Spin-on compositions comprising an inorganic oxide component and an alkynyloxy substituted spin-on carbon component useful as hard masks and filling materials with improved shelf life

Patent metadata

Field	Value
Publication number	US-2022025109-A1
Application number	US-202017423528-A
Country	US
Kind code	A1
Filing date	Feb 20, 2020
Priority date	Feb 22, 2019
Publication date	Jan 27, 2022
Grant date	—

Abstract

The present invention relates to a composition comprising; components a) b) and d); wherein, component a) is a metal compound having the structure (I), component b) is a spin on high carbon polymer, having a polymer backbone comprising mono-cyclic aromatic hydrocarbon, fused-ring ring hydrocarbon moieties, or mixtures of these, having a wt. % of carbon from about 81 wt. % to about 94 wt. %, which is soluble to at least about 5 wt. % in a spin casting solvent, and wherein at least one, of said mono-cyclic aromatic hydrocarbon or said fused-ring ring hydrocarbon moieties, present in said spin on high carbon polymer, is functionalized with at least one alkynyloxy moiety of structure (VIII), and component d) is a spin casting solvent. The present invention further relates to using this composition in methods for manufacturing electronic devices through either the formation of a patterned films of high K material comprised of a metal oxide on a semiconductor substrate, or through the formation of patterned metal oxide comprised layer overlaying a semiconductor substrate which may be used to selectively etch the semiconductor substrate with a fluorine plasma.

First claim

1 . A composition comprising:
a) a metal compound having the structure (I):

wherein,
M is a metal having a valence of four (4);
n is an integer from 1 to 20;
each R 1 , R 2 , R 3 , and R 4 is independently selected from the group consisting of:
1) a first organic moiety having the structure (II):

wherein, R 5 is selected from the group consisting of C 2 to C 10 alkylenes, C 3 to C 12 branched alkylenes, C 5 to C 12 cycloalkylenes, C 2 to C 10 alkylenes containing a C═C double bond, C 3 to C 12 branched alkylenes containing a C═C double bond, and C 5 to C 12 cycloalkylenes containing a C═C double bond; and R 6 is hydrogen or an alkyloxycarbonyl having the structure (III),

wherein, R 7 is a C 1 to C 8 alkyl;
2) a silicon bearing organic moiety having at least 2 carbons and having the structure (IV):

wherein,
R 8 and R 9 are each independently selected from the group consisting of C 1 to C 8 alkyls, C 3 to C 12 branched alkyls, C 1 to C 8 alkyloxys, C 3 to C 12 branched alkyloxys, and C 6 to C 16 aryls;
R 10 is selected from the group consisting of C 1 to C 8 alkyls, C 6 to C 16 aryls, hydroxyl and siloxanes having the structure (V):

wherein,
R 11 is selected from the group consisting of hydrogen, C 1 to C 8 alkyls, C 1 to C 8 alkyls substituted with a hydroxyl, a C 6 to C 16 aryl, and a silyl moiety having structure (IVa) wherein, R 8a and R 9a are each independently selected from the group consisting of C 1 to C 8 alkyls, C 3 to C 12 branched alkyls, C 1 to C 8 alkyloxys, C 3 to C 12 branched alkyloxys, and C 6 to C 16 aryls, and R 10 , is selected from the group consisting of C 1 to C 8 alkyls, and C 6 to C 16 aryls;

R 12 and R 13 are each independently selected from the group consisting of C 1 to C 8 alkyls, C 3 to C 12 branched alkyls, C 1 to C 8 alkyloxys, C 3 to C 12 branched alkyloxys, and C 6 to C 16 aryls; and
p represents the number of repeat units in the siloxane moiety (V);
3) a second organic moiety selected from the group consisting of C 2 to C 8 alkyls, C 2 to C 8 alkyl carboxyls, C 6 to C 20 aryl carboxyls, fluorenyl carboxyls, fluorinated C 2 to C 8 alkyl carboxyls, C 2 to C 8 alkyl sulfonyls, fluorinated C 2 to C 8 alkyl sufonyls, and mixtures thereof; and
4) mixtures thereof;

b) a spin on high carbon polymer, having a polymer backbone comprising mono-cyclic aromatic hydrocarbon moieties, fused-ring ring hydrocarbon moieties, or mixtures of these having a wt. % of carbon from about 81 wt. % to about 94 wt. %, which is soluble to at least about 5 wt. % in a spin casting solvent, and wherein at least one, of said mono-cyclic aromatic hydrocarbon or said fused-ring ring hydrocarbon moieties, present in said spin on high carbon polymer, is functionalized with at least one alkynyloxy moiety of structure (VIII),

wherein
represents the attachment point of said alkynyloxy moiety to said mono-cyclic aromatic hydrocarbon moieties or to said fused-ring ring hydrocarbon moieties and R a1 is hydrogen, halogen, cyano, unsubstituted C 1 to C 6 alkyl, C 1 to C 6 alkyl substituted with at least one substituent selected from the group consisting of C 1 to C 6 alkyl, halogen and cyano, unsubstituted C 3 to C 20 aromatic ring, or C 3 to C 20 aromatic ring substituted with at least one substituent selected from the group consisting of C 1 to C 6 alkyl, halogen and cyano,
R a2 and R a3 are each independently hydrogen, halogen, cyano, unsubstituted C 1 to C 6 alkyl, C 1 to C 6 alkyl substituted with at least one substituent selected from the group consisting of C 1 to C 6 alkyl, halogen and cyano, unsubstituted C 3 to C 20 aromatic ring, or C 3 to C 20 aromatic ring substituted with at least one substituent selected from the group consisting of C 1 to C 6 alkyl, halogen and cyano,
c) an optional component comprised of a polyol additive having the structure (VI):

wherein,
X is C or N;
r is at least 2;
q is from 0 to 2;
provided that the sum of q and r is 4 when X is C, and the sum of q and r is 3 when X is N;
R 14 is selected from the group consisting of hydrogen, C 1 to C 8 alkyls and C 2 to C 8 hydroxyalkyls;
when X is N, Y is a C 1 to C 8 alkylene, or, when X is C, Y is selected from the group consisting of a direct valence bond, C 1 to C 8 alkylenes and moieties having the structure (VII):

wherein,
R 15 is a C 2 to C 8 alkylene;
s is 0 to 2; and
t is 1 to 2;
d) a spin casting solvent.

2 . The composition according to claim 1 , wherein said polymer backbone of said spin on high carbon polymer comprises moieties selected from the group consisting of

and mixtures thereof.

3 . The composition of claim 1 , wherein said spin on high carbon polymer comprises a repeat unit having structure (X),
A-B   (X),
wherein A is selected from the group consisting of

and mixtures thereof, and

wherein B is selected from the group consisting of

and mixtures thereof,
wherein Rx 1 and Rx 2 are independently hydrogen, a C 1 to C 6 alkyl, an aryl moiety, or an alkynyloxy moiety of structure (VIII).

4 . The composition of claim 1 , wherein said spin on high carbon polymer comprises a repeat unit having structure (XI);

5 - 8 . (canceled)

9 . The composition of claim 1 , wherein said spin on high carbon polymer comprises a repeat unit of structure (XII), wherein fAr is a fused aromatic ring, R 16 and R 17 are each independently hydrogen or a C 1 to C 4 alkyl:

10 . The composition of claim 9 , wherein fAr is a group comprising 2-8 fused aromatic rings.

11 . The composition of claim 9 , w

Assignees

• Merck Patent Gmbh

Inventors

• Rahman M Dalil
• Sekito Takashi

Classifications

• H10P14/6922 Primary

  the material containing Si, O and at least one of H, N, C, F or other non-metal elements, e.g. SiOC, SiOC:H or SiONC · CPC title

• G03F1/56

  Organic absorbers, e.g. of photo-resists · CPC title

• C08G2261/344

  containing heteroatoms · CPC title

• C08G8/02

  of ketones · CPC title

• C08L65/00 Primary

  Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C08L7/00 - C08L57/00, C08L61/00 take precedence); Compositions of derivatives of such polymers · CPC title