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US 12,098,473 B2Granted
Composition for cobalt plating comprising additive for void-free submicron feature filling
AssigneeBASF SE
InventorsSathana Kitayaporn, Charlotte Emnet, Dieter Mayer, Nadine Engelhardt, Marco Arnold, Lucas Benjamin Henderson, Alexander Fluegel
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Abstract
Described herein is a composition including metal ions consisting essentially of cobalt ions, and a specific monomeric and polymeric suppressing agent including a carboxylic, sulfonic, sulfinic, phosphonic, or phosphinic acid functional groups which show a suppressing effect that is required for void-free bottom-up filling of nanometer-sized recessed features.
Claims19
A composition for cobalt electroplating consisting essentially of:
- (a) cobalt ions,
- (b) from 1 ppm to 1000 ppm, relative to a total weight of the composition, of a suppressing agent of formula S1
- [B]n[A]p (S1)
- or of formula S2
- or of formula S3a or S3b
- or of formula S4
- Ø-R1 (S4)
- and their salts,
- (c) boric acid,
- (d) an inorganic or organic acid,
- (e) optionally a wetting agent,
- (f) optionally a leveling agent different from the suppressing agent, and
- (g) water,
- wherein
- R1 is selected from the group consisting of X1—CO—O—R11, X1—SO2—O—R11, X1—PR11O(OR11), X1—P(OR11)2, X1—PO(OR11)2, and X1—SO—O—R11;
- R2, R3, R4 are independently selected from the group consisting of R1 and (i) H, (ii) aryl, (iii) C1 to C10 alkyl (iv) arylalkyl, (v) alkylaryl, and (vi) —(O—C2H3R12)m—OH, wherein if one of R2, R3 or R4 are selected from the group consisting of R1, each other one of R2, R3 or R4 is different from R1,
- Ø is a C6 to C14 carbocyclic or a C3 to C10 nitrogen or oxygen containing heterocyclic aryl group, which may be unsubstituted or substituted by up to three C1 to C12 alkyl groups or up to two OH, NH2 or NO2 groups,
- R31 is selected from the group consisting of R1, H, OR32 and R32,
- R32 is selected from the group consisting of (i) H and (ii) C1 to C6 alkyl,
- X1 is a divalent group selected from the group consisting of (i) a chemical bond (ii) aryl, (iii) C1 to C12 alkanediyl, which may be interrupted by one or more O atoms, (iv) an arylalkyl group —X12—X11—, (v) an alkylaryl group —X11—X12—, and (vi) —(O—C2H3R12)mO—,
- X2 is (i) a chemical bond or (ii) methanediyl,
- R11 is selected from the group consisting of H and C1 to C4 alkyl,
- R12 is selected from the group consisting of H and C1 to C4 alkyl,
- X12 is a divalent aryl group,
- X11 is a divalent C1 to C15 alkanediyl group,
- A is a co-monomer selected from the group consisting of vinyl alcohol, which may optionally be (poly)ethyoxylated, acrylonitrile, styrene and acrylamide,
- B is selected from the group consisting of formula Sla
- n is an integer from 2 to 10 000,
- m is an integer from 2 to 50,
- o is an integer from 2 to 1 000, and
- p is 0 or an integer from 1 to 10 000;
- wherein the composition facilitates substantially void-free, bottom up filling of a recessed feature on a semiconductor substrate with cobalt, the recessed feature having an aperture size below 100 nm.
29 more elements
A method of using a compound of formula S1
- [B]n[A]p (S1)
- or of formula S2
- or of formula S3a or S3b
- or of formula S4
- Ø-R1 (S4)
- and their salts,
- the method comprising using the compound as a suppressing agent for void-free deposition of a metal comprising cobalt on a semiconductor substrate comprising recessed features having an aperture size below 100 nm,
- wherein
- R1 is selected from the group consisting of X1—CO—O—R11, X1—SO2—O—R11, X1—PR11O(OR11), X1—P(OR11)2, X1—PO(OR11)2, X1—SO—O—R11;
- R2, R3, R4 are independently selected from the group consisting of R1 and (i) H, (ii) aryl, (iii) C1 to C10 alkyl (iv) arylalkyl, (v) alkylaryl, and (vi) —(O—C2H3R12)m—OH, wherein if one of R2, R3 or R4 are selected from the group consisting of R1, each other one of R2, R3 or R4 is different from R1
- Ø is a C6 to C14 carbocyclic or a C3 to C10 nitrogen or oxygen containing heterocyclic aryl group, which may be unsubstituted or substituted by up to three C1 to C12 alkyl groups or up to two OH, NH2 or NO2 groups,
- R31 is selected from the group consisting of R1, H, OR32 and R32,
- R32 is selected from the group consisting of (i) H and (ii) C1 to C6 alkyl,
- X1 is a divalent group selected from the group consisting of (i) a chemical bond (ii) aryl, (iii) C1 to C12 alkanediyl, which may be interrupted by O atoms, (iv) arylalkyl group —X11—X12—, (v) alkylaryl group —X12—X11—, and (vi) —(O—C2H3R12)mO—,
- X2 is (i) a chemical bond or (ii) methanediyl,
- R11 is selected from the group consisting of H and C1 to C4 alkyl,
- R12 is selected from the group consisting of H and C1 to C4 alkyl,
- X12 is a divalent aryl group,
- X11 is a divalent C1 to C15 alkanediyl group,
- A is a co-monomer selected from the group consisting of vinyl alcohol, which may optionally be (poly)ethyoxylated, acrylonitrile, styrene and acrylamide,
- B is selected from the group consisting of formula Sla
- n is an integer from 2 to 10 000,
- m is an integer from 2 to 50,
- o is an integer from 2 to 1 000, and
- p is 0 or an integer from 1 to 10 000.
22 more elements
Dependencies are inferred from the claim text.