Implementations of the disclosure may include methods of electroplating features formed on a semiconductor device, such as the trenches and vias formed by single or dual Damascene processes using a cobalt plating bath. The cobalt electroplating bath may contain “additive packages” or “additive systems” that include a combination of additives in certain ratios that facilitate the metal filling of high aspect ratio sub-micrometer features. Implementations of the disclosure provide new cobalt plating bath methods and chemistries and that include alkyl modified imidazoles, imidazolines, and imidazolidines suppressor compounds.

A metal material having thermodynamic anisotropy has an X-axis hardness of 160-180 HV, an X-axis hardness thermal expansion coefficient of 5×10-6-100×10-6 K.sup.−1; a Y-axis hardness of 160-180 HV, a Y-axis hardness thermal expansion coefficient of 5×10-6-100×10-6 K.sup.−1; and a Z-axis hardness of 180-250 HV, a Z-axis hardness thermal expansion coefficient of 50×10-6-1000×10-6 K.sup.−1. A method for preparing a metal material having thermodynamic anisotropy is also disclosed.

In a deposition method of Ni—P—B system plating film, electroplating is performed in a plating bath containing Ni ions, phosphorous acid ions, alkylamine borane, acetic acid, at least one sort of a primary brightening agent, and a secondary brightening agent including at least one sort of a surface active agent. In the above-mentioned plating bath, concentration of alkylamine borane in said plating bath is 1.37 mmol/L or more, and concentration of acetic acid in said plating bath is 0.70 mol/L or more and less than 2.80 mol/L. Thereby, plating film having high hardness of Hv 700 or more can be deposited with high manufacturing efficiency without baking processing, while reducing occurrence of poor appearance, such as burning and abnormal precipitation, even when current density is increased to 80 A/dm.sup.2 or more to raise deposition rate.

A metal material having thermodynamic anisotropy has an X-axis hardness of 160-180 HV, an X-axis hardness thermal expansion coefficient of 5×10-6-100×10-6 K.sup.−1; a Y-axis hardness of 160-180 HV, a Y-axis hardness thermal expansion coefficient of 5×10-6-100×10-6 K.sup.−1; and a Z-axis hardness of 180-250 HV, a Z-axis hardness thermal expansion coefficient of 50×10-6-1000×10-6 K.sup.−1. A method for preparing a metal material having thermodynamic anisotropy is also disclosed.

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.

A process is provided comprising submerging a substrate in an electrochemical deposit bath having at least a metal salt and saccharin. In embodiments, the film is further treated with anodization, and in other cases chemical vapor deposition. Films are also provided formed by the disclosed processes. The films are nanoporous on at least a portion of a surface of the films. Also disclosed are electronic devices having the films disclosed, including lithium-ion batteries, storage devices, supercapacitors, electrodes, semiconductors, fuel cells, and/or combinations thereof.

A process is provided comprising submerging a substrate in an electrochemical deposit bath having at least a metal salt and saccharin. In embodiments, the film is further treated with anodization, and in other cases chemical vapor deposition. Films are also provided formed by the disclosed processes. The films are nanoporous on at least a portion of a surface of the films. Also disclosed are electronic devices having the films disclosed, including lithium-ion batteries, storage devices, supercapacitors, electrodes, semiconductors, fuel cells, and/or combinations thereof.

Described herein is a cobalt electrodeposition composition including cobalt ions, and particular leveling agents including X.sup.1—CO—O—R.sup.11, X.sup.1—SO.sub.2—O—R.sup.11, X.sup.1—PO(OR.sup.11).sub.2, X.sup.1—SO—O—R.sup.11 functional groups, where X.sup.1 is a divalent group selected from (i) a chemical bond (ii) aryl, (iii) C.sub.1 to C.sub.12 alkandiyl, which may be interrupted by O atoms, (iv) an arylalkyl group —X.sup.11—X.sup.12—, (v) an alkylaryl group —X.sup.12—X.sup.11— and (vi) —(O—C.sub.2H.sub.3R.sup.12).sub.mO—, R.sup.11 is selected from H and C.sub.1 to C.sub.4 alkyl. R.sup.12 is selected from H and C.sub.1 to C.sub.4 alkyl, X.sup.12 is a divalent aryl group, and X.sup.11 is a divalent C.sub.1 to C.sub.15 alkandiyl group.

Described herein is a cobalt electrodeposition composition including cobalt ions, and particular leveling agents including X.sup.1—CO—O—R.sup.11, X.sup.1—SO.sub.2—O—R.sup.11, X.sup.1—PO(OR.sup.11).sub.2, X.sup.1—SO—O—R.sup.11 functional groups, where X.sup.1 is a divalent group selected from (i) a chemical bond (ii) aryl, (iii) C.sub.1 to C.sub.12 alkandiyl, which may be interrupted by O atoms, (iv) an arylalkyl group —X.sup.11—X.sup.12—, (v) an alkylaryl group —X.sup.12—X.sup.11— and (vi) —(O—C.sub.2H.sub.3R.sup.12).sub.mO—, R.sup.11 is selected from H and C.sub.1 to C.sub.4 alkyl. R.sup.12 is selected from H and C.sub.1 to C.sub.4 alkyl, X.sup.12 is a divalent aryl group, and X.sup.11 is a divalent C.sub.1 to C.sub.15 alkandiyl group.

A cobalt electrodeposition composition comprising cobalt ions, and particular leveling agents comprising X.sup.1—CO—O—R.sup.11, X.sup.1—SO.sub.2—O—R.sup.11, X.sup.1—PO(OR.sup.11).sub.2, X.sup.1—SO—O—R.sup.11 functional groups, wherein X.sup.1 is a divalent group selected from (i) a chemical bond (ii) aryl, (iii) C.sub.1 to C.sub.12 alkandiyl, which may be interrupted by O atoms, (iv) an arylalkyl group —X.sup.11—X.sup.12—, (v) an alkylaryl group —X.sup.12—X.sup.11—, and (vi) —(O—C.sub.2H.sub.3R.sup.12).sub.mO—, R.sup.11 is selected from H and C.sub.1 to C.sub.4 alkyl. R.sup.12 is selected from H and C.sub.1 to C.sub.4 alkyl, X.sup.12 is a divalent aryl group, X.sup.11 is a divalent C.sub.1 to C.sub.15 alkandiyl group.