Process and apparatus for cleaning imprinting molds, and process for manufacturing imprinting molds

Abstract

The cleaning process of cleaning an imprinting mold including a release layer coupled via siloxane bonds to a substrate of that release layer includes a first cleaning step and a second cleaning step. In the first cleaning step, the angle of contact of the surface of the release layer with water is made small, and in the second cleaning step, the alkali cleaning agent is brought in contact with the release layer that has gone through the first cleaning step.

1 . A cleaning process for cleaning an imprinting mold including a release layer coupled via siloxane bonds to a substrate of said imprinting mold, comprising:
 a first cleaning step of making small an angle of contact of a surface of said release layer with water, and   a second cleaning step of bringing an alkali cleaning agent in contact with said release layer that has gone through said first cleaning step.   
     
     
         2 . The cleaning process for cleaning an imprinting mold according to  claim 1 , wherein said first cleaning step is such that the angle of contact of the surface of said release layer with water is not greater than 95°. 
     
     
         3 . The cleaning process for cleaning an imprinting mold according to  claim 1 , wherein said first cleaning step includes at least one step of a step of irradiating said release layer with light including a wavelength range of less than 190 nm, a step of irradiating said release layer with light including a wavelength range of 190 nm to 370 nm, a step of applying ashing to said release layer, and a step of irradiating said release layer with electron radiation. 
     
     
         4 . The cleaning process for cleaning an imprinting mold according to  claim 3 , wherein irradiation of said release layer with light including a wavelength range of less than 190 nm in said first cleaning step is implemented such that a dose of light including a wavelength range of less than 190 nm is within a range of 1 to 10,000 ml/cm 2 . 
     
     
         5 . The cleaning process for cleaning an imprinting mold according to  claim 3 , wherein irradiation of said release layer with light including a wavelength range of 190 nm to 370 nm in said first cleaning step is implemented such that a dose of light including a wavelength range of 190 nm to 370 nm is in a range of 1 to 100,000 mJ/cm 2 . 
     
     
         6 . The cleaning process for cleaning an imprinting mold according to  claim 3 , wherein the ashing applied to said release layer in said first cleaning step is implemented with at least one species of active radicals and ions. 
     
     
         7 . The cleaning process for cleaning an imprinting mold according to  claim 6 , wherein the ashing applied to said release layer in said first cleaning step is implemented with at least one species of oxygen radicals, fluorine radicals, argon radicals, oxygen ions, fluorine ions, argon ions, and ozone. 
     
     
         8 . The cleaning process for cleaning an imprinting mold according to  claim 6 , including a moisture removal step prior to said first cleaning step. 
     
     
         9 . A cleaning process for cleaning an imprinting mold including a release layer coupled via siloxane bonds to a substrate of said imprinting mold, comprising:
 a first cleaning step of cleaving water repellent groups contained in a surface of said release layer, and   a second cleaning step of bringing an alkali cleaning agent in contact with said release layer that has gone through said first cleaning step.   
     
     
         10 . The cleaning process for cleaning an imprinting mold according to  claim 9 , wherein said first cleaning step includes at least one step of a step of irradiating said release layer with light including a wavelength range of less than 190 nm, a step of irradiating said release layer with light including a wavelength range of 190 nm to 370 nm, a step of applying ashing to said release layer, and a step of irradiating said release layer with electron radiation. 
     
     
         11 . The cleaning process for cleaning an imprinting mold according to  claim 10 , wherein irradiation of said release layer with light including a wavelength range of less than 190 nm in said first cleaning step is implemented such that a dose of light including a wavelength range of less than 190 nm is within a range of 1 to 10,000 mJ/cm 2 . 
     
     
         12 . The cleaning process for cleaning an imprinting mold according to  claim 10 , wherein irradiation of said release layer with light including a wavelength range of 190 nm to 370 nm in said first cleaning step is implemented such that a dose of light including a wavelength range of 190 nm to 370 nm is in a range of 1 to 100,000 mJ/cm 2 . 
     
     
         13 . The cleaning process for cleaning an imprinting mold according to  claim 10 , wherein the ashing applied to said release layer in said first cleaning step is implemented with at least one species of active radicals and ions. 
     
     
         14 . The cleaning process for cleaning an imprinting mold according to  claim 13 , wherein the ashing applied to said release layer in said first cleaning step is implemented with at least one species of oxygen radicals, fluorine radicals, argon radicals, oxygen ions, fluorine ions, argon ions, and ozone. 
     
     
         15 . The cleaning process for cleaning an imprinting mold according to  claim 9 , further comprising a moisture removal step prior to said first cleaning step. 
     
     
         16 . A cleaning apparatus for cleaning an imprinting mold including a release layer coupled via siloxane bonds to a substrate of said imprinting mold, comprising:
 a first cleaning unit of applying hydrophilic treatment to a surface of said release layer,   a second cleaning unit of applying alkali cleaning to the imprinting mold to which the hydrophilic treatment has been applied in said first cleaning unit,   at least one measuring unit of measuring a surface state of said imprinting mold,   a first judgment unit of, based on the result of measurement in said measuring unit, judging whether or not the surface of said release layer to which the hydrophilic treatment has been applied in said first cleaning unit can be alkali-cleaned, and a second judgment unit of, based on the result of measurement in said measuring unit, judging whether or not said release layer is removed from the surface of the imprinting mold to which the alkali cleaning has been applied in said second cleaning unit.   
     
     
         17 . The cleaning apparatus for cleaning an imprinting mold according to  claim 16 , wherein:
 said first cleaning unit is operable to make small a angle of contact of a surface of said release layer with water, thereby implementing said hydrophilic treatment,   said measuring unit is operable to measure an angle of contact with water,   said first judgment unit is operable to judge alkali cleaning as being to be done when the angle of contact with water of the surface of said release layer to which the hydrophilic treatment has been applied in said first cleaning unit is not greater than a first reference value, and   said second judgment unit is operable to judge said release layer as being removed when the angle of contact with water of the surface of the imprinting mold to which the alkali cleaning has been applied in said second cleaning unit is not greater than a second reference value set less than said first reference value.   
     
     
         18 . The cleaning apparatus for cleaning an imprinting mold according to  claim 17  wherein said first cleaning unit includes a light source for implementing irradiation of the surface of said release layer with light, wherein light irradiated out of said light source includes light having a wavelength range of less than 190 nm. 
     
     
         19 . The cleaning apparatus for cleaning an imprinting mold according to  claim 17 , wherein said first cleaning unit includes a light source for implementing irradiation of the surface of said release layer with light, wherein light irradiated out of said light source includes light having a wavelength range of 190 nm to 370 nm. 
     
     
         20 . The cleaning apparatus for cleaning an imprinting mold according to  claim 17 , wherein said first cleaning unit includes a treatment device for applying ashing to the surface of said release layer. 
     
     
         21 . The cleaning apparatus for cleaning an imprinting mold according to  claim 17 , wherein said first cleaning unit includes a device for irradiating the surface of said release layer with electron radiation. 
     
     
         22 . The cleaning apparatus for cleaning an imprinting mold according to  claim 17 , wherein said first reference value is 95°, and said second reference value is an angle that is 2° larger than the angle of contact of said substrate with water before formation of said release layer. 
     
     
         23 . The cleaning apparatus for cleaning an imprinting mold according to  claim 17 , wherein said measuring unit includes a first measuring unit operable to measure the angle of contact with water of the surface of said release layer to which the hydrophilic treatment has been applied in the first cleaning unit, and a second measuring unit operable to measure the angle of contact with water of the surface of the imprinting mold to which the alkali cleaning has been applied in the second cleaning unit, wherein while the angle of contact of the surface of said release layer with water is measured in said first measuring unit, the hydrophilic treatment is applied to the surface of said release layer in said first cleaning unit. 
     
     
         24 . A process for manufacturing an imprinting mold comprising a substrate, an uneven structure positioned on one surface of said substrate, and a release layer coupled via siloxane bonds to said substrate in such a way as to cover at least said uneven structure, comprising:
 a first cleaning step of making a surface of said release layer hydrophilic, and   a second cleaning unit of brining an alkali cleaning agent in contact with said release layer that has gone through said first cleaning step.   
     
     
         25 . A process for manufacturing an imprinting mold comprising a substrate, an uneven structure positioned on one surface of said substrate, and a release layer coupled via siloxane bonds to said substrate in such a way as to cover at least said uneven structure, comprising:
 a cleaning step of removing said release layer, and   a reformation step of forming a fresh release layer coupled via siloxane bonds to said substrate in such a way as to cover at least said uneven structure, wherein said cleaning step comprises a first cleaning step of making small an angle of contact of a surface of said release layer with water, and a second cleaning step of bringing an alkali cleaning agent in contact with said release layer that have gone through said first cleaning step.   
     
     
         26 . The process for manufacturing an imprinting mold according to  claim 25 , wherein a fluoroalkyl- or alkyl-based silane coupling agent is used in said reformation step to form a fresh release layer. 
     
     
         27 . The process for manufacturing an imprinting mold according to  claim 25 , wherein the fresh release layer formed in said reformation step has a thickness of 0.3 to 100 nm. 
     
     
         28 . A process for manufacturing an imprinting mold comprising a substrate, an uneven structure positioned on one surface of said substrate, and a release layer coupled via siloxane bonds to said substrate in such a way as to cover at least said uneven structure, comprising:
 a cleaning step of removing said release layer, and   a reformation step of forming a fresh release layer coupled via siloxane bonds to said substrate in such a way as to cover at least said uneven structure, wherein said cleaning step comprises a first cleaning step of cleaving water repellent groups contained in a surface of said release layer, and a second cleaning step of bringing an alkali cleaning agent in contact with said release layer that has gone through said first cleaning step.   
     
     
         29 . The process for manufacturing an imprinting mold according to  claim 28 , wherein a fluoroalkyl- or alkyl-based silane coupling agent is used in said reformation step to form a fresh release layer. 
     
     
         30 . The process for manufacturing an imprinting mold according to  claim 28 , wherein the fresh release layer formed in said reformation step has a thickness of 0.3 to 100 nm.