Molecular organometallic resists for EUV

Patent metadata

Field	Value
Publication number	US-9372402-B2
Application number	US-201314026761-A
Country	US
Kind code	B2
Filing date	Sep 13, 2013
Priority date	Sep 13, 2013
Publication date	Jun 21, 2016
Grant date	Jun 21, 2016

Abstract

Described herein are organometallic or inorganic complexes with high extreme ultraviolet (EUV) optical density (OD) and high mass density for use in thin films. These thin films are used as high resolution, low line edge roughness (LER) EUV photoresists. The complexes may also be included in nanoparticle form for use in photoresists.

First claim

What is claimed is:

1. A photoresist comprising at least one complex (BD 2 ) z M(L a ) n (L b ) o (L c ) p (L d ) q or (A) y M(L e ) n (L f ) o (L g ) p (L h ) q , wherein:
M is a metal having a coordination number of Q, wherein M is selected from zirconium, manganese, aluminum, vanadium, titanium, chromium, manganese, iron, cobalt, copper, zinc, gallium, germanium, arsenic, molybdenum, ruthenium, rhodium, silver, cadmium, indium, tin, antimony, tellurium, iodine, thulium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, gold, mercury, thallium, lead, and bismuth;
Q is an integer selected from 2, 3, 4, 5, 6, 7, or 8;
BD 2 is oxalate or carbonate;
L a , L b , L c and L d are ligands, each having a denticity of, respectively, w a , w b , w c and w d ;
z is 1, 2 or 3;
n, o, p, and q are independently zero, one or two;
the sum of (n·w a ) plus (o·w b ) plus (p·w c ) plus (q·w d ) is equal to (Q minus 2z);
A is selected in each instance from azide and (—NO 2 );
L e , L f , L g and L h are ligands, each having a denticity of, respectively, w e , w f , w g and w h ;
y is any integer up to and including Q; and
the sum of (n·w e ) plus (o·w f ) plus (p·w g ) plus (q·w h ) is equal to (Q minus y);
wherein said complex is balanced by a counter ion, if necessary.

2. The photoresist according to claim 1 , wherein BD 2 is oxalate.

3. The photoresist according to claim 1 , wherein M is selected from manganese, iron, antimony, tellurium, tin, cobalt, bismuth, chromium, and copper.

4. The photoresist according to claim 1 , wherein M is selected from chromium, copper, iron, tin, cobalt, and bismuth.

5. The photoresist according to claim 1 , wherein Q is selected from 4 or 6.

6. The photoresist according to claim 1 , wherein L a , L b , L c , L d , L e , L f , L g and L h , when present, are selected independently in each instance from:
carbonyl; cyano; nitrite; thiocyanate; nitrile; aqua; hydroxy; oxo; alkoxy; phenoxy; thiol; sulfide; halogen; phenanthroline; polymine; bis(diphenylphosphino)ethane; bis(diphenylphosphino)methane; imine; ethylenediaminetetraacetate; cyclopentadienyl; R a NC; R a CN; NR a ; P(R a ) 3 ;
a heterocyclic compound;

wherein R a is selected from (C 1-6 )alkyl and aryl;
R 1 and R 2 each represent one, two or three substituents and are each independently selected from hydrogen, halogen, (C 1-4 )alkoxy, hydroxyl, nitro, amino, cyano, and (C 1-6 )alkyl optionally substituted with halogen, hydroxyl, nitro, amino, cyano, and phenyl, wherein the phenyl may be optionally substituted with (C 1-6 )alkyl, halogen, hydroxyl, nitro, amino, and cyano;
R 3 and R 4 are each independently selected from and (C 1-6 )alkyl optionally substituted with halogen, (C 1-4 )alkoxy, or aryl; and
R 5 is aryl or (C 1-6 )alkyl.

7. The photoresist according to claim 6 , wherein L a , L b , L c , L d , L e , L f , L g and L h , when present, are selected independently from ethylenediammine, phenanthroline,

8. The photoresist according to claim 1 , wherein BD 2 is oxalate; and z is 2 or 3.

9. The photoresist according to claim 8 , wherein z is 2; Q is 6; (L a ) is 2-2′-bipyridine optionally substituted with (C 1-6 )alkyl; and o, p, and q are each zero.

10. The photoresist according to claim 8 , wherein M is cobalt, iron, or chromium.

11. The photoresist according to claim 10 , wherein z is 2; Q is 6; (L a ) is 2-2′-bipyridine optionally substituted with ((C 1-6 )alkyl; and o, p, and q are each zero.

12. The photoresist according to claim 1 , wherein y is 2.

13. The photoresist according to claim 1 , wherein y is 2; (L e ) and (L f ) are each 2-2′-bipyridine optionally substituted with (C 1-6 )alkyl; and p and q are each zero.

14. The photoresist according to claim 1 , wherein the minimum solubility of said complex is 0.5% by weight.

15. The photoresist according to claim 1 , wherein said complex is in the form of a nanoparticle.

16. The photoresist according to claim 1 , wherein said counter ion is selected from P(R) 4 + , N(R) 4 + , S(R) 3 + , and I(R) 2 + , wherein R is independently selected in each instance from (C 1 -C 8 )alkyl, aryl, and aryl(C 1-8 )alkyl.

17. The photoresist according to claim 1 , wherein at least two of said complexes are present, forming a multi-nuclear structure.

18. A nanoparticle comprising at least one complex (BD 2 ) z M(L a ) n (L b ) o (L c ) p (L d ) q or (A) y M(L e ) n (L f ) o (L g ) p (L h ) q , wherein:
M is a metal having a coordination number of Q;
Q is an integer selected from 2, 3, 4, 5, 6, 7, or 8;
BD 2 is oxalate or carbonate;
L a , L b , L c and L d are ligands, each having a denticity of, respectively, w a , w b , w c and w h ;
z is 1, 2 or 3;
n, o, p, and q are independently zero, one or two;
the sum of (n·w a ) plus (o·w b ) plus (p·w c ) plus (q·w d ) is equal to (Q minus 2z);
A is selected in each instance from azide and (—NO 2 );
L e , L f , L g and L h are ligands, each having a denticity of, respectively, w e , w f , w g and w h ;
y is any integer up to and including Q; and
the sum of (n·w e ) plus (o·w f ) plus (p·w g ) plus (q·w h ) is equal to (Q minus y);
wherein said complex is balanced by a counter ion, if necessary; and
wherein one of the ligands L a , L b , L c , L d , L e , L f , L g , or L h , when present, optionally may be native to the nanoparticle.

19. The nanoparticle of claim 18 , wherein M is selected from zirconium, manganese, aluminum, vanadium, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, thulium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, lead, and bismuth.

Assignees

• Univ New York State Res Found

Inventors

• Freedman Daniel
• Marnell Miles
• Brainard Robert
• Cardineau Brian

Classifications

• G03F7/0042 Primary

  with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists (G03F7/075 takes precedence) · CPC title

• Y10T428/2982

  Particulate matter [e.g., sphere, flake, etc.] · CPC title

• G03F7/0043 Primary

  Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof (G03F7/0044 takes precedence) · CPC title