Nano-twinned Cu—Ni alloy layer and method for manufacturing the same

Patent metadata

Field	Value
Publication number	US-12037670-B2
Application number	US-202217708371-A
Country	US
Kind code	B2
Filing date	Mar 30, 2022
Priority date	Jan 10, 2022
Publication date	Jul 16, 2024
Grant date	Jul 16, 2024

Abstract

A nano-twinned Cu—Ni alloy layer is provided, wherein more than 50% in volume of the nano-twinned Cu—Ni alloy layer comprises plural twinned grains, the plural twinned grains comprise plural columnar twinned grains, and a Ni content in the nano-twinned Cu—Ni alloy layer is in a range from 0.05 at % to 20 at %. In addition, a method for manufacturing the aforesaid nano-twinned Cu—Ni alloy layer is also provided.

First claim

What is claimed is:

1. A nano-twinned Cu—Ni alloy layer, wherein more than 50% in volume of the nano-twinned Cu—Ni alloy layer comprises plural twinned grains, the plural twinned grains comprise plural columnar twinned grains, and a Ni content in the nano-twinned Cu—Ni alloy layer is in a range from 0.1 at % to 15 at %;
wherein the plural twinned grains further comprise plural oblique twinned grains stacked on the plural columnar twinned grains;
wherein the plural oblique twinned grains are formed by stacking plural nano-twins along a direction within ±15 degrees of a [111] crystal axis, and an included angle between a stacking direction of at least part of the plural nano-twins of the plural oblique twinned grains and a thickness direction of the nano-twinned Cu—Ni alloy layer is ranged from 10 degrees to 60 degrees.

2. The nano-twinned Cu—Ni alloy layer of claim 1 , wherein the plural columnar twinned grains are formed by stacking the plural nano-twins along the direction within ±15 degrees of the [111] crystal axis.

3. The nano-twinned Cu—Ni alloy layer of claim 1 , wherein the plural columnar twinned grains are formed by stacking plural nano-twins along the direction within ±15 degrees of the [111] crystal axis, and an included angle between a stacking direction of at least part of the plural nano-twins of the plural columnar twinned grains and the thickness direction of the nano-twinned Cu—Ni alloy layer is ranged from 0 degree to 20 degrees.

4. The nano-twinned Cu—Ni alloy layer of claim 3 , wherein 50% or more of an area of a surface of the nano-twinned Cu—Ni alloy layer exposes a (111) surface of the nano-twins.

5. The nano-twinned Cu—Ni alloy layer of claim 1 , wherein the plural twinned grains further comprises plural fine grains stacked on the plural columnar twinned grains, and nano-twins of the plural fine grains are stacked without a preferred direction.

6. The nano-twinned Cu—Ni alloy layer of claim 5 , wherein a surface of the nano-twinned Cu—Ni alloy layer is not a preferred surface.

7. The nano-twinned Cu—Ni alloy layer of claim 1 , wherein a surface of the nano-twinned Cu—Ni alloy layer is not a preferred surface.

8. The nano-twinned Cu—Ni alloy layer of claim 1 , wherein diameters of the plural columnar twinned grains are respectively in a range from 0.1 μm to 50 μm.

9. The nano-twinned Cu—Ni alloy layer of claim 1 , wherein thicknesses of the plural columnar twinned grains are respectively in a range from 0.1 μm to 500 μm.

10. The nano-twinned Cu—Ni alloy layer of claim 1 , wherein at least part of the plural columnar twinned grains are connected to each other.

11. A method for manufacturing a nano-twinned Cu—Ni alloy layer, comprising the following steps:
providing an electrodeposition device, comprising an anode, a cathode, a plating solution and a power supply, wherein the power supply is respectively connected to the cathode and the anode, and the cathode and the anode are immersed into the plating solution; and
performing an electrodeposition process with the electrodeposition device to grow a nano-twinned Cu—Ni alloy layer on a surface of the cathode,
wherein more than 50% in volume of the nano-twinned Cu—Ni alloy layer comprises plural twinned grains, the plural twinned grains comprise plural columnar twinned grains, and a Ni content in the nano-twinned Cu—Ni alloy layer is in a range from 0.1 at % to 15 at %;
wherein the plural twinned grains further comprise plural oblique twinned grains stacked on the plural columnar twinned grains;
wherein the plural oblique twinned grains are formed by stacking plural nano-twins along a direction within ±15 degrees of a [111] crystal axis, and an included angle between a stacking direction of at least part of the plural nano-twins of the plural oblique twinned grains and a thickness direction of the nano-twinned Cu—Ni alloy layer is ranged from 10 degrees to 60 degrees, and
wherein the plating solution comprises a Cu salt, an acid and a Ni salt.

12. The method of claim 11 , further comprising a step of: annealing the nano-twinned Cu—Ni alloy layer after growing the nano-twinned Cu—Ni alloy layer on the surface of the cathode.

13. The method of claim 12 , wherein a temperature for annealing the nano-twinned Cu—Ni alloy layer is in a range from 50° C. to 250° C.

14. The method of claim 11 , wherein the electrodeposition process is a direct current electrodeposition.

15. The method of claim 11 , wherein the electrodeposition process is a pulse electrodeposition.

16. The method of claim 15 , wherein the plural twinned grains further comprises plural fine grains stacked on the plural columnar twinned grains, and nano-twins of the plural fine grains are stacked without a preferred direction.

Assignees

• National Yang Ming Chiao Tung Univ

Inventors

• Chen Chih
• Lee Kang-Ping
• Chang Yu-I
• Chen Yun-Hsuan

Classifications

• C25D3/58

  containing more than 50% by weight of copper · CPC title

• C25D5/50

  by heat-treatment · CPC title

• C25D5/18

  Electroplating using modulated, pulsed or reversing current · CPC title

• C22F1/08

  of copper or alloys based thereon · CPC title

• C25D7/12

  Semiconductors · CPC title