Preparation and use of EXO-2-fluoroalkyl(bicyclo[2.2.1] hept-5-enes)
AssigneeE.I. du Pont de Nemours and Company
InventorsAndrew Edward Feiring, Viacheslav Alexandrovich Petrov, Frank Leonard Schadt, III
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Abstract
There is disclosed a composition comprising a mixture of endo- and exo-2-(bicyclo[2.2.1]hept-5-en-2-yl)-2,2-fluoroalkyl-ethan-2-ol which is rich in the exo isomer, preferably the endo/exo concentration ratio is no greater than 5/95. The composition is useful for forming a repeat unit of a polymer which polymer may further comprise additional repeat units derived-from tert-butyl acrylate, hydroxyadamantyl acrylate, protected or unprotected fluorinated-olefins, 2-methyl-2-adamantyl acrylate, 2-propenoic acid, 2-hydroxy-1,1,2-trimethylpropyl ester. Polymers of this invention are useful as the binder component of a photoresist composition for microlithography.
Claims51
A composition comprising endo- and exo-2-(bicyclo[2.2.1]hept-5-en-2-yl)-2,2-fluoroalkyl-ethan-2-ol whereof the endo/exo concentration ratio is no greater than 5/95, as represented by the structure (I)
- wherein the Rf and Rf′ groups are the same or different fluoroalkyl groups of from 1 to about 10 carbon atoms, or taken together in cyclic form are (CF2)n where n is an integer from 2 to 10.
A polymer comprising about 10 mol % to about 60 mole % of a repeat unit derived from a composition comprising endo and exo monomer units represented by structure (II)
- wherein the Rf and Rf′ groups are the same or different fluoroalkyl groups of from 1 to 10 carbon atoms, or taken together in cyclic form are (CF2)n;
- n is an integer from 2 to 10;
- the monomer units of the composition having an endo/exo ratio no greater than 5/95.
A process for preparing a composition comprising endo- and exo-2-bicyclo[2.2.1]hept-5-en-2-yl)-2,2-fluoroalkyl-ethan-2-ol whereof the endo/exo concentration ratio is no greater than about 5/95, the process, comprising the steps of:
- contacting in the presence of a source of free radicals a substituted norbornene with ICH2C(Rf)(Rf′)OH;
- wherein said substituted norbornene is represented by the structure (III)
- to form an iodine-containing substituted norbornane compound represented by structure (IV);
- contacting said iodine-containing compound with a reducing agent to form a substituted norbornane represented by structure (V);
- forming an olefin from the substituted norbornane (V) to form a composition comprising endo and exo 2-(bicyclo[2.2.1]hept-5-en-2-yl)-2,2-perfluoroalkyl-ethan-2-ol, whereof the endo/exo concentration ratio is no greater than 5/95 as represented by the structure (I);
- wherein in the foregoing structures the Rf and Rf′ groups are the same or different fluoroalkyl groups of from 1 to 10 carbon atoms, or taken together in cyclic form are (CF2)n, n is an integer from 2 to 10, and wherein X is selected from the group consisting of Cl, Br, and R8SO2—O—, where R8 is an alkyl-, fluoroalkyl, aryl or fluoroaryl radical.
A photoresist suitable for use in the preparation of electronic circuits said photoresist comprising a photoactive agent and a polymer compromising 10 mol-% to 60 mol-% of a repeat unit represented by the structure (II)
- and whereof said repeat unit is derived from a composition comprising endo- and exo-2-(bicyclo[2.2.1]hept-5-en-2-yl)-2,2-fluoroalkyl-ethan-2-ol, as represented by the structure (I)
- wherein the Rf and Rf′ groups are the same or different fluoroalkyl groups of from 1 to about 10 carbon atoms, or taken together in cyclic form are (CF2)n where n is an integer from 2 to 10, whereof the endo/exo ratio is no greater than 5/95.
An article comprising a semiconducting substrate having a surface, and a photoresist film disposed upon at least a portion of said surface, said photoresist film comprising a photoactive agent and a polymer comprising about 10 mol-% to 60 mol-% of a repeat unit represented by the structure (II)
- and whereof said repeat unit is derived from a composition comprising endo- and exo-2-(bicyclo[2.2.1]hept-5-en-2-yl)-2,2-fluoroalkyl-ethan-2-ol, as represented by the structure (I)
- wherein the Rf and Rf′ groups are the same or different fluoroalkyl groups of from 1 to about 10 carbon atoms, or taken together in cyclic form are (CF2)n where n is an integer from 2 to 10, whereof the endo/exo ratio is no greater than 5/95.
A process for preparing a patterned article the process comprising:
- forming a target surface by disposing upon a semiconducting substrate a photoresist film comprising a photoactive agent and a polymer comprising about 10 mol-% to 60 mol-% of a repeat unit represented by the structure (II)
- whereof said repeat unit is derived from a composition comprising endo- and exo-2-(bicyclo[2.2.1]hept-5-en-2-yl)-2,2-fluoroalkyl-ethan-2-ol, as represented by the structure (I)
- wherein the Rf and Rf′ groups are the same or different fluoroalkyl groups of from 1 to about 10 carbon atoms, or taken together in cyclic form are (CF2)n where n is an integer from 2 to 10, whereof the endo/exo ratio is no greater than 5/95;
- illuminating said target surface in such a manner as to form a pattern of shadowed and illuminated areas, the illuminating step causing a change in solubility of said polymer;
- removing the soluble portions of said polymer, thereby producing a patterned article.
Dependencies are inferred from the claim text.