Release surfaces, particularly for use in nanoimprint lithography

Abstract

The addition of thin coatings (less than and approaching monomolecular coatings) of persistent release materials comprising preferred compounds of the formula: RELEASE-M(X) n -1 RELEASE-M(X) n-m-1 Q m , or RELEASE-M(OR) n -1 -, wherein RELEASE is a molecular chain of from 4 to 20 atoms in length, preferably from 6 to 16 atoms in length, which molecule has either polar or non-polar properties; M is a metal atom, semiconductor atom, or semimetal atom; X is halogen or cyano, especially Cl, F, or Br; Q is hydrogen or alkyl group; m is the number of Q groups; R is hydrogen, alkyl or phenyl, preferably hydrogen or alkyl of 1 to 4 carbon atoms; and; n is the valence −1 of M, and n-m-1 is at least 1 provides good release properties. The coated substrates are particularly good for a lithographic method and apparatus for creating ultra-fine (sub-25 nm) patterns in a thin film coated on a substrate is provided, in which a mold having at least one protruding feature is pressed into a thin film carried on a substrate. The protruding feature in the mold creates a recess of the thin film. The mold is removed from the film. The thin film then is processed such that the thin film in the recess is removed exposing the underlying substrate. Thus, the patterns in the mold is replaced in the thin film, completing the lithography. The patterns in the thin film will be, in subsequent processes, reproduced in the substrate or in another material which is added onto the substrate.

What is claimed is:  
     
         1 . A lithographic method for forming a pattern in a film carried on a substrate, comprising the steps of: 
 depositing a film on a substrate to provide a mold having a protruding feature and a recess formed thereby, the feature and the recess having a shape forming a mold pattern;    urging the mold into the film whereby the thickness of the film under the protruding feature is reduced and a thin region is formed in the film;    removing the mold from the film;    processing the relief whereby the thin region is removed exposing a portion of the surface of the substrate which underlies the thin region; and    whereby the exposed portion of the surface of the substrate substantially replicates the mold pattern,    the improvement comprising at least a portion of said protruding feature and a portion of said release have bonded thereto a release material comprising an inorganic linking group bonded to a molecular chain having release properties.    
     
     
         2 . The method of  claim 1  wherein said release material comprises a material having the formula:  
       RELEASE-M(X) n-1 - or RELEASE-M(OR) n-1 -, wherein  RELEASE is a molecular chain of from 4 to 20 atoms in length, preferably from 6 to 16 atoms in length, which molecule has either polar or non-polar properties;    M is a metal or semimetal atom;    X is halogen or cyano, especially Cl, F, or Br;    R is hydrogen, alkyl or phenyl, preferably hydrogen or alkyl of 1 to 4 carbon atoms; and;    (n) is the valence −1 of M.    
     
     
         3 . The process of  claim 2  wherein RELEASE comprises a highly fluorinated organic group.  
     
     
         4 . The process of  claim 3  wherein said highly fluorinated group comprises a perfluorinated alkyl group.  
     
     
         5 . The process of  claim 2  wherein M is Si.  
     
     
         6 . The process of  claim 2  wherein X is halogen.  
     
     
         7 . The process of  claim 2  wherein X is chloro or bromo.  
     
     
         8 . The process of  claim 6  wherein M is Si.  
     
     
         9 . The process of  claim 7  wherein M is Si.  
     
     
         10 . A process for improving the release properties of a surface comprising: 
 a) providing a surface;    b) contacting that surface with a release forming material wherein said release forming material comprises a material having the formula:    RELEASE-M(X) n-1  or RELEASE-M(OR) n-1 -, wherein    RELEASE is a molecular chain of from 4 to 20 atoms in length, preferably from 6 to 16 atoms in length, which molecule has either polar or non-polar properties;    M is a metal or semimetal atom;    X is halogen or cyano, especially Cl, F, or Br;    R is hydrogen, alkyl or phenyl, preferably hydrogen or alkyl of 1 to 4 carbon atoms; and;    (n) is the valence −1 of M.    
     
     
         11 . The process of  claim 10  wherein said release forming material comprises a material of the formula:  
       RELEASE-M(X) n-1 -  wherein 
 RELEASE is a molecular chain of from 4 to 20 atoms in length, which molecular chain has either polar or non-polar properties;  
 M is a metal or semimetal atom;  
 X is halogen or cyano, especially Cl, F, or Br; and  
 (n) is the valence −1 of M.  
   
     
     
         12 . The process of  claim 11  wherein RELEASE comprises a highly fluorinated organic group.  
     
     
         13 . The process of  claim 12  wherein said highly fluorinated group comprises a perfluorinated organic group.  
     
     
         14 . The process of  claim 11  wherein said highly fluorinated group comprises a perfluorinated alkyl group of from 4 to 16 carbon atoms.  
     
     
         15 . The process of  claim 11  wherein M is Si.  
     
     
         16 . The process of  claim 12  wherein M is Si.  
     
     
         17 . The process of  claim 13  wherein M is Si.  
     
     
         18 . The process of  claim 14  wherein M is Si.  
     
     
         19 . A surface having good antiadherent properties comprising a surface having bonded thereto the residue of material of the formula:  
       RELEASE-M(X) n-1 - or RELEASE-M(OR) n-1 -, wherein  RELEASE is a molecular chain of from 4 to 20 atoms in length, preferably from 6 to 16 atoms in length, which molecule has either polar or non-polar properties;    M is a metal or semimetal atom;    X is halogen or cyano, especially Cl, F, or Br;    R is hydrogen, alkyl or phenyl, preferably hydrogen or alkyl of  1  to  4  carbon atoms; and;    (n) is the valence −1 of M, said material being bonded to said surface only through a bond directly to M where a group X or OR has been removed to enable bonding to said surface, with the group RELEASE still attached to M.    
     
     
         20 . The surface of  claim 19  wherein said material comprises a material of the formula:  
       RELEASE-M(X) n-1 - wherein  RELEASE is a molecular chain of from 4 to 20 atoms in length, preferably from 6 to 16 atoms in length, which molecule has either polar or non-polar properties;    M is a metal or semimetal atom;    X is halogen or cyano, especially Cl, F, or Br; and    (n) is the valence −1 of M.    
     
     
         21 . The surface of  claim 20  wherein RELEASE comprises a highly fluorinated group.  
     
     
         22 . The surface of  claim 21  wherein said highly fluorinated group comprises a perfluorinated group.  
     
     
         23 . The surface of  claim 22  wherein said highly fluorinated group comprises a perfluorinated group of from 4 to 16 carbon atoms.  
     
     
         24 . The surface of  claim 20  wherein M is Si.  
     
     
         25 . The surface of  claim 21  wherein M is Si.  
     
     
         26 . The surface of  claim 22  wherein M is Si.  
     
     
         27 . The surface of  claim 23  wherein M is Si.  
     
     
         28 . A surface having good antiadherent properties comprising a surface having bonded thereto the material of the formula:  
       RELEASE-M(X) p-2  or RELEASE-M(OR) p-2 , wherein  RELEASE is a molecular chain of from 4 to 20 atoms in length, preferably from 6 to 16 atoms in length, which molecule has either polar or non-polar properties;    M is a metal or semimetal atom;    X is halogen or cyano, especially Cl, F, or Br;    R is hydrogen, alkyl or phenyl, preferably hydrogen or alkyl of 1 to 4 carbon atoms; and;    p is the valence of M, said material being bonded to said surface only through a bond directly to M.    
     
     
         29  The surface of  claim 19  wherein the surface comprises a patterned mold surface.  
     
     
         30 . The method of  claim 1  including heating the thin film to a temperature to allow sufficient softening of the film relative to the mold prior to the step of urging.  
     
     
         31 . The method of  claim 1  wherein the feature on the mold is formed from material selected from the group consisting of: semiconductors, dielectrics, metals, ceramics, polymers and their combination.  
     
     
         32 . The surface of  claim 19  wherein said surface comprises a material selected from the group consisting of: semiconductors, dielectrics, metals, ceramics, polymers and their combination.  
     
     
         33 . The method of  claim 1  wherein the step of processing comprises reactive ion etching.  
     
     
         34 . The method of  claim 1  including repeating the steps of obtaining a mold, urging, removing, and processing to form a multilayered device.  
     
     
         35 . The method of  claim 9  wherein the material is selected from the group consisting of semiconductors, dielectrics, metals, ceramics, polymers, and their combination.  
     
     
         36 . A lithographic method for forming a pattern in a film carried on a substrate, comprising the steps of: 
 obtaining a substrate having a release coating thereon formed by the reaction of a compound of the formula    RELEASE-M(X) n-1 - or RELEASE-M(OR) n-1 -, wherein    RELEASE is a molecular chain of from 4 to 20 atoms in length, preferably from 6 to 16 atoms in length, which molecule has either polar or non-polar properties;    M is a metal or semimetal atom;    X is halogen or cyano, especially Cl, F, or Br;    R is hydrogen, alkyl or phenyl, preferably hydrogen or alkyl of 1 to 4 carbon atoms; and;    (n) is the valence −1 of M,    depositing a film on the substrate;    obtaining a mold having a protruding feature and a recess formed thereby, the feature and the recess having a shape forming a mold pattern;    urging the mold into the film creating a thickness contrast pattern in the film;    removing the mold from the film; and    transferring the thickness contrast pattern in the film onto the substrate.    
     
     
         37 . A process for improving the release properties of a surface comprising: 
 a) providing a surface;    b) contacting that surface with a release forming material wherein said release forming material comprises a material having the formula:    RELEASE-M(X) n-m-1 Q m ,    RELEASE is a molecular chain of from 4 to 20 atoms in length, preferably from to 16 atoms in length, which molecule has either polar or non-polar properties;    M is a metal or semimetal atom;    X is halogen or cyano, especially Cl, F, or Br;    Q is a hydrogen or alkyl group,    m is the number of Q groups,    n-m-1 is at least 1, and    n is the valence −1 of M.    
     
     
         38 . The process of  claim 2  wherein said release material comprises a material having the formula:  
       RELEASE-M(X) n-1 -.  
     
     
         39 . The surface of  claim 28  wherein said release material comprises a material having the formula:  
       RELEASE-M(X) n-1 -.  
     
     
         40 . The process of  claim 38  wherein M is Si; 
 X is halogen Cl or Br;  
 RELEASE is perfluoroalkyl of 6 to 20 carbon atoms;  
 and  
 n is 3.  
 
     
     
         41 . The surface of  claim 39  wherein M is Si; 
 X is halogen Cl or Br;  
 RELEASE is perfluoroalkyl of 6 to 20 carbon atoms  
 and  
 n is 3.