Composition for metal electroplating comprising an additive for bottom-up filling of though silicon vias and interconnect features

Patent metadata

Field	Value
Publication number	US-9631292-B2
Application number	US-201214123129-A
Country	US
Kind code	B2
Filing date	May 31, 2012
Priority date	Jun 1, 2011
Publication date	Apr 25, 2017
Grant date	Apr 25, 2017

Abstract

A composition comprising a source of metal ions and at least one polyaminoamide, said polyaminoamide comprising amide and amine functional groups in the polymeric backbone and aromatic moieties attached to or located within said polymeric backbone.

First claim

The invention claimed is:

1. A composition comprising a source of metal ions and a polyaminoamide, wherein the polyaminoamide comprises a structural unit represented by formula I
[A] p [B] q [D] r   (I)

or a derivative thereof obtained by complete or partial protonation, N-functionalization, or N-quaternization,
wherein
A is a diradical represented by formula Ia

B is a chemical bond or a diradical represented by formula Ib

D is a chemical bond or a divalent group represented by formula Ic

D 1 is, for each repeating unit 1 to p independently, a chemical bond or a divalent group that is a saturated or unsaturated C 1 to C 20 organic radical,
D 2 , D 3 are independently straight chain or branched C 1 to C 10 alkanediyl, optionally substituted by N or O,
D 4 is a straight chain or branched C 2 to C 6 alkanediyl, a C 6 to C 10 aryl or heteroaryl diradical, or C 8 to C 20 arylalkanediyl, C 8 to C 20 heteroarylalkanediyl
D 5 is a straight chain or branched C 1 - to C 7 -alkanediyl, optionally substituted by a heteroatom,
R 1 is, for each repeating unit 1 to n independently, H, C 1 -C 20 -alkyl, C 5 -C 20 -aryl or C 5 -C 20 -heteroaryl, optionally substituted by hydroxyl, alkoxy or alkoxycarbonyl,
n is an integer from 2 to 250,
p is an integer from 2 to 150,
q is an integer from 0 to 150,
r is an integer from 0 to 150,
and wherein either (i) at least one of D 4 or R 1 comprises a C 5 to C 20 aromatic moiety or (ii) the polyaminoamide is functionalized, quaternized, or both functionalized and quaternized with a C 5 to C 20 aromatic moiety.

2. The composition according to claim 1 wherein the polyaminoamide is represented by formula II

wherein
E 1 , E 2 are each independently
(a) a nucleophilically displaceable leaving group,
(b) NH—(C 1 -C 20 -alkyl) or NH—(C 1 -C 20 -alkenyl) or NH-aryl,
(c) H—{NH-[D 2 -NR 1 ] n -D 3 -NH},
(d) (C 1 -C 20 -alkyl)-CO—{NH-[D 2 -NR 2 ] n -D 3 -NH},
(e) (C 1 -C 20 -alkenyl)-CO—{NH-[D 2 -NR 2 ] n -D 3 -NH}, or
(f) (C 1 -C 20 -aryl)-CO—{NH-[D 2 -NR 2 ] n -D 3 -NH},

and wherein R 1 comprises a C 5 to C 20 aromatic moiety.

3. The composition according to claim 1 , wherein D 1 is a C 1 -C 20 alkanediyl group.

4. The composition according to claim 1 , wherein D 2 and D 3 are each independently (CH 2 ) 2 or (CH 2 ) 3 .

5. The composition according to claim 1 , wherein R 1 is hydrogen or methyl.

6. The composition according to claim 1 , wherein R 1 is a C 5 to C 20 aryl, a C 5 to C 20 heteroaryl, a C 5 to C 20 arylalkyl, or a C 5 to C 20 heteroarylalkyl.

7. The composition according to claim 1 , wherein the polyaminoamide is obtained by reacting at least one polyalkylenepolyamine with at least one dicarboxylic acid.

8. The composition according to claim 7 , wherein the polyalkylenepolyamine is at least one member selected from the group consisting of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, diaminopropylethylenediamine, ethylenepropylenetriamine, 3-(2-aminoethyl)aminopropylamine, dipropylenetriamine, a polyethyleneimine, H 2 N—(CH 2 ) 2 —O—(CH 2 ) 2 —NH 2 and H 2 N—(CH 2 ) 2 —O—(CH 2 ) 2 —O—(CH 2 ) 2 —NH 2 .

9. The composition according to claim 7 , wherein the dicarboxylic acid is at least one member selected from the group consisting of oxalic acid, malonic acid, succinic acid, tartaric acid, maleic acid, itaconic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, iminodiacetic acid, aspartic acid, and glutamic acid.

10. A composition comprising a source of metal ions and a polyaminoamide, wherein the polyaminoamide comprises an amide and an amine functional group in its polymeric backbone and wherein at least one aromatic moiety is attached to or located within the polymeric backbone, wherein the polyaminoamide comprises a group represented by formula III

or a derivative of a polyaminoamide of formula III obtained by complete or partial protonation, N-functionalization, or N-quaternization
wherein
D 6 is, for each repeating unit 1 to s independently, a divalent group that is a saturated, unsaturated or aromatic C 1 -C 20 organic radical,
D 7 is a straight chain or branched C 2 -C 6 alkanediyl, C 6 -C 10 aryldiradical, or C 8 -C 20 arylalkanediyl,
R 2 is, for each repeating unit 1 to s independently, H, C 1 -C 20 alkyl, C 1 -C 20 alkenyl, optionally substituted by hydroxyl, alkoxy or alkoxycarbonyl, or aryl, and wherein two R 2 may together form a ring system, and
s is an integer from 1 to 250,
and wherein either (i) at least one of D 6 , D 7 or R 2 comprises a C 5 -C 20 aromatic moiety or (ii) the polyaminoamide is functionalized, quaternized, or both functionalized and quaternized with a C 5 -C 20 aromatic moiety.

11. The composition according to claim 10 being represented by formula IV

wherein
E 3 , E 4 are each independently
(a) NH—C 1 -C 20 -alkyl or NH—C 1 -C 20 -alkenyl or NH-aryl,
(b) N—(C 1 -C 20 -alkyl) 2 or N—(C 1 -C 20 -alkenyl) 2 or N-(aryl) 2 or N—(C 1 -C 20 -alkyl)(C 1 -C 20 -alkenyl) or N—(C 1 -C 20 -alkyl)(aryl) or N—(C 1 -C 20 -alkenyl)(aryl),
(c) NR 2 -D 7 -NR 2 H, or
(d) NR 2 -D 7 -NR 2 —CH 2 —CH 2 —CO—NH—(C 1 -C 20 -alkyl) or NR 2 -D 7 -NR 2 —CH 2 —CH 2 —CO—NH—(C 1 -C 20 -alkenyl) or NR 2 -D 7 -NR 2 —CH 2 —CH 2 —CO—NH-aryl,

and wherein at least one of D 6 or R 2 comprises a C 5 to C 20 aromatic moiety.

12. The composition according to claim 1 , wherein the metal ions comprise a copper ion.

13. The composition according to claim 1 , further comprising an accelerating agent.

14. The composition according to claim 1 , further comprising a suppressing agent.

15. A bath comprising the composition of claim 1 , wherein the bath is suitable for depositing a metal containing layer.

16. A process for depositing a metal layer on a substrate, the process comprising
a) contacting a metal plating bath comprising the composition according to claim 1 with the substrate, and
b) applying a current density to the substrate for a time sufficient to deposit a metal layer onto the substrate.

17. The composition according to claim 1 , wherein B is a diradical represented by formula Ib, and D 4 comprises a C 5 to C 20 aromatic moiety.

18. The composition according to claim 17 , wherein D 4 is a C 6 to C 10 aryl or heteroaryl diradical.

19. The composition according to claim 1 , wherein the polyaminoamide is functionalized, quaternized, or both functionalized and quaternized with a C 5 to C 20 aromatic moiety.

20. The composition according to claim 1 , wherein R 1 comprises a C 5 to C 20 aromatic moiety.

Assignees

• Roeger-Goepfert Cornelia
• Arnold Marco
• Fluegel Alexander
• Emnet Charlotte
• Raether Roman Benedikt
• Mayer Dieter
• Basf Se

Inventors

• Roeger-Goepfert Cornelia
• Arnold Marco
• Fluegel Alexander
• Emnet Charlotte
• Raether Roman Benedikt
• Mayer Dieter

Classifications

• H10P14/47

  Electrolytic deposition, i.e. electroplating; Electroless plating · CPC title

• H10W20/023

  the interconnections being through-semiconductor vias · CPC title

• H10W20/0245

  comprising use of blind vias during the manufacture · CPC title

• C23C18/38

  Coating with copper · CPC title

• C25D7/123

  Semiconductors first coated with a seed layer or a conductive layer · CPC title