 a process for forming a photo-resist mask having a photo-resist pattern on an under-layer and for processing said under-layer subsequently by using said photo-resist mask, and 
 an ashing process for ashing processing so as to remove said photo-resist mask, and  
 a washing process for washing processing said processed under-layer by using a separation-material composition for a photo-resist such that at least one of said photo-resist mask residuals and the by-product polymer residuals is separated and removed,  
 wherein a separation-material composition for a photo-resist which is a water solution including at least phosphonic acid (H 2 PHO 3 ) and a water-soluble organic solvent is used as said separation-material composition for the photo-resist.  
   
   
   
       29 . A manufacturing method of a semiconductor device according to  claim 27  or  28 , wherein in the process for processing said under-layer, an insulation film is film-made as said under-layer on a semiconductor substrate and a photo-resist mask having a photo-resist pattern of a wiring groove or a connecting aperture as said photo-resist mask is subsequently formed on said insulation film, and said insulation film is dry-etching processed such that a wiring groove or a connecting aperture having a predetermined pattern is formed.  
   
   
       30 . A manufacturing method of a semiconductor device according to  claim 29 , wherein a silicon oxide film is film-made as said insulation film.  
   
   
       31 . A manufacturing method of a semiconductor device according to  claim 29 , wherein a low dielectric-constant insulation film or a stacked insulation film having a low dielectric-constant insulation film is film-made as said insulation film.  
   
   
       32 . A manufacturing method of a semiconductor device according to  claim 27  or  28 , wherein in the process for processing said under-layer, an etching-stopper layer having a metal diffusion prohibiting effect is film-made as said under-layer on a lower layer wiring, a photo-resist mask having a photo-resist pattern of a connecting aperture is subsequently formed as said photo-resist mask on the etching-stopper layer, and a connecting aperture which reaches the lower layer wiring is formed on the etching-stopper layer by subsequently dry-etching the etching-stopper layer.  
   
   
       33 . A manufacturing method of a semiconductor device according to  claim 32 , wherein a silicon nitride film or a silicon carbide film is film-made as said etching-stopper layer having the metal diffusion prohibiting effect.  
   
   
       34 . A manufacturing method of a semiconductor device according to  claim 27  or  28 , wherein in the process for processing said under-layer, a metal film is film-made as the under-layer, a photo-resist mask having a photo-resist pattern of a wiring is subsequently formed as said photo-resist mask on said metal film, and a wiring having a predetermined pattern is subsequently formed by dry-etching said metal film.  
   
   
       35 . A manufacturing method of a semiconductor device according to  claim 34 , wherein an aluminum film or an aluminum-alloy film is film-made as said metal film.  
   
   
       36 . A manufacturing method of a semiconductor device comprising: 
 a process for film-making a hard mask forming layer on an under-layer;    a process for forming a photo-resist mask having a photo-resist pattern on said hard mask forming layer, for subsequently etching said hard mask forming layer by using said photo-resist pattern and for forming a hard mask transferred with said photo-resist pattern;    a process for subsequently processing said under-layer by using said hard mask; and    a washing process for washing processing said processed under-layer by using a separation-material composition for a photo-resist such that at least one of said photo-resist mask residuals and the by-product polymer is separated and removed;    wherein a separation-material composition for a photo-resist which is a water solution including at least phosphonic acid (H 2 PHO 3 ) and a water-soluble organic solvent is used as said separation-material composition for the photo-resist.    
   
   
       37 . A manufacturing method of a semiconductor device according to  claim 36 , wherein in said washing process, a photo-resist separation-material composition which further includes salt formed by hydroacid fluoride and a base which does not include a metal additively to said water solution including at least phosphonic acid (H 2 PHO 3 ) and a water-soluble organic solvent is used as said separation-material composition for the photo-resist.  
   
   
       38 . A manufacturing method of a semiconductor device according to  claim 37 , wherein said salt formed by hydroacid fluoride and a base which does not include a metal has a molar ratio in a range from 1:0.1 or more to 1:10 or less between said hydroacid fluoride and said a base which does not include a metal.  
   
   
       39 . (canceled)