Nickel-iron (80:20) alloy thin film electroplating method and electrochemical treatment and plating apparatus

• US 4,102,756 A
• Filed: 12/30/1976
• Issued: 07/25/1978
• Est. Priority Date: 12/30/1976
• Status: Expired due to Term

• Current Assignee: International Business Machines Corporation
• Original Assignee: International Business Machines Corporation
• Inventors: Romankiw, Lubomyr Taras, Powers, John Vincent, Castellani, Eugene Evans
• Primary Examiner(s): Mack, J. H.
• Assistant Examiner(s): Valentine, D. R.
• Application Number:
  US05/755,893
• Time in Patent Office: 572 Days
• Field of Search: 204/237, 204/239, 204/43 T, 204/273, 204/274, 204/123
• US Class Current: 205/82
• CPC Class Codes: C25D 21/12 Process control or regulation controlling or regulating in general G05
• CPC Class Codes: C25D 3/562 containing more than 50% by weight of iron or nickel or cobalt
• CPC Class Codes: C25D 5/08 Electroplating with moving electrolyte e.g. jet electroplating using locally applied jets of electrolyte C25D5/026
• CPC Class Codes: C25D 5/605 Surface topography of the layers, e.g. rough, dendritic or nodular layers
• CPC Class Codes: G11B 5/3163 Fabrication methods or processes specially adapted for a particular head structure, e.g. using base layers for electroplating, using functional layers for masking, using energy or particle beams for shaping the structure or modifying the properties of the basic layers
• CPC Class Codes: H01F 41/14 for applying magnetic films to substrates
• CPC Class Codes: H01F 41/26 using electric currents , e.g. electroplating

Abstract

A thin film of low magnetostriction Permalloy 80% nickel - 20% iron ± 1% is electroplated in a bath having a ratio of about 1.8:1 to 24:1 g/liter ratio of Ni to Fe ions with a plating current density from 10 ma/cm² - 200 ma/cm² when plating in sheet form or an Ni/Fe ratio of 25:1 to 85:1 with a current density of 2 ma/cm² - 110 ma/cm² when plating through a mask. The fluid in the system is constantly mixed, replenished with fresh iron, acid, and other reagents, is adjusted in temperature and subjected to a continuous laminar regime of mixing. Fresh solution is added to the bath from a reservoir where the above adjustments are made. The inlet for the fresh solution is at the lower end of the plating chamber and directed at a bath mixer which includes a slot through which the fresh solution is directed to optimize mixing in the plating chamber. Complexing agents are avoided. High speed plating is obtained with about 24.4 g/l of Ni⁺⁺, 1.05 g/l of Fe⁺⁺, 25 g/l of H₃ BO₃, 0.2 g/l of Na saccharin and a pH of 1.5 to 3.6.

Claims

1. A nickel-iron electroplating method for coating a substrate having a mask deposited thereon including means for electroplating a nickel-iron film onto a sheet substrate of a metallic material,

said method including employing a plating current density of about 2 - 60 ma/cm²,

a plating bath fluid having an Fe⁺⁺ ion concentration of about 0.3 g/l to about 1.0 g/l,

an Ni⁺⁺ ion concentration of about 17-44 g/l, a pH of about 1 - 3.6, and maintaining said fluid at a temperature of about 20°

- 35°

C,

wherein Fe⁺⁺ ion concentration required for plating is inverse to circulation of said plating bath fluid across said substrate.

2. An electroplating method in accordance with claim 1 including

cell means for containing said plating bath fluid, an anode, a cathode including said substrate to be plated with said nickel-iron film,

said cell including means for holding said cathode with the surface to be plated facing the anode of said cell,

an inlet to said cell aligned with the surface of said cathode whereby said inlet is adapted to pass plating bath fluid directly onto the surface of said cathode,

a reservoir for said plating bath fluid having an outlet connected by conduit means to said inlet, means for pumping said fluid up from said reservoir into said inlet via said conduit means,

an outlet from said cell for carrying said plating bath fluid into said reservoir,

a chemical sensor for producing an electrical signal as a function of a chemical concentration present in said system, and

a reagent dispenser for automatically dispensing at least one reagent including Fe⁺⁺ ions through a valve into said reservoir in response to said signal from said sensor.

3. A method in accordance with claim 1 wherein said bath fluid has a nickel-iron ion ratio of about 25:

1 to about 86;

1.

4. An electroplating method in accordance with claim 2 wherein said cell includes a mixer for providing agitation without substantial turbulence.

5. An electroplating method in accordance with claim 2 wherein said chemical sensor comprises a pH sensor, and said reagent dispenser dispenses acid and Fe⁺⁺ ions.

6. A method in accordance with claim 2 wherein said reservoir includes a temperature sensor, a thermostatic control, and heating means for automatically maintaining the temperature of said plating bath.

7. A nickel-iron electroplating method for coating a substrate having a mask deposited thereon including means for electroplating nickel-iron alloy films containing about 20% iron onto a sheet substrate of a metallic material having said mask thereon,

said method including employing a plating current density of about 2 - 60 ma/cm²,

a plating bath fluid having an Fe⁺⁺ ion concentration of about 0.3 g/l to about 0.7 g/l, an Ni⁺⁺ ion concentration of about 17 - 44 g/l, a pH of about 1 - 3.6, and

maintaining said bath at a temperature of about 20°

- 35°

C,

wherein Fe⁺⁺ ion concentration required for plating 20% iron is inverse to circulation of said plating bath fluid across said substrate.

8. An electroplating method in accordance with claim 7 including

cell means for containing said plating bath, an anode, a cathode including said substrate to be plated with an NiFe metallic film,

said cell including means for holding said cathode with the surface to be plated facing the anode of said cell,

an inlet to said cell aligned with the surface of said cathode whereby said inlet is adapted to pass plating bath fluid directly onto the surface of said cathode,

a reservoir for said plating bath fluid having an outlet connected by conduit means to said inlet, means for pumping said plating bath fluid up from said reservoir into said inlet via said conduit means,

an outlet from said cell for carrying said plating bath fluid into said reservoir,

a chemical sensor for producing an electrical signal as a function of a chemical concentration present in said system, and

a reagent dispenser for automatically dispensing at least including Fe⁺⁺ ions one reagent through a valve into said reservoir in response to said signal from said sensor.

9. A method in accordance with claim 7 wherein said bath fluid has a nickel-iron ratio of from about 25:

1 to about 85;

1.

10. A method in accordance with claim 8 wherein said cell includes a mixer for providing agitation without substantial turbulence.

11. A method in accordance with claim 8 wherein said chemical sensor comprises a pH sensor, and said reagent dispenser dispenses acid and Fe⁺⁺ ions.

12. A method in accordance with claim 8 wherein said reservoir includes a temperature sensor, a thermostatic control, and heating means for automatically maintaining the temperature of said plating bath.

13. A nickel-iron electroplating method including means for electroplating a nickel-iron film onto a sheet substrate of a metallic material,

said method including employing a plating current density of about 10 - 200 ma/cm²,

a plating bath fluid with an Fe⁺⁺ ion concentration of about 1 - 14 g/l an Ni⁺⁺ ion concentration of about 7 - 37 g/l, and a pH of about 1 - 3.6 maintaining said bath at a temperature of 20°

- 35°

C,

wherein Fe⁺⁺ ion concentration required in the bath for a predetermined Ni percentage in the nickel-iron film is an inverse function of circulation of bath fluid across said substrate.

14. An electroplating method in accordance with claim 13 including

cell means for containing said plating bath fluid, an anode, and a cathode including said substrate to be plated with said nickel-iron film,

said cell including means for holding said cathode with the surface to be plated facing the anode of said cell,

an inlet to said cell aligned with the surface of said cathode whereby said inlet is adapted to pass said plating bath fluid directly onto the surface of said cathode,

a reservoir for said plating bath fluid having an outlet connected by conduit means to said inlet, means for pumping fluid up from said reservoir into said inlet via said conduit means,

an outlet from said cell for carrying said plating bath fluid into said reservoir,

a chemical sensor for producing an electrical signal as a function of a chemical concentration present in said system, and

a reagent dispenser for automatically dispensing at least one reagent including Fe⁺⁺ ions through a valve into said reservoir in response to said signal from said sensor.

15. A method in accordance with claim 13 wherein said bath fluid has a nickel-iron ratio of about 5.8:

1 to about 23;

1.

16. A method in accordance with claim 14 wherein said cell includes a mixer for providing agitation without substantial turbulence.

17. A method in accordance with claim 14 wherein said chemical sensor comprises a pH sensor, and said reagent dispenser dispenses acid and Fe⁺⁺ ions.

18. A method in accordance with claim 14 wherein said reservoir includes a temperature sensor, a thermostatic control, and heating means for automatically maintaining the temperature of said plating bath.

19. A nickel-iron electroplating method including the process of electroplating nickel-iron films containing about 20% iron ±

1% onto a sheet substrate of a metallic material,

said method including employing a plating current density of about 10 - 200 ma/cm²,

a plating bath fluid with an Fe⁺⁺ ion concentration of about 1.1 - 1.7 g/l, an Ni⁺⁺ ion concentration of about 7 - 37 g/l, and a pH of about 1 - 3.6,

and maintaining said fluid at a temperature of 20°

- 35°

C,

wherein required Fe⁺⁺ ion concentration required to produce said films with 20% iron ±

1% is an inverse function of circulation of bath fluid across said substrate.

20. An electroplating method in accordance with claim 19 including

cell means for containing a plating bath fluid, an anode, and a cathode including said substrate to be plated with said nickel-iron film,

said cell including means for holding said cathode with the surface to be plated facing the anode of said cell,

an inlet to said cell aligned with the surface of said cathode whereby said inlet is adapted to pass said plating bath fluid directly onto the surface of said cathode,

a reservoir for said plating bath fluid having an outlet connected by conduit means to said inlet, means for pumping fluid up from said reservoir into said inlet via said conduit means,

an outlet from said cell for carrying said plating bath fluid into said reservoir,

a chemical sensor for producing an electrical signal as a function of a chemical concentration present in said system, and

a reagent dispenser for automatically dispensing at least one reagent including Fe⁺⁺ ions through a valve into said reservoir in response to said signal from said sensor.

21. A method in accordance with claim 20 wherein said bath has a nickel-iron ratio of about 10:

1 to about 20;

1.

22. A method in accordance with claim 20 wherein said cell includes a mixer for providing agitation without substantial turbulence.

23. A method in accordance with claim 20 wherein said chemical sensor comprises a pH sensor, and said reagent dispenser dispenses acid and Fe⁺⁺ ions.

24. A method in accordance with claim 20 wherein said reservoir includes a temperature sensor, a thermostatic control, and heating means for automatically maintaining the temperature of said plating bath.

25. A nickel-iron electroplating system including

cell means for containing a plating bath fluid, an anode, and a cathode to be plated with a nickel-iron alloy comprising a constant percentage of iron,

said cell including first and second vertical end walls,

said cell including means for holding a wafer to be plated at the cathode of said cell with the surface to be plated supported facing the anode of said cell,

a reciprocable mixer for agitation without substantial turbulence, supported by bearing means for providing longitudinal stirring action by reciprocation between said end walls cyclically, said mixer including a pair of confronting transverse blocks having a substantial slot therebetween and each having a symmetrical wedge shape with substantial opening between said blocks, said blocks having sharp edges facing the directions towards which said blade is adapted to reciprocate,

an inlet to said cell in one of said end walls aligned with the surface of said cathode whereby said inlet is adapted to pass said plating bath fluid directly onto the surface of the cathode and through said slot,

a reservoir for said plating bath fluid having an outlet connected by conduit means to said inlet, means for pumping said plating bath fluid up from said reservoir into said inlet via said conduit means,

an outlet from said cell at an upper portion thereof high above the base of said cell having second conduit means for carrying said plating bath fluid into said reservoir,

a thermostatic control, a temperature sensor and heating means connected to said reservoir for maintaining said reservoir substantially at 25°

C,

a pH sensor and a dilute acid and an Fe⁺⁺ ion dispenser for dispensing said acid and said Fe⁺⁺ ion through a valve into said reservoir, and stirring means in said reservoir for maintaining a uniform temperature, and uniform values of pH, and Fe⁺⁺ ion concentration and related conditions.

26. A method of electroplating nickel-iron alloys of 20% iron ±

1% including a plating bath solution of Ni⁺⁺ ions and Fe⁺⁺ ions,

maintaining a substantially constant ratio of Ni⁺⁺ ions and Fe⁺⁺ ions near the cathode of said system, said bath having a relatively low slope curve of weight percent of Fe in the film to current density, whereby a several percent change in current density will yield a deviation in Fe composition less than 1%.