Electrolytic method for filling holes and cavities with metals

1. A galvanic method for filling cavities, blind holes or micro blind holes of a work piece with metals, comprising

bringing into contact the work piece containing cavities, blind holes or micro blind holes with a metal deposition electrolyte and

applying a voltage between the work piece and at least one anode such that a current flow is fed to the work piece, and

wherein the electrolyte contains a Fe(II)/Fe(III) redox system and the Fe(II) ion concentration is contained at at least 1 g/l and the Fe(III) ion concentration is contained at 7-30 g/l, and wherein the metal deposition predominantly occurs in the cavities, blind holes or micro blind holes, rather than at the surface of the work piece;

wherein a first voltage is applied between a first side of the work piece and at least one first anode such that a first pulse reverse current is fed to the first side of the work piece, wherein at least one first forward current pulse and at least one first reverse current pulse flow in each cycle of said first pulse reverse current, a second voltage is applied between a second side of the work piece and at least one second anode such that a second pulse reverse current is fed to the second side of the work piece, wherein at least one second forward current pulse and at least one second reverse current pulse flow in each cycle of said second pulse reverse current.

2. A method according to claim 1 , wherein the Fe(II) ion concentration is contained at 2-25 g/l and the Fe(III) ion concentration is contained at 7-15 g/l.

3. A method according to claim 2 , wherein the Fe(III) ion concentration is contained at 7-9 g/l.

4. A method according to claim 1 , wherein the electrolyte contains 15-75 g/l copper, 50-300 g/l H 2 SO 4 and 20-200 mg/l chloride.

5. A method according to claim 1 , wherein the Fe(III) ion concentration is contained at 7-8 g/l.

6. A method according to claim 1 , wherein the cavities, blind holes or micro blind holes have a maximum height of 3.5 mm.

7. A method according to claim 1 , wherein the cavities, blind holes or micro blind holes have a maximum diameter of 1000 μm.

8. A method according to claim 1 , wherein the work piece is a circuit board or another electric circuit support in board form.

9. A method according to claim 1 , wherein the cavities, blind holes or micro blind holes have a height of 0.05 mm-0.5 mm.

10. A method according to claim 1 , wherein the cavities, blind holes or micro blind holes have a diameter of 60 μm-150 μm.

11. A method according to claim 1 wherein the Fe(II) ion concentration is 2-25 g/l, the Fe(III) ion concentration is contained at 7-15 g/l, and the electrolyte further contains 15-75 g/l copper, 50-300 g/l H 2 SO 4 and 20-200 mg/l chloride, and wherein the cavities, blind holes or micro blind holes have a maximum height of 3.5 mm and a maximum diameter of 1000 μm.

12. A galvanic method for filling cavities, through holes, blind holes or micro blind holes of a work piece with metals, comprising

bringing into contact the work piece containing cavities, through holes, blind holes or micro blind holes with a metal deposition electrolyte and

applying a voltage between the work piece and at least one anode such that a current flow is fed to the work piece and a metal deposition completely fills the cavities, through holes, blind holes or micro blind holes, and

wherein the electrolyte contains a Fe(II)/Fe(III) redox system and the Fe(II) ion concentration is contained at at least 1 g/l and the Fe(III) ion concentration is contained at 7-30 g/l, and wherein the metal deposition predominantly occurs in the cavities, through holes, blind holes or micro blind holes, rather than at the surface of the work piece,

wherein a first voltage is applied between a first side of the work piece and at least one first anode such that a first pulse reverse current is fed to the first side of the work piece, wherein at least one first forward current pulse and at least one first reverse current pulse flow in each cycle of said first pulse reverse current, a second voltage is applied between a second side of the work piece and at least one second anode such that a second pulse reverse current is fed to the second side of the work piece, wherein at least one second forward current pulse and at least one second reverse current pulse flow in each cycle of said second pulse reverse current.

13. A method according to claim 12 , wherein the electrolyte contains 15-75 g/l copper, 50-300 g/l H 2 SO 4 and 20-200 mg/l chloride.

14. A method according to claim 12 , wherein the current flow in a first step (i) is selected such that a preferred deposition occurs in the center of the through holes and as a result the through holes grow together completely or almost completely, and in a further step (ii) further bringing into contact the work piece with a metal deposition electrolyte and applying a voltage between the work piece and at least one anode is carried out such that a current flow is fed to the work piece, wherein the through holes obtained according to step (i), which are completely or almost completely separated into two halves, are filled by the metal,

wherein the current flow according to step (i) is a pulse reverse current and at least one forward current pulse and at least one reverse current pulse occurs in each current cycle and that the current flow according to step (ii) is either a pulse reverse current, a direct current or an alternating current, and wherein in step (i) the ratio of the duration of the at least one forward current pulse to the duration of the at least one reverse current pulse is adjusted to 5-75, the duration of the at least one forward current pulse is adjusted to 5-250 ms and the duration of the at least one reverse current pulse is adjusted to 20 ms at the most;

wherein during the carrying out of step (i), the ratio of the peak current density of the forward current pulse to the peak current density of the reverse current pulse is increased or during the carrying out of step (i), the ratio of the duration of the forward current pulse to the duration of the reverse current pulse is lowered.

15. A method according to claim 12 , wherein the first current pulse is shifted with respect to the second current pulse by about 180°.

16. A method according to claim 12 , wherein the current flow in a first step (i) is selected such that a preferred deposition occurs in the center of the through holes and as a result the through holes grow together completely or almost completely, and in a further step (ii) further bringing into contact the work piece with a metal deposition electrolyte and applying a voltage between the work piece and at least one anode is carried out such that a current flow is fed to the work piece, wherein the through holes obtained according to step (i), which are completely or almost completely separated into two halves, are filled by the metal,

wherein the current flow according to step (i) is a pulse reverse current and at least one forward current pulse and at least one reverse current pulse occurs in each current cycle and that the current flow according to step (ii) is either a pulse reverse current, a direct current or an alternating current, and wherein in step (i) the ratio of the duration of the at least one forward current pulse to the duration of the at least one reverse current pulse is adjusted to 5-75, the duration of the at least one forward current pulse is adjusted to 5-250 ms and the duration of the at least one reverse current pulse is adjusted to 20 ms at the most.

17. A method according to claim 16 , wherein the metallization steps (i) and (ii) are carried out in the same electrolyte.

18. A method according to claim 16 , wherein the ratio of the duration of the at least one forward current pulse to the duration of the at least one reverse current pulse is adjusted to about 20.

19. A method according to claim 16 , wherein the duration of the at least one reverse current pulse is adjusted to 1-10 ms.

20. A method according to claim 16 , wherein the peak current density of the at least one forward current pulse at the work piece is adjusted to a maximum of 15 A/dm 2 .

21. A method according to claim 16 , wherein the peak current density of the at least one reverse current pulse at the work piece is adjusted to a maximum of 60 A/dm 2 .

22. A method according to claim 16 , wherein the peak current density of the at least one forward current pulse at the work piece is adjusted to a maximum of 1.5-8 A/dm 2 in horizontal methods and to a maximum of 2 A/dm 2 in vertical methods.

23. A method according to claim 16 , wherein the peak current density of the at least one reverse current pulse at the work piece is adjusted to a maximum of 30-50 A/dm 2 in horizontal methods and to a maximum of 3-10 A/dm 2 in vertical methods.

24. A method according to claim 16 wherein during the carrying out of step (i), the ratio of the peak current density of the forward current pulse to the peak current density of the reverse current pulse is increased.

25. A method according to claim 16 wherein during the carrying out of step (i), the ratio of the duration of the forward current pulse to the duration of the reverse current pulse is lowered.