Abstract
An apparatus for substrate metallization from electrolyte is provided. The apparatus comprises: an immersion cell containing metal salt electrolyte; at least one electrode connecting to at least one power supply; an substrate holder holding at least one substrate to expose a conductive side of the substrate to face the at least one electrode, the substrate holder being electricity conducting; an oscillating actuator oscillating the substrate holder with an amplitude and a frequency; at least one ultrasonic device with an operating frequency and an intensity, disposed in the metallization apparatus; at least one ultrasonic power generator connecting to the ultrasonic device; at least one inlet for metal salt electrolyte feed; and at least one outlet for metal salt electrolyte drain.
Claims
1.-21. (canceled)
22. An apparatus for substrate metallization from electrolyte comprising: an immersion cell containing metal salt electrolyte; at least one electrode connecting to at least one power supply, wherein the at least one electrode acts as an anode; an substrate holder holding at least one substrate to expose a conductive side of the substrate to face the at least one electrode, the substrate holder being electricity conducting; an oscillating actuator oscillating the substrate holder along the axis with an amplitude and a frequency; at least one ultrasonic device with an operating frequency and an intensity disposed at the side of the anode; at least one ultrasonic power generator connecting to the ultrasonic device; at least one inlet for metal salt electrolyte feed; at least one outlet for metal salt electrolyte drain; wherein the ultrasonic power generator drives the ultrasonic device to apply an ultrasonic wave to the oscillating actuator for oscillating the substrate holder so that the substrate moves periodically along a wave propagation direction with an amplitude and a frequency, wherein the wave propagation direction is perpendicular to the substrate surface and the anode plane, wherein each portion on the substrate receives full cycle of intensity when the substrate moves a full distance d of integer times of half wavelength, wherein each location of substrate receives the same amount of acoustic intensity including the same average intensity, the same maximum intensity, and the same minimum intensity, wherein wherein n is an integer number starting from 1 and is the wavelength of the ultrasonic wave.
23. The apparatus of claim 1, wherein the amplitude is 0.25 mm to 25 mm and the frequency is 0.01 to 0.5 Hz; and the operating frequency is 5 KHz to 5 MHz and the intensity is 0.1 to 3 W/cm.sup.2.
24. The apparatus of claim 1 comprising a rotating actuator rotating the substrate holder around an axis perpendicular to a surface of the substrate and passing a center of said substrate, wherein the rotating actuator rotates the substrate holder at a speed of 10 to 300 rpm.
25. The apparatus of claim 1, wherein the at least one ultrasonic device is disposed in a position at the side wall of the metallization apparatus,
26. The apparatus of claim 1, wherein the at least one ultrasonic device is disposed in a position behind the electrode of the metallization apparatus.
27. The apparatus of claim 1, wherein the metal salt electrolyte contains at least one cationic form of the following metals: Cu, Au, Ag, Pt, Ni, Sn, Co, Pd, Zn.
28. The apparatus of claim 1, wherein the deep cavities on the substrate have dimensions of 0.5 to 50 m in width and 5 to 500 m in depth.
29. The apparatus of claim 1, wherein the substrate holder oscillates at constant speed equal to where is the wavelength of the ultrasonic wave and t is the full process time, and n and N are integers.
30. The apparatus of claim 1, wherein an electrical current is applied in DC mode,
31. The apparatus of claim 1, wherein an electrical current is applied in pulse reverse mode with a pulse period of 5 ms to 2 s.
32. The apparatus of claim 1, wherein electrolyte agitation is provided proximate the deep cavities.
33. The apparatus of claim 1, wherein electrolyte agitation is provided inside the deep cavities.
34. The apparatus of claim 1, wherein material exchange rate of reactants and byproducts between the inside and outside of the deep cavities are increased.
35. The apparatus of claim 1, wherein impurity levels in deposit in the deep cavities are reduced.
36. The apparatus of claim 1, wherein a diffusion boundary layer with a thickness of 0.1 to 10 micrometers is reformed proximate the surface of the substrate.
37. The apparatus of claim 1, wherein metal deposition rate is increased by increasing limiting current density.
38. The apparatus of claim 1, wherein an acoustic intensity received by substrate is uniform over the course of a process.
39. The apparatus of claim 1, wherein a metalized film with uniform thickness is formed.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1a-1c show one exemplary apparatus for metallization of substrate from electrolyte solutions.
[0019] FIG. 2a-2b show another exemplary apparatus for metallization of substrate from electrolyte solutions and the solution distribution plate in the apparatus.
[0020] FIG. 3 show another exemplary apparatus for metallization of substrate from electrolyte solutions.
[0021] FIGS. 4a-4b show another exemplary apparatus for metallization of substrate from electrolyte solutions and the anode system in the apparatus.
[0022] FIG. 5 shows another exemplary apparatus for metallization of substrate from electrolyte solutions.
[0023] FIG. 6 shows another exemplary apparatus for metallization of substrate from electrolyte solutions.
[0024] FIG. 7a-7c show another exemplary apparatus for metallization of substrate from electrolyte solutions.
[0025] FIG. 8 shows another exemplary apparatus for metallization of substrate from electrolyte solutions.
[0026] FIG. 9 shows another exemplary apparatus for metallization of substrate from electrolyte solutions.
[0027] FIG. 10 shows another exemplary apparatus for metallization of substrate from electrolyte solutions.
[0028] FIG. 11 shows a method of controlling the movement of substrate during the metallization process.
DETAILED DESCRIPTION OF EMBODIMENTS
[0029] According to the embodiments of the present invention, ultrasonic devices are utilized, an example an ultrasonic device that may be applied to the present invention is described in U.S. Pat. No. 6,391,166 and WO/2009/055992.
[0030] FIG. 1a-1c show an exemplary apparatus for substrate metallization from electrolyte according to an embodiment of the present invention. The apparatus includes an ultrasonic device 1002. The apparatus for substrate metallization from electrolyte normally comprises an immersion cell 1016 containing at least one metal salt electrolyte, at least one electrode 1000 connecting to independent power supply 1050, an electricity conducting substrate holder 1006 holding the substrate 1004 to expose its conductive side to face said electrode 1000. The metal salt electrolyte flows from chamber bottom to chamber top. At least one inlet and one outlet are positioned in the cell for electrolyte circulation. The substrate holder 1006 is connected to an oscillating actuator 1010, and the substrate holder 1006 is oscillated by an oscillating actuator 1010 with an amplitude from 0.25 to 25 mm and a frequency from 0.01 to 0.5 Hz. it holds substrate 1004 to move up and down periodically along a direction which is perpendicular to the bottom plane of the metallization apparatus during process. The independent power supply 1050 connects to at least one electrode 1000 and works in voltage-controlled mode or current-controlled mode with pre-programmed waveforms, and switch between the two modes at desire time. The applying electrical current is operable in DC mode or pulse reverse mode with pulse period from 5 ms to 2 s. The ultrasonic device 1002 is fixed in a position at the sidewall of the metallization apparatus, to generate the ultrasonic wave with a frequency from 10 KHz to 5 MHz and an intensity from 0.1 to 3 W/cm2. An example of the metallization apparatus from electrolyte solutions to apply the ultrasonic device is described in U.S. Pat. No. 6,391,166 and WO/2009/055992.
[0031] FIG. 2a shows another exemplary apparatus for substrate metallization from electrolyte according to an embodiment of the present invention. The apparatus includes an ultrasonic device 1002. The apparatus for substrate metallization from electrolyte iron malty comprises an immersion cell 1016 containing at least one metal salt electrolyte, at least one electrode 1000 connecting to independent power supply 1050, an electricity conducting substrate holder 1006 holding the substrate 1004 to expose its conductive side to face said electrode 1000. The metal salt electrolyte flows from chamber bottom to chamber top. At least one inlet and one outlet are positioned in the cell for electrolyte circulation. The substrate holder 1006 is connected to an oscillating actuator 1010, and the substrate holder 1006 is oscillated by an oscillating actuator 1010 with an amplitude from 0.25 to 25 mm and a frequency from 0.01 to 0.5 Hz. It holds substrate 1004 to move up and down periodically along z direction during process which is perpendicular to the bottom plane of the metallization apparatus. There is a shielding plate 1020 in between the anode 1000 and the substrate 1004 in the metallization apparatus, providing a uniform electrical field distribution across the substrate 1004 surface. FIG. 2b shows an exemplary design of the shielding plate 1020. The independent power supply 1050 connects to at least one electrode 1000 and works in voltage-controlled mode or current-controlled mode with pre-programmed waveforms, and switch between the two modes at desire time. The applying electrical current is operable in DC mode or pulse reverse mode with pulse period from 5 ms to 2 s. The ultrasonic device 1002 is fixed in a position at the sidewall of the metallization apparatus, to generate the ultrasonic wave with a frequency from 10 KHz to 5 MHz and an intensity from 0.1 to 3 W/cm2.
[0032] FIG. 3 shows another exemplary apparatus for substrate metallization from electrolyte according to an embodiment of the present invention. The apparatus includes two ultrasonic devices 1002 and 1003. The apparatus for substrate metallization from electrolyte normally comprises an immersion cell 1016 containing at least one metal salt electrolyte, at least one electrode 1000 connecting to independent power supply 1050, an electricity conducting substrate holder 1006 holding the substrate 1004 to expose its conductive side to face said electrode 1000. The metal salt electrolyte flows from chamber bottom to chamber top. At least one inlet and one outlet are positioned in the cell for electrolyte circulation. The substrate holder 1006 is connected to an oscillating actuator 1010, and the substrate holder 1006 is oscillated by an oscillating actuator 1010 with an amplitude from 0.25 to 25 mm and a frequency from 0.01 to 0.5 Hz. It holds substrate 1004 to move up and down periodically along a direction which is perpendicular to the bottom plane of the metallization apparatus during process. There is a shielding plate 1020 in between the anode 1000 and the substrate 1004 in the metallization apparatus, providing a uniform electrical field distribution across the substrate 1004 surface. The independent power supply 1050 connects to at least one electrode 1000 and works in voltage-controlled mode or current-controlled mode with pre-programmed waveforms, and switch between the two modes at desire time. The applying electrical current is operable in DC mode or pulse reverse mode with pulse period from 5 ms to 2 s. The ultrasonic devices 1002 and 1003 are fixed at the sidewall of the metallization apparatus and at the different side of the shielding plate 1020, to generate the ultrasonic wave with a frequency from 10 KHz to 5 MHz and an intensity from 0.1 to 3 W/cm2.
[0033] FIG. 4a shows another exemplary apparatus for substrate metallization from electrolyte according to an embodiment of the present invention. The apparatus includes an ultrasonic device 1002. The apparatus for substrate metallization from electrolyte normally comprises an immersion cell 1016 containing at least one metal salt electrolyte, multiple electrodes 1000A, 1000B, 1000C and 1000D connecting to independent power supplies 1050, 1052, 1054, 1056 specifically, an electricity conducting substrate holder 1006 holding the substrate 1004 to expose its conductive side to face said electrodes 1000 A, 1000B, 1000C and 1000D. FIG. 4b shows an exemplary design of the multiple electrodes 1000A, 1000B, 1000C and 1000D. The metal salt electrolyte flows from chamber bottom to chamber top. At least one inlet and one outlet are positioned in the cell for electrolyte circulation. The substrate bolder 1006 is connected to an oscillating actuator 1010, and the substrate holder 1006 is oscillated by an oscillating actuator 1010 with an amplitude from 0.25 to 25 mm and a frequency from 0.01 to 0.5 Hz. It holds substrate 1004 to move up and down periodically along a direction which is perpendicular to the bottom plane of the metallization apparatus during process. The independent power supplies 1050, 1052, 1054 and 1056 connect to multiple electrodes 1000A, 1000B 1000C and 1000D, and work in voltage-controlled mode or current-controlled mode with pre-programmed waveforms, and switch between the two modes at desire time. The applying electrical current is operable in DC mode or pulse reverse mode with pulse period from 5 ms to 2 s. The ultrasonic device 1002 is fixed in a position at the sidewall of the metallization apparatus, to generate the ultrasonic wave with a frequency from 10 KHz to 5 MHz and an intensity from 0.1 to 3 W/cm2.
[0034] FIG. 5 shows another exemplary apparatus for substrate metallization from electrolyte according to an embodiment of the present invention. The apparatus includes two ultrasonic devices 1002 and 1003. The apparatus for substrate metallization from electrolyte normally comprises an immersion cell 1016 which is divided into a anode cell and a cathode cell by a membrane 1032, containing one metal salt anolyte and one catholyte, at least one electrode 1000 connecting to independent power supply 1050, an electricity conducting substrate holder 1006 holding the substrate 1004 to expose its conductive side to face said electrode 1000. The metal salt electrolyte flows from chamber bottom to chamber top. One inlet and one outlet are positioned in the anode cell for anolyte circulation with an anolyte circulation mechanism 1024, and another inlet and another outlet are positioned in the cathode cell for catholyte circulation with a catholyte circulation mechanism 1026. The substrate holder 1006 is connected to an oscillating actuator 1010, and the substrate holder 1006 is oscillated by an oscillating actuator 1010 with an amplitude from 0.25 to 25 mm and a frequency from 0.01 to 0.5 Hz. It holds substrate 1004 to move up and down periodically along a direction which is perpendicular to the bottom plane of the metallization apparatus during process. There is a shielding plate 1020 in between the anode 1000 and the substrate 1004 in the metallization apparatus, providing a uniform electrical field distribution across the substrate 1004 surface. The independent power supply 1050 connects to at least one electrode 1000 and works in voltage-controlled mode or current-controlled mode with pre-programmed waveforms, and switch between the two modes at desire time. The applying electrical current is operable in DC mode or pulse reverse mode with pulse period from 5 ms to 2 s. The ultrasonic devices 1002 and 1003 are fixed at the sidewall of the metallization apparatus and at the different side of the shielding plate 1020, to generate the ultrasonic wave with a frequency from 10 KHz to 5 MHz and an intensity from 0.1 to 3 W/cm2.
[0035] FIG. 6 shows another exemplary apparatus for substrate metallization from electrolyte according to an embodiment of the present invention. The apparatus includes an ultrasonic device 1002. The apparatus for substrate metallization from electrolyte normally comprises an immersion cell 1016 containing at least one metal salt electrolyte, multiple electrodes 1000A, 1000B, 1000C and 1000D connecting to independent power supplies 1050, 1052, 1054, 1056 specifically, an electricity conducting substrate holder 1006 holding the substrate 1004 to expose its conductive side to face said electrodes 1000 A, 1000B, 1000C and 1000D. FIG. 4b shows an exemplary design of the multiple electrodes 1000A, 1000B, 1000C and 1000D. The metal salt electrolyte flows from chamber bottom to chamber top. At least one inlet and one outlet are positioned in the cell for electrolyte circulation. Both the substrate holder 1006 and the multiple electrode system are connected to an oscillating actuator 1010, and the substrate holder 1006 and the multiple electrode system are oscillated by an oscillating actuator 1010 with an amplitude from 0.25 to 25 mm and a frequency from 0.01 to 0.5 Hz. It holds substrate 1004 to move up and down periodically along a direction which is perpendicular to the bottom plane of the metallization apparatus during process. The independent power supplies 1050, 1052, 1054 and 1056 connect to multiple electrodes 1000A, 1000B, 1000C and 1000D, and work in voltage-controlled mode or current-controlled mode with pre-programmed waveforms, and switch between the two modes at desire time. The applying electrical current is operable in DC mode or pulse reverse mode with pulse period from 5 ms to 2 s. The ultrasonic device 1002 is fixed in a position at the sidewall of the metallization apparatus, to generate the ultrasonic wave with a frequency from 10 KHz to 5 MHz and an intensity from 0.1 to 3 W/cm2.
[0036] FIG. 7a-7c show another exemplary apparatus for substrate metallization from electrolyte according to an embodiment of the present invention. The apparatus includes an ultrasonic device 1002 at the sidewall of the apparatus. The substrate holder 1006 holds substrate 1004 to move periodically along a direction which is perpendicular to the sidewall plane of the metallization apparatus during process.
[0037] FIG. 8 shows another exemplary apparatus for substrate metallization from electrolyte according to an embodiment of the present invention. The apparatus includes an ultrasonic device 1002 which is disposed at the anode side and insulated from the electrolyte by an oaring 1022. The apparatus for substrate metallization from electrolyte normally comprises an immersion cell 1016 containing at least one metal salt electrolyte, at least one electrode 1000, an electricity conducting substrate holder 1006 holding the substrate 1004 to expose its conductive side to face said electrode 1000. The metal salt electrolyte flows from chamber bottom to chamber top. At least one inlet and one outlet are positioned in the cell for electrolyte circulation. The substrate holder 1006 is connected to an oscillating actuator 1010, and the substrate holder 1006 is oscillated by an oscillating actuator 1010 with an amplitude from 0.25 to 25 mm and a frequency from 0.01 to 0.5 Hz. It holds substrate 1004 to move periodically along a direction which is perpendicular to the anode plane of the metallization apparatus during process. The independent power supply 1050 connects to at least one electrode 1000 and works in voltage-controlled mode or current-controlled mode with pre-programmed waveform, and switch between the two modes at desire time. The applying electrical current is operable in DC mode or pulse reverse mode with pulse period from 5 ms to 2 s. The ultrasonic device 1002 is fixed in a position at the sidewall of the metallization apparatus, to generate the ultrasonic wave with a frequency from 10 KHz to 5 MHz and an intensity from 0.1 to 3 W/cm2.
[0038] FIG. 9 shows another exemplary apparatus for substrate metallization from electrolyte according to an embodiment of the present invention. The apparatus includes an ultrasonic device 1002 which is disposed at the anode side and insulated from the electrolyte by an o-ring 1022. The apparatus for substrate metallization from electrolyte normally comprises an immersion cell 1016 containing at least one metal salt electrolyte, at least one electrode 1000, an electricity conducting substrate holder 1006 holding the substrate 1004 to expose its conductive side to face said electrode 1000 and a rotating mechanism 1026 to rotate the substrate holder 1006 during the process. The metal salt electrolyte flows from chamber bottom to chamber top. At least one inlet and one outlet are positioned in the cell for electrolyte circulation. The substrate holder 1006 is connected to an oscillating actuator 1010, and the substrate holder 1006 is oscillated by an oscillating actuator 1010 with an amplitude from 0.25 to 25 mm and a frequency from 0.01 to 0.5 Hz. It holds substrate 1004 to move periodically along a direction which is perpendicular to the anode plane of the metallization apparatus during process. The independent power supply 1050 connects to at least one electrode 1000 and works in voltage-controlled mode or current-controlled mode with pre-programmed waveforms, and switch between the two modes at desire time. The applying electrical current is operable in DC mode or pulse reverse mode with pulse period from 5 ms to 2 s. The ultrasonic device 1002 is fixed in a position at the sidewall of the metallization apparatus, to generate the ultrasonic wave with a frequency from 10 KHz to 5 MHz and an intensity from 0.1 to 3 W/cm2.
[0039] FIG. 10 shows another exemplary apparatus for substrate metallization from electrolyte according to an embodiment of the present invention. The apparatus includes two ultrasonic devices 1002 and 1003. The apparatus for substrate metallization from electrolyte normally comprises an immersion cell 1016 containing at least one metal salt electrolyte, two electrodes 1000, an electricity conducting substrate holder 1006 holding two substrates 1004 simultaneously to expose their conductive sides to face said electrodes 1000. The metal salt electrolyte flows from chamber bottom to chamber top. At least one inlet and one outlet are positioned in the cell for electrolyte circulation. The substrate holder 1006 is connected to an oscillating actuator 1010, and the substrate holder 1006 is oscillated by an oscillating actuator 1010 with an amplitude from 0.25 to 25 mm and a frequency from 0.01 to 0.5 Hz. It holds two substrates 1004 to move up and down periodically along a direction which is perpendicular to the bottom plane of the metallization apparatus simultaneously during process. The ultrasonic devices 1002 and 1003 are fixed in a position at the sidewall of the metallization apparatus, to generate the ultrasonic wave with a frequency from 10 KHz to 5 MHz and an intensity from 0.1 to 3 W/cm2 for each substrate 1004 independently.
[0040] The deposition rate in an electrochemical process is controlled by the mass transport rate of the chemicals at the solid and fluid interface near the semiconductor substrate surface, when a high deposition rate is used and current density is very close to the limiting current density, By Fick's law, reducing the diffusion boundary layer thickness increases the mass transport rate. In a conventional electrochemical deposition chamber, deposition rate can be increased by enhancing the rotation rate of the spin disk to lower the diffusion boundary layer thickness on a surface of the substrate. However, the deposition rate is restricted by the rotation speed increase in a practical application due to the high rotation speed in a fluid chamber generating vortices, gas and splashing during the electrochemical deposition process. The ultrasonic device decreases the diffusion boundary layer thickness by acoustic streaming. Hence, it increases the deposition rate without increasing the rotation speed of the substrate. The acoustic boundary layer a introduced by sonic energy is employed to approximate the diffusion layer thickness. It is a function of acoustic frequency f and liquid viscosity :
[00001]
[0041] Table 1 shows the boundary layer thickness near the substrate with and without sonic device in a low acid copper deposition process. Herein, Cu.sup.2+ concentration is 0.0625 mol/L, and acid concentration is 1.25E-03 mol/L.
TABLE-US-00001 TABLE 1 Condition m Spin-Substrate without Sonic 15 RPM 106.3 Device 60 RPM 53.2 10 kHz 5.6 20 kHz 4.0 Spin Disk with Sonic Device 80 kHz 2.0 1 MHz 0.6 5 MHz 0.3
[0042] A much smaller boundary layer on the substrate surface can be achieved by applying the ultrasonic device in the metallization apparatus, which leads to a higher deposition rate of metal film. And the high rate deposition can be achieved by enhancing intensity or frequency of sonic source.
[0043] Another advantage of applying the ultrasonic device in the metallization apparatus is enhancing the chemical exchange rate in small features where convection is limited. With very thin boundary layer and high velocity, the acoustic streaming generated by ultrasonic device can reach to the steady flow area in the small feature, stimulating the vortex destruction and flow regeneration. Furthermore, local flow direction in the vicinity of sonic cavitation sites is isotropic, meaning flow normal to the surface of the substrate also exists, which, in turn, increases the chemical exchange rate by enhancing convection of fresh chemicals and byproducts inside the features. The effect of both thin boundary layer and cavitation-induced convective flow is the freshness of electrolyte mixture in the features, especially for the organic additive molecules, so as to enhance the deposition rate and the bottom-up filling performance. Meanwhile, this also prevents the break-down byproducts generated by electrochemical reactions from being trapped and incorporated into the deposit film, which, in turn, improves the gapfill performance and other physical properties of the deposited film.
[0044] However, the distribution of the ultrasonic energy in the electrolyte near the substrate surface is not uniform. While the ultrasonic wave propagates in the electrolyte, the intensity of the ultrasonic wave presents a periodic distribution which generates high energy and low energy spots in the electrolyte with a periodic distribution based on the wavelength of the ultrasonic wave, . The non-uniform energy distribution will lead to the non-uniform film deposition rate on the substrate surface. In one embodiment of the present invention, the oscillation actuator 1010, oscillating substrate holder 1006 periodically, is used to keep the acoustic intensity distribution across substrate the same in a cumulative time. The amplitude and frequency of the oscillation can be precisely controlled by the oscillation actuator 1010. It is critical to let each portion of the surface of the substrate receiving same total acoustic intensity in each oscillation, while substrate oscillating N turns in the full process time t. The movement of the substrate in a single oscillating turn changes d, determined by the amplitude of oscillation, is
[00002]
ensuring the intensity going through the minimum to maximum. Therefore, the speed of substrate holder oscillation v should be set at:
[00003]
[0045] where n is an integer number starting from 1, N is the number of revolutions, which is also an integer number.
[0046] As shown further in detail in FIG. 11, when the position of substrate changes, the acoustic intensity at the same portion of substrate changes from P1 to P2. When the gap increases total half wavelength of sonic wave, the intensity varies a full cycle from P1 to P11. The cycle starting point depends on the position of the portion of substrate in the metallization apparatus. However, each portion on substrate will receive full cycle of intensity when the substrate moves a full distance of n.Math./2. This will guarantee each location of substrate to receive the same mount of acoustic intensity including the same average intensity, the same maximum intensity, and the same minimum intensity. This further ensures a uniform deposition rate across substrate during the whole electrochemical deposition process.
[0047] The method applied to the metallization apparatus with an ultrasonic device can be set as follows:
[0048] Process Sequence
[0049] Step 1: introduce a metal salt electrolyte into said apparatus;
[0050] Step 2: transfer a substrate to a substrate holder with electrical conduction. path to substrate conductive layer that is to be exposed to the electrolyte, the substrate holder is electricity conducting;
[0051] Step 3: apply a small bias voltage up to 10V to substrate;
[0052] Step 4: bring substrate into electrolyte, and the front surface of the substrate is in full contact with the electrolyte;
[0053] Step 5: apply electrical current to each electrode; the power supplies connected to electrodes switch from voltage mode to current mode at desired times;
[0054] Step 6; maintain constant electrical current on electrode with the electrical current range from 0.1 A to 100 A; in another embodiment, the applying electrical current is operable pulse reverse mode with pulse period from 5 ms to 2 s;
[0055] Step 7: turn on ultrasonic device and oscillate substrate holder; the intensity of ultrasonic device is in the range of 0.1 to 3 W/cm.sup.2; the frequency of ultrasonic device is set between 5 KHz to 5 MHz; the substrate holder oscillation amplitude range is from 0.01. to 0.25 mm; the substrate holder oscillation frequency range is from 0.01 to 0.25 Hz; the substrate holder oscillation is at constant seed of
[00004]
where is the wavelength of the ultrasonic wave and t is the fill process time, n and N are integers;
[0056] Step 8: turn off ultrasonic device and stop oscillation;
[0057] Step 9: switch power supply to a small bias voltage mode from 0.1V to 0.5V, and apply it on the substrate;
[0058] Step 10: bring the substrate out of the electrolyte;
[0059] Step 11: stop power supply and clean off the residue electrolyte on a surface of the substrate.
[0060] Although the present invention has been described with respect to certain embodiments, examples, and applications, it will be apparent to those skilled in the art that various modifications and changes may be made without departing from the invention.
