Method for etching high dielectric constant materials and for cleaning deposition chambers for high dielectric constant materials

Abstract

A process for the removal of a substance from a substrate for etching and/or cleaning applications is disclosed herein. In one embodiment, there is provided a process for removing a substance having a dielectric constant greater than silicon dioxide from a substrate by reacting the substance with a reactive agent that comprises at least one member from the group consisting a halogen-containing compound, a boron-containing compound, a hydrogen-containing compound, nitrogen-containing compound, a chelating compound, a carbon-containing compound, a chlorosilane, a hydrochlorosilane, or an organochlorosilane to form a volatile product and removing the volatile product from the substrate to thereby remove the substance from the substrate.

1 . A process for cleaning a substance from a reactor surface, said process comprising: 
 providing a reactor containing the reactor surface, wherein: (a) the reactor surface is at least partially coated with a film of the substance; (b) the substance is at least one member selected from the group consisting of a transition metal oxide, a transition metal silicate, a Group 13 metal oxide, a Group 13 metal silicate, a nitrogen containing Group 13 metal oxide, a nitrogen containing Group 13 metal silicate, a nitrogen containing transition metal oxide, a nitrogen containing transition metal silicate, or a laminate comprising at least one layer selected from the group consisting of a transition metal oxide, a transition metal silicate, a Group 13 metal oxide, a Group 13 metal silicate, a nitrogen containing transition metal oxide, a nitrogen containing transition metal silicate, a nitrogen containing Group 13 metal oxide, or a nitrogen containing Group 13 metal silicate; and (c) the substance has a dielectric constant greater than the dielectric constant of silicon dioxide;    reacting the substance with a reactive agent to form a volatile product, wherein the reactive agent comprises at least one member selected from the group consisting of a halogen-containing compound; a boron-containing compound, a carbon-containing compound, a hydrogen-containing compound, a nitrogen-containing compound, a chelating compound, a chlorosilane compound, a hydrochlorosilane compound, or an organochlorosilane compound; and    removing the volatile product from the reactor to thereby remove the substance from the surface.    
     
     
         2 . The process of  claim 1 , wherein the reactor is an atomic layer deposition reactor.  
     
     
         3 . The process of  claim 1 , wherein the substance is at least one member selected from the group consisting of Al 2 O 3 , HfO 2 , ZrO 2 , HfSi x O y , and ZrSi x O y  wherein x is a number greater than 0 and y is 2x +2, and any of the aforementioned compounds containing nitrogen.  
     
     
         4 . The process of  claim 1  wherein the reactive agent is at least one member selected from the group consisting of BCl 3 , COCl 2 , HCl, Cl 2 , ClF 3 , and NF z Cl 3-z , where z is an integer from 0 to 2.  
     
     
         5 . The process of  claim 4 , wherein the reactive agent is COCl 2  formed by an in situ reaction of CO and Cl 2 .  
     
     
         6 . The process of  claim 4 , wherein the reactive agent is BCl 3 .  
     
     
         7 . The process of  claim 1  wherein the reactive agent is a carbon-containing compound having the formula C x H y Cl z , wherein x is a number ranging from 1 to 6, y is a number ranging from 0 to 13, and z is a number ranging 1 from 14.  
     
     
         8 . The process of  claim 1 , wherein the reactive agent is conveyed to the substance from a gas cylinder, a safe delivery system or a vacuum delivery system.  
     
     
         9 . The process of  claim 1 , wherein the reactive agent is formed in situ by a point-of-use generator.  
     
     
         10 . The process of  claim 1 , wherein the substance is contacted with the reactive agent diluted with an inert gas diluent.  
     
     
         11 . A process for removing a substance from at least a portion of the surface of a reaction chamber, the process comprising: 
 providing a reaction chamber wherein at least a portion of the surface is at least partially coated with the substance and wherein the substance has a dielectric constant of 4.1 or greater and is at least one member of the group consisting of a transition metal oxide, a transition metal silicate, a Group 13 metal oxide, a Group 13 metal silicate, a nitrogen containing Group 13 metal oxide, a nitrogen containing Group 13 metal silicate, a nitrogen containing transition metal oxide, a nitrogen containing transition metal silicate, or a laminate comprising at least one layer of the group consisting of a transition metal oxide, a transition metal silicate, a Group 13 metal oxide, a Group 13 metal silicate, a nitrogen containing Group 13 metal oxide, a nitrogen containing Group 13 metal silicate, a nitrogen containing transition metal oxide, a nitrogen containing transition metal silicate;    introducing a reactive agent into the reaction chamber wherein the reactive agent comprises at least one member selected from the group consisting of a halogen-containing compound; a boron-containing compound, a carbon-containing compound, a hydrogen-containing compound, a nitrogen-containing compound, a chelating compound, a chlorosilane compound, a hydrochlorosilane compound, or an organochlorosilane compound;    exposing the reactive agent to one or more energy sources sufficient to react the substance with the reactive agent and form a volatile product; and    removing the volatile product from the reaction chamber.    
     
     
         12 . The process of  claim 11 , wherein the reactive agent is conveyed to the substance from a gas cylinder, a safe delivery system or a vacuum delivery system.  
     
     
         13 . The process of  claim 11 , wherein the reactive agent is formed in situ by a point-of-use generator.  
     
     
         14 . The process of  claim 11 , wherein the substance is contacted with the reactive agent diluted with an inert gas diluent.  
     
     
         15 . The process of  claim 11  wherein the reactive agent is deposited onto a nonreactive support.  
     
     
         16 . The process of  claim 11  wherein the reactive agent is exposed to one or more energy sources and the exposing step is conducted prior to the introducing step.  
     
     
         17 . The process of  claim 11  wherein the reactive agent is exposed to one or more energy sources and the exposing step is conducted during at least a portion of the introducing step.  
     
     
         18 . The process of  claim 11  wherein a temperature of the exposing step is at least 150° C.  
     
     
         19 . The process of  claim 11  wherein a pressure of the exposing step is at least 10 mTorr.  
     
     
         20 . An apparatus for removing a substance from at least one surface of a reactor, the apparatus comprising: 
 an at least one reactive agent selected from the group consisting of a halogen-containing compound; a boron-containing compound, a carbon-containing compound, a hydrogen-containing compound, a nitrogen-containing compound, a chelating compound, a chlorosilane compound, a hydrochlorosilane compound, or an organochlorosilane compound; and    a non-reactive support having the at least one reactive agent deposited thereupon.    
     
     
         21 . A mixture for removing a substance from at least one surface of a reactor, the mixture comprising: 
 an at least one reactive agent selected from the group consisting of a halogen-containing compound; a boron-containing compound, a carbon-containing compound, a hydrogen-containing compound, a nitrogen-containing compound, a chelating compound, a chlorosilane compound, a hydrochlorosilane compound, or an organochlorosilane compound; and    an inert diluent.    
     
     
         22 . A process for removing a substance from an at least one surface of a substrate, said process comprising: 
 providing the substrate wherein the substrate is at least partially coated with a film of the substance that is at least one member selected from the group consisting of a transition metal oxide, a transition metal silicate, a Group 13 metal oxide other than Al 2 O 3 , a Group 13 metal silicate, a nitrogen containing Group 13 metal oxide, a nitrogen containing Group 13 metal silicate, a nitrogen containing transition metal oxide, a nitrogen containing transition metal silicate, or a laminate comprising at least one layer of the group consisting of a transition metal oxide, a transition metal silicate, a Group 13 metal oxide, a Group 13 metal silicate, a nitrogen containing Group 13 metal oxide, a nitrogen containing Group 13 metal silicate, a nitrogen containing transition metal oxide, or a nitrogen containing transition metal silicate; and wherein the substance has a dielectric constant greater than a dielectric constant of silicon dioxide;    reacting the substance with a reactive agent to form a volatile product, wherein the reactive agent comprises at least one member from the group consisting of a halogen-containing compound ; a boron-containing compound, a carbon-containing compound, a hydrogen-containing compound, a nitrogen-containing compound, a chelating compound, a chlorosilane compound, a hydrochlorosilane compound, or an organochlorosilane compound; and    removing the volatile product from the substrate to thereby remove the substance from the substrate.    
     
     
         23 . The process of  claim 22 , wherein the substance is at least one member selected from the group consisting of HfO 2 , ZrO 2 , HfSi x O y , ZrSi x O y  where x is greater than 0 and y is 2x +2, Al 2 Si w O z , where w is greater than 0 and z is 2w +3, or any of the aforementioned compounds containing nitrogen.  
     
     
         24 . The process of  claim 22 , wherein the substance is a laminate comprising layers of at least one material selected from the group consisting of a transition metal oxide, a transition metal silicate, a Group 13 metal oxide, a Group 13 metal silicate, a nitrogen containing transition metal oxide, a nitrogen containing transition metal silicate, a nitrogen containing Group 13 metal oxide, or a nitrogen containing Group 13 metal silicate.  
     
     
         25 . The process of  claim 22 , wherein the reactive agent is at least one member selected from the group consisting of BCl 3 , COCl 2 , HCl, Cl 2 , ClF 3 , and NF z Cl 3-z , where z is an integer from 0 to 2.  
     
     
         26 . The process of  claim 25 , wherein the substance is at least one member selected from the group consisting of HfO 2 , ZrO 2 , HfSi x O y , ZrSi x O y , where x is greater than 0 and y is 2x +2, Al 2 Si w O z , where w is greater than 0 and z is 2w +3, or any of the aforementioned compounds containing nitrogen.  
     
     
         27 . The process of  claim 25 , wherein the reactive agent is COCl 2  formed by an in situ reaction of CO and Cl 2 .  
     
     
         28 . The process of  claim 25 , wherein the reactive agent is BCl 3 .  
     
     
         29 . The process of  claim 22  wherein the reactive agent is a carbon-containing compound having the formula C x H y Cl z , wherein x is a number ranging from 1 to 6, y is a number ranging from 0 to 13, and z is a number ranging 1 from 14.  
     
     
         30 . The process of  claim 22  wherein the reactive agent is conveyed to the substance from a gas cylinder, a safe delivery system or a vacuum delivery system.  
     
     
         31 . The process of  claim 22  wherein the reactive agent is formed in situ by a point-of-use generator.  
     
     
         32 . The process of  claim 22  wherein the substance is contacted with the reactive agent diluted with an inert gas diluent.  
     
     
         33 . The process of  claim 22 , wherein the substance is coated on the substrate by atomic layer deposition.