The invention provides an apparatus and a method for achieving reliable, consistent metal electroplating or electrochemical deposition onto semiconductor substrates. More particularly, the invention provides uniform and void-free deposition of metal onto metal seeded semiconductor substrates having sub-micron, high aspect ratio features. The invention provides an electrochemical deposition cell comprising a substrate holder, a cathode electrically contacting a substrate plating surface, an electrolyte container having an electrolyte inlet, an electrolyte outlet and an opening adapted to receive a substrate plating surface and an anode electrically connect to an electrolyte. Preferably, a vibrator is attached to the substrate holder to vibrate the substrate in at least one direction, and an auxiliary electrode is disposed adjacent the electrolyte outlet to provide uniform deposition across the substrate surface. Preferably, a periodic reverse current is applied during the plating period to provide a void-free metal layer within high aspect ratio features on the substrate.
|
17. An apparatus for electrochemical deposition of a metal onto a substrate having a substrate plating surface, comprising:
a) a substrate holder adapted to hold the substrate in a position wherein the substrate plating surface is exposed to an electrolyte in an electrolyte container;
b) a cathode electrically contacting the substrate plating surface;
c) an electrolyte container having an electrolyte inlet, an electrolyte outlet and an opening adapted to receive the substrate plating surface;
d) an anode electrically connected to the electrolyte; and
e) a reference electrode adapted to monitor the cathode and the anode.
18. An apparatus for electrochemical deposition of a metal onto a substrate having a substrate plating surface, comprising:
a) a substrate holder adapted to hold the substrate in a position wherein the substrate plating surface is exposed to an electrolyte in an electrolyte container;
b) a cathode electrically contacting the substrate plating surface;
c) an electrolyte container having an electrolyte inlet, an electrolyte outlet and an opening adapted to receive the substrate plating surface;
d) an anode electrically connected to the electrolyte; and
e) a rinsing solution supply selectively connected to the electrolyte inlet.
16. An apparatus for electrochemical deposition of a metal onto a substrate having a substrate plating surface, comprising:
a) a substrate holder adapted to hold the substrate in a position wherein the substrate plating surface is exposed to an electrolyte in an electrolyte container;
b) a cathode electrically contacting the substrate plating surface;
c) an electrolyte container having an electrolyte inlet, an electrolyte outlet and an opening adapted to receive the substrate plating surface;
d) an anode electrically connected to the electrolyte; and
e) a wafer catcher disposed at a top portion within the electrolyte container.
14. An apparatus for electrochemical deposition of a metal onto a substrate having a substrate plating surface, comprising:
a) a substrate holder adapted to hold the substrate in a position wherein the substrate plating surface is exposed to an electrolyte in an electrolyte container;
b) a cathode electrically contacting the substrate plating surface;
c) an electrolyte container having an electrolyte inlet, an electrolyte outlet and an opening adapted to receive the substrate plating surface;
d) an anode electrically connected to the electrolyte; and
e) a flow adjuster wedge disposed at a top portion within the electrolyte container.
28. A method for electrochemical deposition of a metal onto a substrate, comprising:
a) providing an electrochemical deposition cell comprising:
1) a substrate holder;
2) a cathode electrically contacting a substrate plating surface;
3) an electrolyte container having an electrolyte inlet, an electrolyte outlet and an opening adapted to receive a substrate plating surface; and
4) an anode electrically connected to an electrolyte;
b) applying electrical power to the cathode and the anode;
c) flowing an electrolyte to contact the substrate plating surface;
d) rotating the substrate holder about a central axis through the substrate.
15. An apparatus for electrochemical deposition of a metal onto a substrate having a substrate plating surface, comprising:
a) a substrate holder adapted to hold the substrate in a position wherein the substrate plating surface is exposed to an electrolyte in an electrolyte container;
b) a cathode electrically contacting the substrate plating surface;
c) an electrolyte container having an electrolyte inlet, an electrolyte outlet and an opening adapted to receive the substrate plating surface;
d) an anode electrically connected to the electrolyte; and
e) a gas knife to supply a gas flow across the wafer plating surface to remove residual electrolyte.
20. A method for electrochemical deposition of a metal onto a substrate, comprising:
a) providing an electrochemical deposition cell comprising:
1) a substrate holder;
2) a cathode electrically contacting a substrate plating surface;
3) an electrolyte container having an electrolyte inlet, an electrolyte outlet and an opening adapted to receive a substrate plating surface; and
4) an anode electrically connected to an electrolyte;
b) applying electrical power to the cathode and the anode; and
c) flowing an electrolyte to contact the substrate plating surface, wherein the electrolyte flows between about 0.25 gallons per minute (gpm) to about 15 gpm.
26. A method for electrochemical deposition of a metal onto a substrate, comprising:
a) providing an electrochemical deposition cell comprising:
1) a substrate holder;
2) a cathode electrically contacting a substrate plating surface;
3) an electrolyte container having an electrolyte inlet, an electrolyte outlet and an opening adapted to receive a substrate plating surface; and
4) an anode electrically connected to an electrolyte;
b) applying electrical power to the cathode and the anode;
c) flowing an electrolyte to contact the substrate plating surface; and
d) vibrating a component of the electrochemical deposition cell in one or more directions.
11. An apparatus for electrochemical deposition of a metal onto a substrate having a substrate plating surface, comprising:
a) a substrate holder adapted to hold the substrate in a position wherein the substrate plating surface is exposed to an electrolyte in an electrolyte container;
b) a cathode electrically contacting the substrate plating surface;
c) an electrolyte container having an electrolyte inlet, an electrolyte outlet and an opening adapted to receive the substrate plating surface;
d) an anode electrically connected to the electrolyte; and
e) a vibrator attached to the substrate holder, the vibrator transferring a vibration to the substrate holder.
19. An apparatus for electrochemical deposition of a metal onto a substrate having a substrate plating surface, comprising:
a) a substrate holder adapted to hold the substrate in a position wherein the substrate plating surface is exposed to an electrolyte in an electrolyte container;
b) a cathode electrically contacting the substrate plating surface;
c) an electrolyte container having an electrolyte inlet, an electrolyte outlet and an opening adapted to receive the substrate plating surface;
d) an anode electrically connected to the electrolyte; and
e) gas bubble diverting vanes disposed within the electrolyte container to divert gas bubbles toward an electrolyte container sidewall.
13. An apparatus for electrochemical deposition of a metal onto a substrate having a substrate plating surface, comprising:
a) a substrate holder adapted to hold the substrate in a position wherein the substrate plating surface is exposed to an electrolyte in an electrolyte container;
b) a cathode electrically contacting the substrate plating surface;
c) an electrolyte container having an electrolyte inlet, an electrolyte outlet and an opening adapted to receive the substrate plating surface;
d) an anode electrically connected to the electrolyte; and
e) a sleeve insert disposed at a top portion of the electrolyte container, the sleeve insert defining the opening of the electrolyte container.
8. An apparatus for electrochemical deposition of a metal onto a substrate having a substrate plating surface, comprising:
a) a substrate holder adapted to hold the substrate in a position wherein the substrate plating surface is exposed to an electrolyte in an electrolyte container;
b) a cathode electrically contacting the substrate plating surface;
c) an electrolyte container having an electrolyte inlet, an electrolyte outlet and an opening adapted to receive the substrate plating surface;
d) an anode electrically connected to the electrolyte; and
e) a control electrode disposed in electrical contact with the electrolyte, the control electrode adapted to provide an adjustable electrical power.
0. 30. An apparatus for electrochemically depositing a metal onto a semiconductor substrate, comprising:
a container having a fluid inlet, a fluid outlet, and an open portion, the container being configured to contain an electrochemical plating solution therein;
a substrate holder assembly configured to electrically contact a substrate plating surface and support the plating surface in fluid communication with the electrochemical plating solution via the open portion;
an anode in fluid communication with the electrochemical plating solution; and
a porous fluid flow adjustment member positioned across the container between the anode and the open portion, wherein the porous fluid flow adjustment member comprises a ceramic member.
6. An apparatus for electrochemical deposition of a metal onto a substrate having a substrate plating surface, comprising:
a) a substrate holder adapted to hold the substrate in a position wherein the substrate plating surface is exposed to an electrolyte in an electrolyte container;
b) a cathode electrically contacting the substrate plating surface;
c) an electrolyte container having an electrolyte inlet, an electrolyte outlet and an opening adapted to receive the substrate plating surface, wherein the electrolyte outlet is defined by a gap between a first surface on the substrate holder extending radially outward from the substrate plating surface and a surface of the electrolyte container; and
d) an anode electrically connected to the electrolyte.
0. 42. An apparatus for electrochemically depositing a metal onto a semiconductor substrate, comprising:
a container having a fluid inlet, a fluid outlet, and an open portion, the container being configured to contain an electrochemical plating solution therein;
a substrate holder assembly configured to electrically contact a substrate plating surface and support the plating surface in fluid communication with the electrochemical plating solution via the open portion;
an anode in fluid communication with the electrochemical plating solution;
a porous fluid flow adjustment member positioned across the container between the anode and the open portion; and
at least one auxiliary electrode positioned in fluid communication with the electrochemical plating solution.
24. A method for electrochemical deposition of a metal onto a substrate, comprising:
a) providing an electrochemical deposition cell comprising:
1) a substrate holder;
2) a cathode electrically contacting a substrate plating surface;
3) an electrolyte container having an electrolyte inlet an electrolyte outlet and an opening adapted to receive a substrate plating surface; and
4) an anode electrically connected to an electrolyte;
b) applying electrical power to the cathode and the anode;
c) flowing an electrolyte to contact the substrate plating surface;
d) providing a control electrode in electrical contact with an electrolyte of an electrochemical deposition cell; and
e) adjusting the electrical power provided by the control electrode during deposition.
27. A method for electrochemical deposition of a metal onto a substrate, comprising:
a) providing an electrochemical deposition cell comprising:
1) a substrate holder;
2) a cathode electrically contacting a substrate plating surface;
3) an electrolyte container having an electrolyte inlet, an electrolyte outlet and an opening adapted to receive a substrate plating surface; and
4) an anode electrically connected to an electrolyte;
b) applying electrical power to the cathode and the anode;
c) flowing an electrolyte to contact the substrate plating surface; and
d) vibrating a component of the electrochemical deposition cell at a vibrational frequency between about 10 Hz and about 20,000 Hz and a vibrational amplitude between about 0.5 micron and about 100,000 micron.
21. A method for electrochemical deposition of a metal onto a substrate, comprising:
a) providing an electrochemical deposition cell comprising:
1) a substrate holder;
2) a cathode electrically contacting a substrate plating surface;
3) an electrolyte container having an electrolyte inlet, an electrolyte outlet and an opening adapted to receive a substrate plating surface; and
4) an anode electrically connected to an electrolyte;
b) applying electrical power to the cathode and the anode; and
c) flowing an electrolyte to contact the substrate plating surface;
wherein the step of applying an electrical power to the cathode and the anode comprises:
1) applying a cathodic current density between about 5 mA/cm2 and about 40 mA/cm2 for about 1 second to about 240 seconds.
1. An apparatus for electrochemical deposition of a metal onto a substrate having a substrate plating surface, comprising:
a) a substrate holder adapted to hold the substrate in a position wherein the substrate plating surface is exposed to an electrolyte in an electrolyte container; wherein the substrate holder comprises:
i) a vacuum chuck having a substrate support surface; and
ii) an elastomer ring disposed around the substrate support surface, the elastomer ring contacting a peripheral portion of the substrate;
b) a cathode electrically contacting the substrate plating surface;
c) an electrolyte container having an electrolyte inlet, an electrolyte outlet and an opening adapted to receive the substrate plating surface; and
d) an anode electrically connected to the electrolyte.
3. An apparatus for electrochemical deposition of a metal onto a substrate having a substrate plating surface, comprising:
a) a substrate holder adapted to hold the substrate in a position wherein the substrate plating surface is exposed to an electrolyte in an electrolyte container; wherein the substrate holder comprises:
i) a vacuum chuck having a substrate support surface; and
ii) a gas bladder disposed around the substrate support surface, the gas bladder adapted to contact a peripheral portion of the substrate;
b) a cathode electrically contacting the substrate plating surface;
c) an electrolyte container having an electrolyte inlet, an electrolyte outlet and an opening adapted to receive the substrate plating surface; and
d) an anode electrically connected to the electrolyte.
0. 31. An apparatus for electrochemically depositing a metal onto a semiconductor substrate, comprising:
a container having a fluid inlet, a fluid outlet, and an open portion, the container being configured to contain an electrochemical plating solution therein;
a substrate holder assembly configured to electrically contact a substrate plating surface and support the plating surface in fluid communication with the electrochemical plating solution via the open portion, wherein the substrate holder assembly comprises a cathode contact member and a backside substrate engaging member configured to urge the substrate plating surface against the cathode contact member;
an anode in fluid communication with the electrochemical plating solution; and
a porous fluid flow adjustment member positioned across the container between the anode and the open portion.
0. 41. An apparatus for electrochemically depositing a metal onto a semiconductor substrate, comprising:
a container having a fluid inlet, a fluid outlet, and an open portion, the container being configured to contain an electrochemical plating solution therein;
a substrate holder assembly configured to electrically contact a substrate plating surface and support the plating surface in fluid communication with the electrochemical plating solution via the open portion;
an anode in fluid communication with the electrochemical plating solution;
a porous fluid flow adjustment member positioned across the container between the anode and the open portion; and
an egress gap of between about 1 mm and about 30 mm between an outer surface of the substrate holder assembly and an inner surface of the container, wherein the egress gap is between about 2 mm and about 6 mm.
4. An apparatus for electrochemical deposition of a metal onto a substrate having a substrate plating surface, comprising:
a) a substrate holder adapted to hold the substrate in a position wherein the substrate plating surface is exposed to an electrolyte in an electrolyte container;
b) a cathode electrically contacting the substrate plating surface, wherein the cathode comprises a cathode contact member disposed at a peripheral portion of the substrate plating surface, the cathode contact member having a contact surface adapted to electrically contact the substrate surface, wherein the cathode contact member comprises a radial array of contact pins and a resistor connected in series with each contact pin;
c) an electrolyte container having an electrolyte inlet, an electrolyte outlet and an opening adapted to receive the substrate plating surface; and
d) an anode electrically connected to the electrolyte.
23. A method for electrochemical deposition of a metal onto a substrate, comprising:
a) providing an electrochemical deposition cell comprising:
1) a substrate holder;
2) a cathode electrically contacting a substrate plating surface;
3) an electrolyte container having an electrolyte inlet, an electrolyte outlet and an opening adapted to receive a substrate plating surface; and
4) an anode electrically connected to an electrolyte;
b) applying electrical power to the cathode and the anode; and
c) flowing an electrolyte to contact the substrate plating surface;
wherein the step of applying an electrical power to the cathode and the anode comprises:
1) applying a cathode current density between about 5 mA/cm2 and about 40 mA/cm2 for about 1 second to about 240 seconds;
2) applying a dissolution reverse current between about 5 mA/cm2 and about 80 mA/cm2 for about 0.1 seconds to about 100 seconds;
3) applying a cathodic current density between about 5 mA/cm2 and about 40 mA/cm2 for about 1 seconds to about 240 seconds; and
4) repeating step 2 and step 3.
29. An apparatus for electrochemical deposition of a metal onto a substrate, comprising:
a) a substrate holder comprising:
i) a vacuum chuck having a substrate support surface; and
ii) an elastomer ring disposed around the substrate support surface, the elastomer ring contacting a peripheral portion of the substrate;
b) a cathode electrically contacting a substrate plating surface;
c) an electrolyte container having an electrolyte inlet, an electrolyte outlet and an opening adapted to receive a substrate plating surface, wherein the electrolyte outlet is defined by a gap between a first surface extending radially outward from the substrate plating surface and a surface of the electrolyte container;
d) an anode electrically connected to the electrolyte, the anode comprising:
i) a porous enclosure for flow of an electrolyte therethrough;
ii) a metal disposed within the enclosure; and
iii) an electrode disposed within the enclosure;
e) a control electrode in electrical contact with an electrolyte, the control electrode adapted to provide an adjustable electrical power; and
f) a vibrator attached to the substrate holder, the vibrator adapted to transfer a vibration in one or more directions in the substrate holder.
2. The apparatus of
iii) one or more bubble release ports having one or more openings adjacent an edge of the substrate supporting surface.
5. The apparatus of
7. The apparatus of
9. The apparatus of
10. The apparatus of
12. The apparatus of
22. The method of
2) applying a dissolution reverse current between about 5 mA/cm2 and about 80 mA/cm2 for about 0.1 seconds to about 100 seconds.
25. The method of
0. 32. The apparatus of
an annular member; and
at least one substrate contact element positioned on the annular member.
0. 33. The apparatus of
0. 34. The apparatus of
0. 35. The apparatus of
0. 36. The apparatus of
0. 37. The apparatus of
0. 38. The apparatus of
0. 39. The apparatus of
0. 40. The apparatus of
0. 43. The apparatus of
|
This application claims the benefit of U.S. Provisional Application Ser. No. 60/082,521, entitled “Electroplating on Substrates,” filed on Apr. 21, 1998.
1. Field of the Invention
The present invention generally relates to deposition of a metal layer onto a substrate. More particularly, the present invention relates to an apparatus and a method for electroplating a metal layer onto a substrate.
2. Background of the Related Art
Sub-micron multi-level metallization is one of the key technologies for the next generation of ultra large scale integration (ULSI). The multilevel interconnects that lie at the heart of this technology require planarization of interconnect features formed in high aspect ratio apertures, including contacts, vias, lines and other features. Reliable formation of these interconnect features is very important to the success of ULSI and to the continued effort to increase circuit density and quality on individual substrates and die.
As circuit densities increases, the widths of vias, contacts and other features, as well as the dielectric materials between them, decrease to sub-micron dimensions, whereas the thickness of the dielectric layers remains substantially constant, with the result that the aspect ratios for the features, i.e., their height divided by width, increases. Many traditional deposition processes have difficulty filling sub-micron structures where the aspect ratio exceed 2:1, and particularly where it exceeds 4:1. Therefore, there is a great amount of ongoing effort being directed at the formation of void-free, sub-micron features having high aspect ratios.
Elemental aluminum (Al) and its alloys have been the traditional metals used to form lines and plugs in semiconductor processing because of aluminum's low electrical resistivity, its superior adhesion to silicon dioxide (SiO2), its ease of patterning, and the ability to obtain it in a highly pure form. However, aluminum has a higher electrical resistivity than other more conductive metals such as copper and silver, and aluminum also can suffer from electromigration phenomena. Electromigration is considered as the motion of atoms of a metal conductor in response to the passage of high current density through it, and it is a phenomenon that occurs in a metal circuit while the circuit is in operation, as opposed to a failure occurring during fabrication. Electromigration can lead to the formation of voids in the conductor. A void may accumulate and/or grow to a size where the immediate cross-section of the conductor is insufficient to support the quantity of current passing through the conductor, and may also lead to an open circuit. The area of conductor available to conduct heat therealong likewise decreases where the void forms, increasing the risk of conductor failure. This problem is sometimes overcome by doping aluminum with copper and with tight texture or crystalline structure control of the material. However, electromigration in aluminum becomes increasingly problematic as the current density increases.
Copper and its alloys have lower resistivity than aluminum and higher electromigration resistance as compared to aluminum. These characteristics are important for supporting the higher current densities experienced at high levels of integration and increased device speed. Copper also has good thermal conductivity and is available in a highly pure state. Therefore, copper is becoming a choice metal for filling sub-micron, high aspect ratio interconnect features on semiconductor substrates.
Despite the desirability of using copper for semiconductor device fabrication, choices of fabrication methods for depositing copper into high aspect ratio features are limited. Precursors for CVD deposition of copper are ill-developed and involve complex and costly chemistry. Physical vapor deposition into such features produces unsatisfactory results because of limitations in ‘step coverage’ and voids formed in the features.
As a result of these process limitations, electroplating, which had previously been limited to the fabrication of patterns on circuit boards, is just now emerging as a method to fill vias and contacts on semiconductor devices.
Referring to
Referring to
Referring to
Referring to
Referring to
Referring to
Metal electroplating in general is a well-known art and can be achieved by a variety of techniques. Common designs of cells for electroplating a metal on wafer-based substrates involve a fountain configuration. The substrate is positioned with the plating surface at a fixed distance above a cylindrical electrolyte container, and the electrolyte impinges perpendicularly on the substrate plating surface. The substrate is the cathode of the plating system, such that ions in the plating solution deposit on the conductive exposed surface of the substrate and the micro-sites on the substrate. However, a number of obstacles impair consistent reliable electroplating of copper onto substrates having a sub-micron scale, high aspect ratio features. Generally, these obstacles involve difficulty with providing uniform current density distribution across the substrate plating surface, which is needed to form a metal layer having uniform thickness. A primary obstacle is how to get current to the substrate and how to ensure that the current is uniformly distributed thereon.
One current method for providing power to the plating surface uses contacts (e.g., pins, ‘fingers’, or springs) which contact the substrate seed layer. The contacts touch the seed layer as close as practically possible to the edge of the substrate, to minimize the wasted area on the wafer due to the presence of the contacts. The ‘excluded’ area can no longer be used to ultimately form devices on the substrate. However, the contact resistance of the contacts to the seed layer may vary from contact to contact, resulting in a non-uniform distribution of current densities across the substrate. Also, the contact resistance at the contract to seed layer interface may vary from substrate to substrate, resulting in inconsistent plating distribution between different substrates using the same equipment. Furthermore, the plating rate tends to be higher near the region of the contacts and be lower at regions remote from the contacts due to the resistivity of the thin seed layer that has been deposited on the substrate. A fringing effect of the electrical field also occurs at the edge of the substrate due to the highly localized electrical field formed at the edge of the plated region, causing a higher deposition rate near the edge of the substrate.
A resistive substrate effect is usually pronounced during the initial phase of the electroplating process and reduces the deposition uniformity because the seed layer and the electroplated layers on the substrate deposition surface are typically thin. The metal plating tends to concentrate near the current feed contacts, i.e., the plating rate is greatest adjacent the contacts, because the current density across the substrate decreases as the distance from the current feed contacts increases due to insufficient conductive material on the seed layer to provide a uniform current density across the substrate plating surface. As the deposition film layer becomes thicker due to the plating, the resistive substrate effect diminishes because a sufficient thickness of deposited material becomes available across the substrate plating surface to provide uniform current densities across the substrate. It is desirable to reduce the resistive substrate effect during electroplating.
Traditional fountain plater designs also provide non-uniform flow of the electrolyte across the substrate plating surface, which compounds the effects of the non-uniform current distribution on the plating surface by providing non-uniform replenishment of plating ions and where applicable, plating additives, across the substrate, resulting in non-uniform plating. The electrolyte flow uniformity across the substrate can be improved by rotating the substrate at a high rate during the plating process. Such rotation introduces complexity into the plating cell design due to the need to furnish current across and revolving interface. However, the plating uniformity still deteriorates at the boundaries or edges of the substrate because of the fringing effects of the electrical field near the edge of the substrate, the seed layer resistance and the potentially variable contact resistance.
There is also a problem in maintaining an electroplating solution to the system having consistent properties over the duration of a plating cycle and/or over a run of multiple wafers being plated. Traditional fountain plater designs generally require continual replenishing of the metal being deposited into the electrolyte. The metal electrolyte replenishing scheme is difficult to control and causes build-up of co-ions in the electrolyte, resulting in difficult to control variations in the ions concentration in the electrolyte. Thus, the electroplating process produces inconsistent results because of inconsistent ion concentration in the electrolyte.
Additionally, operation of a plating cell incorporating a non-consumable anode may cause bubble-related problems because oxygen evolves on the anode during the electroplating process. Bubble-related problems include plating defects caused by bubbles that reach the substrate plating surface and prevent adequate electrolyte contact with the plating surface. It is desirable to eliminate or reduce bubble formation from the system and to remove formed bubbles from the system.
Therefore, there remains a need for a reliable, consistent metal electroplating apparatus and method to deposit uniform, high quality metal layers on substrates to form sub-micron features. There is also a need to form metal layers on substrates having micron-sized, high aspect ratio features to fill the features without voids in the features.
The invention provides an apparatus and a method for achieving reliable, consistent metal electroplating or electrochemical deposition onto substrates. More particularly, the invention provides uniform and void-free deposition of metal onto substrates having sub-micron features formed thereon and a metal seed layer formed thereover. The invention provides an electro-chemical deposition cell comprising a substrate holder, a cathode electrically contacting a substrate plating surface, an electrolyte container having an electrolyte inlet, an electrolyte outlet and an opening adapted to receive a substrate and an anode electrically connect to an electrolyte. The configuration and dimensions of the deposition cell and its components are designed to provide uniform current distribution across the substrate. The cell is equipped with a flow-through anode and a diaphragm unit that provide a combination of relatively uniform flow of particular-free electrolyte in an easy to maintain configuration. Additionally, an agitation device may be mounted to the substrate holder to vibrate the substrate in one or more directions, ie., x, y and/or z directions. Still further, an auxiliary electrode can be disposed adjacent the electrolyte outlet to provide uniform deposition across the substrate surface and to shape as necessary the electrical field at the edge of the substrate and at the contacts. Still further, time variable current waveforms including periodic reverse and pulsed current can be applied during the plating period to provide a void-free metal layer within sub-micron features on the substrate.
So that the manner in which the above recited features, advantages and objects of the present invention are attained can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to the embodiments thereof which are illustrated in the appended drawings.
It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
A ring or sleeve insert 80 disposed in the upper portion of the container body 42 can be used to precisely define the plating area of the substrate. The insert 80 is modularly changeable to adapt an electroplating cell for various substrate sizes, including 200 mm and 300 mm sizes, and shapes, including circular, rectangular, square, etc. The size and the shape of the container body 42 are preferably changed correspondingly for each size and shape of substrate to approximate the size and shape of the substrate. The insert 80 also insulates and protects the edge of the substrate 48 from non-uniform plating by limiting the current flow to the circumference of the plating surface, thereby reducing the fringing effects encountered when the cell size is larger than the plating surface.
As plating occurs on the substrate, ions in solution plate (deposit) from the solution onto the substrate. To provide additional plating material, ions must diffuse through a diffusion boundary layer adjacent the plating surface. Typically, in the prior art, replenishment is provided through hydrodynamic means by the flow of solution past the substrate and by substrate rotation. However, hydrodynamic replenishment schemes still provide inadequate replenishment because of the no slip condition at the boundary layer where the electrolyte immediately adjacent the plating surface has zero velocity and is stagnant. To address these limitation and increase replenishment, a vibrational agitation member 82 is provided to control the mass transport rates (boundary layer thickness) at the surface of the substrate. The vibrational agitation member 82 is preferably mounted to the substrate holder 44 to vibrate the substrate 48. The vibrational agitation member 82 usually comprises a motor or a vibrational transducer that moves the substrate holder 44 back and forth on one or more axes at a frequency from about 10 Hz to about 20,000 Hz. The amplitude of the vibration is preferably between about 0.5 micron and about 100,000 micron. The vibrational agitation member 82 may also provide additional vibration in a second direction that is parallel to the substrate plating surface 54, such as vibrating the substrate in the x-y directions, or in a direction orthogonal to the substrate plating surface 54, such as in the x-z directions. Alternatively, the vibrational agitation member 82 may vibrate the substrate in multiple directions, such as the x-y-z directions.
The frequency of the vibration can be synchronized to the plating cycles (discussed in detail below) to tailor-fit the mass transport rates to the deposition process needs. Conventional electroplating systems cannot incorporate this feature because high frequency interruptions or reversals cannot be made in pumped induced electrolyte flow due to the fluid's inertia in conventional electroplating systems. The vibration also enhances removal of residual plating and rinse solution from the substrate surface after completion of the plating cycle.
The substrate holder 44 can also be rotated, either fully or partially, in addition to the vibrational agitation to further enhance uniform plating thickness. A rotational actuator (not shown) can be attached to the substrate holder 44 and spin, or partially rotate in an oscillatory manner, the substrate holder about a central axis through the center of the substrate holder. The rotational movement of the plating surface against the electrolyte enhances the exposure of fresh electrolyte across the plating surface to improve deposition uniformity.
Another advantage of vibrating the substrate 48 is that the vibration exposes the vias and trenches to fresh electroplating solutions. As the solution adjacent to the substrate becomes depleted of the deposition metal, the reciprocation of the substrate replenishes the areas adjacent to the vias and trenches with fresh electroplating solution preferably having a high concentration of copper or other deposition metal. This is achieved by translating the mouth of the trench or the via on a substrate plating surface to a region of the solution that has not been facing the trench or via and is therefore less depleted of the reactant. An alternative to vibrating the substrate holder 44 and the substrate 48 is vibrating the electrolyte. A vibrational transducer (not shown) can be placed within the container body to directly agitate the electrolyte, or the vibrational transducer can be placed outside of the container body and indirectly agitate the electrolyte by vibrating the container body. The vibrational agitation member 82 also helps to eliminate bubble related defects by encouraging bubbles to move from the plating surface 54 and be evacuated from the cell 40.
Gas bubbles may be trapped with the substrate installation into the cell, carried by the electrolyte flow through the system, or generated by the electrochemical reaction at the anode or the cathode. The gas bubbles are preferably exhausted from the cell to prevent defects in the plating process. A plurality of gas diverting vanes may be disposed above the anode to divert evolved gases toward the sidewall of the electrolyte container. Generally, gas bubbles will move to a higher elevation because of their lower specific gravity, and the gas bubbles flows along with the electrolyte that flows generally upward and outward with respect to the substrate. The vibration is applied to the electrolyte or the substrate support member detaches the bubbles from the substrate surface and enhances the movement of the gas bubbles out of the cell. Preferably, a plurality of gas release ports 81 (as shown in
In addition to the anode electrode and the cathode electrode, an auxiliary electrode can be disposed in contact with the electrolyte to change the shape of the electrical field over the substrate plating surface. An auxiliary electrode 84 is preferably disposed outside the container body to control the deposition thickness, current density and potential distribution in the electroplating cell to achieve the desired electroplating results on the substrate. As shown in
The auxiliary electrode 84 may comprise a ring, a series of concentric rings, a series of segmented rings, or an array of spaced electrodes to match a corresponding array of cathode contact pins 56. The auxiliary electrode 84 may be positioned on the same plane as the substrate plating surface 54 or on varying planes to tailor fit the current and potential distribution on the substrate 48. Alternatively, a plurality of concentric ring auxiliary electrodes can be configured to activate at different potentials or to activate potentials in sequence according to the desired process.
Alternatively, the auxiliary electrode comprises a segmented resistive material having multiple contact points such that the voltage of the auxiliary electrode varies at different distances from the contact points. This configuration provides corresponding variations of potential for a discrete cathode contacting member configuration. Another variation of the auxiliary electrode provides a variable width electrode that corresponds to a configuration of discrete cathode contacting pins so that an effective higher voltage (and current) is provided at the substrate contacting points of the cathode contact member while an effective lower voltage (and current) is provided in the region between the substrate/cathode contacting points. Because the effective voltage provided by the variable width auxiliary electrode decreases as the distance increases between the auxiliary electrode and the edge of the substrate, the variable width auxiliary electrode provides a closer distance between the auxiliary electrode and the edge of the substrate where the cathode contact member are located.
Preferably, a consumable anode 90 is disposed in the container body 42 to provide a metal source in the electrolyte. As shown in
Preferably, the anode 90 is a modular unit that can be replaced easily to minimize interruptions and to allow easy maintenance. Preferably, the anode 90 is positioned a distance greater than one (1) inch, and more preferably, greater than 4 inches, away from the substrate plating surface 54 (for a 200 mm substrate) to assure that the effects of level variations in the anode copper caused by anode dissolution, particulate fluidization and assembly tolerances become negligible once the electrolyte flow reaches the substrate surface.
A flow adjuster 110 comprising a variable thickness conical profile porous barrier can be disposed in the container body between the anode and the substrate to enhance flow uniformity across the substrate plating surface. Preferably, the flow adjuster 110 comprises a porous material such as a ceramic or a polymer which is used to provide a selected variation in electrolyte flow at discrete locations across the face of the substrate.
A broken substrate catcher (not shown) can be placed within the container body to catch broken substrate pieces. Preferably, the broken substrate catcher comprises a mesh, a porous plate or membrane. The porous wedge or the perforated plate described above may also serve for this purpose.
A refining electrode (not shown) can be placed in the sump (not shown) for pre-electrolysis of the electrolyte and for removal of metal and other chemical deposit buildup in the sump. The refining electrode can be continuously activated or periodically activated according to the needs of the system. The refining electrode when made of copper and polarized anodically can be used to replenish copper in the bath. This external electrode can thus be used to precisely adjust the copper concentration in the bath.
A reference electrode (not shown) can be employed to determine precisely the polarization of the anode, the cathode and the auxiliary electrode.
Once the electroplating process is completed, the electrolyte can be drained from the container body to an electrolyte reservoir or sump, and a gas knife can be incorporated to remove the film of electrolyte remaining on the substrate plating surface. The gas knife comprises a gas inlet, such as a retractable tube or an extension air tube connected to a hollow anode electrode, which supplies a gas stream or a gas/liquid dispersion that pushes the electrolyte off the substrate surface. The gas can also be supplied through the gap between the substrate holder 44 and the container body 42 to blow on the substrate surface.
A deionized water rinse system (not shown) can also be incorporated into the electroplating system to rinse the substrate free of electrolyte. A supply of deionized water or other rinsing solutions can be connected to the inlet 50 and selectively accessed through a inlet valve. After the electrolyte has been drained from the container body, the deionized water or other rinsing solution can be pumped into the system through inlet 50 and circulated through the container body to rinse the substrate surface. While the processed substrate is being rinsed, the cathode and anode power supply is preferably inactivated in the cell. The deionized water fills the cell and flows across the surface of the substrate to rinse the remaining electrolyte off the surface. The vibrational member may be activated to enhance rinsing of the plated surface. A number of separate deionized water tanks can be utilized sequentially to increase the degree of purity of the rinse water. To utilize more than one rinsing solution supply, a rinsing cycle is preferably completed and the rinsing solution completely drained from the cell before the next rinsing solution is introduced into the cell for the next rinsing cycle. The used deionized water rinse can also be purified by plating out the metal traces acquired during the rinse cycle by the rinsing solution or by circulating the used deionized water through an ion exchange system.
A plurality of auxiliary electrodes 216 can be placed in the cell at the corners of the polygon. Alternatively, ring shaped or segmented ring auxiliary electrodes 218 can be placed around each substrate 48 to match the cathode contact members 212 similarly to the arrangement of the auxiliary electrodes shown in FIG. 3. Preferably, the auxiliary electrodes dynamically adjust to compensate current distribution over the substrate by gradually decreasing the current of the auxiliary electrodes as the resistive substrate effect tapers off after the initial deposition period. A porous separator/filter (not shown) can be placed between the anode and the cathode to trap particulates.
A vibrational agitation member (not shown) can be connected to the container body to vibrate the substrates. However, substrate vibration may be unnecessary when the polygonal anode drum is rotated sufficient fast, preferably between about 5 revolutions per minute (RPM) and about 100 RPM, to provide a high degree of agitation to the electrolyte. The rotating polygonal anode also provides a pulsed or transient electrical power (voltage/current combination) due to the varying distance between the active anode surfaces and the substrate because of the rotation. Because the anode is polygonal in shape, as the anode rotates, the distance between cathode and the anode varies from a maximum when the anode polygon faces are aligned with the cathode polygon faces in parallel planes and a minimum when the anode polygon corners are aligned with the centers of the cathode polygon faces. As the distance between the anode and the cathode varies, the electrical current between the anode and the cathode varies correspondingly.
Another variation provides a horizontally positioned polygonal drum. The container body is rotated around the horizontal axis to position one polygon face on top to allow loading and unloading of a substrate while the other substrates are still being processed.
Yet another variation provides the substrates to be mounted on the outer surfaces of the inner polygon drum which now is the cathode, and the container body becomes the anode. This configuration allows the cathode drum to be lifted from the electrolyte for easy loading and unloading of the substrates.
Operating Conditions
In one embodiment of the invention, a periodic reverse potential and/or current pulse or an intermittent pulse current is delivered to the substrate to control the mass transfer boundary layer thickness and the grain size of the deposited material. The periodic reverse and pulse current/potential also enhances deposit thickness uniformity. The process conditions for both the deposition stage and the dissolution stage can be adjusted to provide the desired deposit profile, usually a uniform, flat surface. In general, plating/deposition is accomplished with a relatively low current density for a relatively long interval because low current density promotes deposition uniformity, and dissolution is accomplished with a relatively high current density for a relatively short interval because high current density leads to highly non-uniform distribution that preferentially shaves or dissolves deposited peaks.
For a pre-determined grain size, a current pulse comprising a higher negative current density for a short time (between about 50 mA/cm2 and about 180 mA/cm2 for about 0.1 to 100 ms) is applied to nucleate an initial layer of copper deposits followed by a constant current density applied for a long interval (between about 5 mA/cm2 and about 80 mA/cm2 for up to a few minutes) to continue deposition. The length of the deposition interval can be adjusted according to the deposition rate to achieve the desired deposition thickness over the substrate surface.
To completely fill high aspect ratio trenches, vias or other interconnect features, a current reversal or dissolution interval may be applied to achieve some dissolution of the deposited metal. The dissolution interval is preferably applied at a current density much higher than the current density of the deposition current but for a short time interval to ensure a net deposit. The dissolution interval can be applied once or periodically during a deposition process to achieve the desired results. The deposition interval can be divided into a number of short intervals followed by a corresponding number of even shorter dissolution intervals to completely fill high aspect ratio interconnect features. Then, a constant deposition current density is applied to achieve a uniform deposition thickness across the field. Typically, a deposition cycle comprises a deposition current density of between about 5 mA/cm2 and about 40 mA/cm2 followed by a dissolution current density between about 5 mA/cm2 and about 80 mA/cm2. The deposition cycle is repeated to achieve complete, void-free filling of high aspect ratio features, and optionally, a final application of the deposition current density is applied to form a uniform field deposition thickness across the substrate plating surface. Alternatively, the current reversal/dissolution cycle can be achieved by providing a constant reverse voltage instead of a constant reverse current density.
Because the resistive substrate effect is dominant during the beginning of the plating cycle, a relatively low current density, preferably about 5 mA/cm2, is applied during the initial plating. The low current density provides very conformal plating substantially uniformly over the plating surface, and the current density is gradually increased as the deposition thickness increases. Also, no current reversal for dissolution is applied during the initial stage of the plating process so that the metal seed layer is not at risk of being dissolved. However, if a current reversal is introduced for striking or nucleation purposes, the reverse current density is applied at a low magnitude to ensure that no appreciable metal seed layer is dissolved.
Optionally, a relaxation interval between the deposition interval and the dissolution interval allows recovery of depleted concentration profiles and also provides improved deposition properties. For example, a relaxation interval where no current/voltage is applied between the deposition interval and the dissolution interval, allows the electrolyte to return to optimal conditions for the processes.
Preferably, the vibration frequency, the pulse and/or periodic reverse plating, the auxiliary electrode current/voltage and the electrolyte flow are all synchronized for optimal deposition properties. One example of synchronization is to provide vibration only during the deposition interval so that the boundary diffusion layer is minimized during deposition and to eliminate vibration during the dissolution interval so that the dissolution proceeds under mass transport control.
To improve adhesion of the metal to the seed layer during plating, a very short, high current density strike is applied at the beginning of the plating cycle. To minimize bubble related defects, the strike must be short, and the current density must not exceed values at which hydrogen evolves. This current density, preferably between about 100 mA/cm2 to about 1000 mA/cm2, corresponds to an overpotential not exceeding −0.34 V (cathodic) versus for the reference electrode. A separate striking process using a different electrolyte may be required for adhesion of the metal plating material. Separate striking can be accomplished in a separate cell with different electrolytes or in the same cell by introducing and evacuating different electrolytes. The electrolytes used for separate striking is typically more dilute in metal concentration and may even be a cyanide based formulation.
The metal seed layer is susceptible to dissolution in the electrolyte by the exchange current density of the electrolyte (about 1 mA/cm2 for copper). For example, 1500 Å of copper can be dissolved in about 6 minutes in an electrolyte with no current applied. To minimize the risk of the seed layer being dissolved in the electrolyte, a voltage is applied to the substrate before the substrate is introduced to the electrolyte. Alternatively, the current is applied instantaneously as the substrate comes in contact with the electrolyte. When a deposition current is applied to the substrate plating surface, the metal seed layer is protected from dissolution in the electrolyte because the deposition current dominates over the equilibrium exchange current density of the electrolyte.
The invention also provides for in situ electroplanarization during periodic reverse plating. Preferably, both deposition and dissolution steps are incorporated during a single pulse or a sequence of rapid pulses such that at the end of the process the trenches, vias and other interconnect features are completely filled and planarized. The electrochemical planarization step comprises applying a high current density during dissolution. For example, a dissolution reverse current density of about 300 mA/cm2 is applied for about 45 seconds as an electrochemical planarization step that leads to a substantially flat surface with just a residual dimple of about 0.03 μm. This electrochemical planarization substantially reduces the need for chemical mechanical polishing (CMP) and may even eliminate the need for CMP in some applications.
Chemistry
An electrolyte having a high copper concentration (e.g., >0.5M and preferably between 0.8M to 1.2M) is beneficial to overcome mass transport limitations that are encountered with plating of sub-micron features. In particular, because sub-micron features with high aspect ratios typical allow only minimal or no electrolyte flow therein, the ionic transport relies solely on diffusion to deposit metal into these small features. A high copper concentration preferably about 0.8M or greater, in the electrolyte enhances the diffusion process and eliminates the mass transport limitations because the diffusion flux is proportional in magnitude to the bulk electrolyte concentration. A preferred metal concentration is between about 0.8 and about 1.2 M. Generally, the higher the metal concentration the better; however, one must be careful not to approach the solubility limit where the metal salt will precipitate.
The conventional copper plating electrolyte includes a high sulfuric acid concentration (about 1 M) to provide high conductivity to the electrolyte. The high conductivity is necessary to reduce the non-uniformity in the deposit thickness caused by the cell configuration of conventional copper electroplating cells. However, the present invention (including the cell configuration) provides a more uniform current distribution. In this situation a high acid concentration is detrimental to deposition uniformity because the resistive substrate effects are amplified by a highly conductive electrolyte. Furthermore, the dissolution step during periodic reverse cycle requires a relatively low electrolyte conductivity because a highly conductive electrolyte may promote non-uniformity as a result of the high reverse current density. Also, the presence of a supporting electrolyte, e.g. acid or base, will lower the ionic mass transport rates, which, as explained above, are essential for good quality plating. Also, a lower sulfuric acid concentration provides a higher copper sulfate concentration due to elimination of the common ion effect. Furthermore, particularly for the soluble copper anode, a lower acidic concentration minimizes harmful corrosion and material stability problems. Thus, the invention contemplates an electroplating solution having no acid or very low acid concentrations. Preferably, the sulfuric acid concentration is in the range of 0 (absence) to about 0.2M. Additionally, a pure or relatively pure copper anode can be used in this arrangement.
In addition to copper sulfate, the invention contemplates copper salts other than copper sulfate such as copper gluconate and copper sulfamate that offer high solubility and other benefits, as well as salts such as copper nitrate, copper phosphate, copper chloride and the like.
The invention also contemplates the addition of acids other than sulfuric acid into the electrolyte to provide for better complexation and/or solubility for the copper ions and the copper metal which results in improved deposition properties. These compounds include anthranilic acid, acetic acid, citric acid, lactic acid, sulfamic acid, ascorbic acid, glycolic acid, oxalic acid, benzenedisulfonic acid, tartaric acid and/or malic acid.
The invention also contemplates additives to produce asymmetrical anodic transfer coefficient (α) and cathodic transfer coefficient (β) to enhance filling of the high aspect ratio features during reverse plating cycle.
Ultra pure water can be introduced to the substrate plating surface to ensure complete wetting of the substrate plating surface which enhances the electroplating process into the small features. Steam can also be used to pre-wet the substrate plating surface.
Surfactants improve wetting by reducing surface tension of the solution. Surfactants contemplated by the present invention include: sodium xylene sulfonate, polyethers (polyethylene oxide), carbowax, sodium benzoate, ADMA8 amine, Adogen, Alamine, Amaizo, Brij, Crodesta, Dapral, Darnyl, didodecylmethyl propane sultaine, Dowex, Empol, Ethomeen, Ethomid, Enordet, Generol, Grilloten, Heloxy, hexadecyltrimethylammonium bromide, Hyamine, Hysoft, Igepal, Neodol, Octadecylbenzyl propane sultaine, Olcyl betaine, Peganate, Pluronic, Polystep, Span Surfynol, Tamol, Tergitol, Triton, Trilon, Trylox, Unithox, Varonic, Varamide, Zonyl, Benzylmethyl propane sultaine, alkyl or aryl betaine, alkyl or aryl sultaine.
Levellers improve deposition thickness uniformity. Brighteners improves the the reflectivity of the deposition surface by enhancing uniformity of the crystalline structure. Grain refiners produce smaller grains to be deposited. Levellers, brighteners and grain refiners can be specially formulated and optimized for the low acid, high copper electrolyte provided by the invention. In optimizing these compounds for use with the invention, the effects of the periodic reverse current need to also be considered. Levellers, brighteners and grain refiners contemplated by the present invention include:
inorganic minor components from: Salts of Se, As, In, Ga, Bi, Sb, TI, or Te; and/or
organic minor components selected from (singly or in combination): acetyl-coenzyme, aminothiols; acrylamine; azo dyes; alkane thiols, Alloxazine; 2-Aminopyrimidine; 2-Amino-1,3,4, thiadiazole; Amino methyl thiadiazole; 2-Aminothiadiazole; 3-amino 1,2,4, triazole; benzal acetone, Benzopurpurin; benzophnon, Behzotriazole, hydroxylbenzotriazole, Betizyldene acetone, Benzoic acid, Benzoil acetic acid ethyl ester, Boric acid, cacodylic acid, Corcumin Pyonin Y; Carminic Acid; Cinamic aldehyde, cocobetaine or decyl betaine, cetyl betaine, cysteine; DETAPAC; 2′,7′-dichlorofluorescein; dextrose, dicarboxilic amino acids; dipeptide diaminoacid (camsine=beta alanyl hystadine), 5-p-dimethylamine benzyldene Rhodamine, 5(p-Dimethylamino-benzylidene)-2-thio barbituric, dithizone, 4-(p-Ethoxyphnylazo)-m-phenylendi-amine, ethoxilated tetramethyl decynediol, ethoxilated quarternary amonium salts, ethyl benzoil acetate, ethoxylated beta-naphtol, EDTA, Evan Blue; di ethylene triamine penta acetic acid or salts, diethylenetriamine pentacetate, penta sodium salt, glucamine, glycerol compounds, di-glycine, d-glucamine, triglycine, glycogen, gluter aldehyde, glutamic acid, its salts and esters (MSG), sodium glucoheptonate, hydroxylbenzotriazole, hydroxysuccinimide, hydantoin, 4-(8-Hydroxy-5-quinolylazo)-1-naphtalenesulfonic acid, p-(p-hydroxyphenylazo) benzene sulfonic, insulin, hydroxybenzaldehyde, imidazoline; lignosulfonates; methionine; mercaptobenzi-imidazoles; Martius Yellow; 2-methyl-1-p-tolyltriazene, 3-(p-Nitrophenyl)-1-(p-phenylazophnyl)triazene; 4-(p-Nitrophenylazo) resorcinol, 4-(p-Nitrophenylazo)-1-naphthol, OCBA-orthochloro benzaldehyde, Phenyl propiolic acid, polyoxyethylene alcohols, quarternary amonium ethoxilated alcohols, and their fullyacid esters, polyethyleneimine, phosphalipides, sulfasalicilic acid, linear alkyl sulfonate, sulfacetamide, Solochrome cyanin; sugars; sorbitol, sodium glucoheptonate, sodium glycerophosphate, sodium mercaptobenzotriazole, tetrahydropyranyl amides, thiocarboxylic amides, thiocarbonyl-di-imidazole; thiocarbamid, thiohydantoin; thionine acetate, thiosalicilic acid, 2-thiolhistadine, thionine, thiodicarb, thioglycolic acid, thiodiglycols, thiodiglycolic acid, thiodipropionic acid, thioglycerol, dithiobenzoic acid, tetrabutylamonium, thiosulfone, thiosulfonic acid, thionicotineamide, thionyl chloride or bromide; thiourea; TIPA; tolyltriazole, triethanolamine; tri-benzylamine; 4,5,6, triaminopyrimidine; xylene cyanole.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof. The scope of the invention is determined by the claims which follow.
Patent | Priority | Assignee | Title |
10074879, | Jul 29 2009 | ENTERPRISE SCIENCE FUND, LLC | Instrumented fluid-surfaced electrode |
10197881, | Nov 15 2011 | Ashwin-Ushas Corporation, Inc. | Complimentary polymer electrochromic device |
10444544, | Sep 15 2015 | Ashwin-Ushas Corporation | Electrochromic eyewear |
8221600, | Sep 23 2010 | MAXEON SOLAR PTE LTD | Sealed substrate carrier for electroplating |
8221601, | Sep 23 2010 | MAXEON SOLAR PTE LTD | Maintainable substrate carrier for electroplating |
8317987, | Sep 23 2010 | MAXEON SOLAR PTE LTD | Non-permeable substrate carrier for electroplating |
8460814, | Jul 29 2009 | ENTERPRISE SCIENCE FUND, LLC | Fluid-surfaced electrode |
8784618, | Aug 19 2010 | International Business Machines Corporation | Working electrode design for electrochemical processing of electronic components |
8865361, | Jul 29 2009 | ENTERPRISE SCIENCE FUND, LLC | Instrumented fluid-surfaced electrode |
8889312, | Jul 29 2009 | ENTERPRISE SCIENCE FUND, LLC | Instrumented fluid-surfaced electrode |
8926820, | Aug 19 2010 | International Business Machines Corporation | Working electrode design for electrochemical processing of electronic components |
8968903, | Jul 29 2009 | ENTERPRISE SCIENCE FUND, LLC | Fluid-surfaced electrode |
8974939, | Jul 29 2009 | ENTERPRISE SCIENCE FUND, LLC | Fluid-surfaced electrode |
9207515, | Mar 15 2013 | ASHWIN-USHAS CORPORATION, INC | Variable-emittance electrochromic devices and methods of preparing the same |
9274395, | Nov 15 2011 | ASHWIN-USHAS CORPORATION, INC | Complimentary polymer electrochromic device |
9482880, | Sep 15 2015 | TRI-POWER DESIGN, LLC | Electrochromic eyewear |
9594284, | Nov 15 2011 | Ashwin-Ushas Corporation, Inc. | Complimentary polymer electrochromic device |
9632059, | Sep 03 2015 | ASHWIN-USHAS CORPORATION, INC | Potentiostat/galvanostat with digital interface |
RE46088, | Sep 23 2010 | MAXEON SOLAR PTE LTD | Maintainable substrate carrier for electroplating |
Patent | Priority | Assignee | Title |
2882209, | |||
3649509, | |||
3727620, | |||
3770598, | |||
4027686, | Jan 02 1973 | Texas Instruments Incorporated | Method and apparatus for cleaning the surface of a semiconductor slice with a liquid spray of de-ionized water |
4092176, | Dec 11 1975 | Nippon Electric Co., Ltd. | Apparatus for washing semiconductor wafers |
4110176, | Mar 11 1975 | OMI International Corporation | Electrodeposition of copper |
4113492, | Apr 08 1976 | Fuji Photo Film Co., Ltd. | Spin coating process |
4120711, | Sep 30 1977 | RAYTEC, INC | Process for sealing end caps to filter cartridges |
4120771, | Sep 10 1976 | Fabrication Belge de Disques "Fabeldis" | Device for manufacturing substantially flat dies |
4304641, | Nov 24 1980 | International Business Machines Corporation | Rotary electroplating cell with controlled current distribution |
4315059, | Jul 18 1980 | United States of America as represented by the United States Department of Energy | Molten salt lithium cells |
4326940, | May 21 1979 | ROHCO INCORPORATED, A CORP OF OH | Automatic analyzer and control system for electroplating baths |
4336114, | Mar 26 1981 | Occidental Chemical Corporation | Electrodeposition of bright copper |
4376685, | Jun 24 1981 | M&T HARSHAW | Acid copper electroplating baths containing brightening and leveling additives |
4405416, | Jul 18 1980 | Molten salt lithium cells | |
4428815, | Apr 28 1983 | AT & T TECHNOLOGIES, INC , | Vacuum-type article holder and methods of supportively retaining articles |
4435266, | Oct 01 1981 | Emi Limited | Electroplating arrangements |
4489740, | Dec 27 1982 | General Signal Corporation | Disc cleaning machine |
4510176, | Sep 26 1983 | CHASE MANHATTAN BANK, AS ADMINISTRATIVE AGENT, THE | Removal of coating from periphery of a semiconductor wafer |
4518678, | Dec 16 1983 | Advanced Micro Devices, Inc. | Selective removal of coating material on a coated substrate |
4519846, | Mar 08 1984 | Process for washing and drying a semiconductor element | |
4693805, | Feb 14 1986 | BOE Limited | Method and apparatus for sputtering a dielectric target or for reactive sputtering |
4732785, | Sep 26 1986 | Motorola, Inc. | Edge bead removal process for spin on films |
4789445, | May 16 1983 | Asarco Incorporated | Method for the electrodeposition of metals |
5039381, | May 25 1989 | Method of electroplating a precious metal on a semiconductor device, integrated circuit or the like | |
5055425, | Jun 01 1989 | Hewlett-Packard Company | Stacked solid via formation in integrated circuit systems |
5092975, | Jun 14 1988 | Yamaha Corporation | Metal plating apparatus |
5155336, | Jan 19 1990 | Applied Materials, Inc | Rapid thermal heating apparatus and method |
5162260, | Jun 01 1989 | SHUTTERS, INC | Stacked solid via formation in integrated circuit systems |
5168887, | May 18 1990 | SEMITOOL, INC , A CORP OF MT | Single wafer processor apparatus |
5222310, | May 18 1990 | Semitool, Inc. | Single wafer processor with a frame |
5224504, | May 25 1988 | Semitool, Inc. | Single wafer processor |
5230743, | Jun 25 1988 | Semitool, Inc. | Method for single wafer processing in which a semiconductor wafer is contacted with a fluid |
5252807, | Jul 02 1990 | Heated plate rapid thermal processor | |
5256274, | Aug 01 1990 | Selective metal electrodeposition process | |
5259407, | Jun 15 1990 | MATRIX INC | Surface treatment method and apparatus for a semiconductor wafer |
5290361, | Jan 24 1991 | Wako Pure Chemical Industries, Ltd.; Purex Co., Ltd. | Surface treating cleaning method |
5302256, | Jun 25 1991 | LeaRonal Japan Inc. | Immersion tin/lead alloy plating bath |
5316974, | Dec 19 1988 | Texas Instruments Incorporated | Integrated circuit copper metallization process using a lift-off seed layer and a thick-plated conductor layer |
5328589, | Dec 23 1992 | Enthone-OMI, Inc.; ENTHONE-OMI, INC , A DELAWARE CORPORATION | Functional fluid additives for acid copper electroplating baths |
5349978, | Jun 04 1993 | Tokyo Ohka Kogyo Co., Ltd. | Cleaning device for cleaning planar workpiece |
5368711, | Aug 01 1990 | Selective metal electrodeposition process and apparatus | |
5377708, | Mar 27 1989 | Semitool, Inc. | Multi-station semiconductor processor with volatilization |
5429733, | May 21 1992 | Electroplating Engineers of Japan, Ltd. | Plating device for wafer |
5447615, | Feb 02 1994 | Electroplating Engineers of Japan Limited | Plating device for wafer |
5512163, | Jun 08 1992 | Motorola, Inc. | Method for forming a planarization etch stop |
5516412, | May 16 1995 | GLOBALFOUNDRIES Inc | Vertical paddle plating cell |
5544421, | Apr 28 1994 | Applied Materials Inc | Semiconductor wafer processing system |
5605615, | Dec 05 1994 | SHENZHEN XINGUODU TECHNOLOGY CO , LTD | Method and apparatus for plating metals |
5605866, | Oct 20 1993 | Novellus Systems, Inc | Clamp with wafer release for semiconductor wafer processing equipment |
5608943, | Aug 23 1993 | Tokyo Electron Limited | Apparatus for removing process liquid |
5620581, | Nov 29 1995 | AIWA CO , LTD | Apparatus for electroplating metal films including a cathode ring, insulator ring and thief ring |
5625170, | Jan 18 1994 | Nanometrics Incorporated | Precision weighing to monitor the thickness and uniformity of deposited or etched thin film |
5651865, | Jun 17 1994 | MKS Instruments, Inc | Preferential sputtering of insulators from conductive targets |
5664337, | Mar 26 1996 | Applied Materials Inc | Automated semiconductor processing systems |
5678320, | Apr 28 1994 | SEMITOOL, INC | Semiconductor processing systems |
5705223, | Jul 26 1994 | International Business Machine Corp. | Method and apparatus for coating a semiconductor wafer |
5718813, | Dec 30 1992 | Advanced Energy Industries, Inc | Enhanced reactive DC sputtering system |
5723028, | Aug 01 1990 | Electrodeposition apparatus with virtual anode | |
5744019, | Nov 29 1995 | AIWA CO , LTD | Method for electroplating metal films including use a cathode ring insulator ring and thief ring |
5762751, | Aug 17 1995 | Applied Materials Inc | Semiconductor processor with wafer face protection |
5788454, | Apr 28 1994 | Semitool, Inc. | Semiconductor wafer processing system |
5882168, | Apr 28 1994 | Semitool, Inc. | Semiconductor processing systems |
5972192, | Jul 23 1997 | GLOBALFOUNDRIES Inc | Pulse electroplating copper or copper alloys |
5980706, | Jul 15 1996 | Applied Materials Inc | Electrode semiconductor workpiece holder |
5985126, | Jul 15 1996 | Applied Materials Inc | Semiconductor plating system workpiece support having workpiece engaging electrodes with distal contact part and dielectric cover |
6001234, | Sep 30 1997 | Applied Materials Inc | Methods for plating semiconductor workpieces using a workpiece-engaging electrode assembly with sealing boot |
6004440, | Sep 18 1997 | Applied Materials Inc | Cathode current control system for a wafer electroplating apparatus |
6004828, | Sep 30 1997 | Applied Materials Inc | Semiconductor processing workpiece support with sensory subsystem for detection of wafers or other semiconductor workpieces |
6024857, | Oct 08 1997 | Novellus Systems, Inc. | Electroplating additive for filling sub-micron features |
6027631, | Nov 13 1997 | Novellus Systems, Inc. | Electroplating system with shields for varying thickness profile of deposited layer |
6074544, | Jul 22 1998 | Novellus Systems, Inc. | Method of electroplating semiconductor wafer using variable currents and mass transfer to obtain uniform plated layer |
6090711, | Sep 30 1997 | Applied Materials Inc | Methods for controlling semiconductor workpiece surface exposure to processing liquids |
6091498, | Sep 30 1997 | Applied Materials Inc | Semiconductor processing apparatus having lift and tilt mechanism |
6099712, | Sep 30 1997 | Applied Materials Inc | Semiconductor plating bowl and method using anode shield |
6110346, | Jul 22 1998 | Novellus Systems, Inc. | Method of electroplating semicoductor wafer using variable currents and mass transfer to obtain uniform plated layer |
6126798, | Nov 13 1997 | Novellus Systems, Inc.; International Business Machines Corp. | Electroplating anode including membrane partition system and method of preventing passivation of same |
6132857, | Feb 29 1996 | SNECMA | Hybrid component with high strength/mass ratio and method of manufacturing said component |
6139703, | Sep 18 1997 | Semitool, Inc. | Cathode current control system for a wafer electroplating apparatus |
6139712, | Nov 13 1997 | Novellus Systems, Inc. | Method of depositing metal layer |
6156167, | Nov 13 1997 | Novellus Systems, Inc. | Clamshell apparatus for electrochemically treating semiconductor wafers |
6159354, | Nov 13 1997 | Novellus Systems, Inc.; International Business Machines, Inc. | Electric potential shaping method for electroplating |
6162344, | Jul 22 1998 | Novellus Systems, Inc. | Method of electroplating semiconductor wafer using variable currents and mass transfer to obtain uniform plated layer |
6168693, | Jan 22 1998 | Novellus Systems, Inc | Apparatus for controlling the uniformity of an electroplated workpiece |
6174425, | May 14 1997 | SHENZHEN XINGUODU TECHNOLOGY CO , LTD | Process for depositing a layer of material over a substrate |
6179983, | Nov 13 1997 | Novellus Systems, Inc | Method and apparatus for treating surface including virtual anode |
6197181, | Mar 20 1998 | Applied Materials Inc | Apparatus and method for electrolytically depositing a metal on a microelectronic workpiece |
6203582, | Jul 15 1996 | Applied Materials Inc | Modular semiconductor workpiece processing tool |
6228231, | May 29 1997 | Novellus Systems, Inc | Electroplating workpiece fixture having liquid gap spacer |
6270647, | Sep 30 1997 | SEMITOOL, INC | Electroplating system having auxiliary electrode exterior to main reactor chamber for contact cleaning operations |
6280581, | Dec 29 1998 | Method and apparatus for electroplating films on semiconductor wafers | |
6322674, | Sep 18 1997 | Applied Materials Inc | Cathode current control system for a wafer electroplating apparatus |
6322678, | Jul 11 1998 | SEMITOOL, INC | Electroplating reactor including back-side electrical contact apparatus |
6343793, | Nov 13 1997 | Novellus Systems, Inc. | Dual channel rotary union |
6344125, | Apr 06 2000 | International Business Machines Corporation | Pattern-sensitive electrolytic metal plating |
6391166, | Feb 12 1998 | ACM Research, Inc. | Plating apparatus and method |
6436249, | Nov 13 1997 | Novellus Systems, Inc. | Clamshell apparatus for electrochemically treating semiconductor wafers |
6444101, | Nov 12 1999 | Applied Materials, Inc | Conductive biasing member for metal layering |
6454926, | Sep 30 1997 | Applied Materials Inc | Semiconductor plating system workpiece support having workpiece-engaging electrode with submerged conductive current transfer areas |
6500316, | Aug 30 1999 | International Business Machines Corporation | Apparatus for rotary cathode electroplating with wireless power transfer |
6500317, | Dec 16 1997 | Ebara Corporation | Plating apparatus for detecting the conductivity between plating contacts on a substrate |
6517689, | Jul 10 1998 | Ebara Corporation | Plating device |
6527926, | Jul 11 1998 | Applied Materials Inc | Electroplating reactor including back-side electrical contact apparatus |
6547937, | Jan 03 2000 | Applied Materials Inc | Microelectronic workpiece processing tool including a processing reactor having a paddle assembly for agitation of a processing fluid proximate to the workpiece |
6551483, | Feb 29 2000 | Novellus Systems, Inc. | Method for potential controlled electroplating of fine patterns on semiconductor wafers |
6562204, | Feb 29 2000 | Novellus Systems, Inc. | Apparatus for potential controlled electroplating of fine patterns on semiconductor wafers |
6589401, | Nov 13 1997 | Novellus Systems, Inc. | Apparatus for electroplating copper onto semiconductor wafer |
6627051, | Sep 18 1997 | Semitool, Inc. | Cathode current control system for a wafer electroplating apparatus |
6627052, | Dec 12 2000 | GLOBALFOUNDRIES U S INC | Electroplating apparatus with vertical electrical contact |
6693417, | Feb 08 1999 | Commonwealth of Australia | Micro-electronic bond degradation sensor and method of manufacture |
6761812, | Jun 28 2002 | GLOBALFOUNDRIES Inc | Apparatus and method for electrochemical metal deposition |
6783657, | Aug 29 2002 | U S BANK NATIONAL ASSOCIATION, AS COLLATERAL AGENT | Systems and methods for the electrolytic removal of metals from substrates |
6802946, | Dec 21 2000 | Novellus Systems, Inc | Apparatus for controlling thickness uniformity of electroplated and electroetched layers |
6843894, | Dec 18 1997 | Semitool, Inc. | Cathode current control system for a wafer electroplating apparatus |
6849167, | Jul 11 1998 | Semitool, Inc. | Electroplating reactor including back-side electrical contact apparatus |
6908540, | Jul 13 2001 | Applied Materials, Inc. | Method and apparatus for encapsulation of an edge of a substrate during an electro-chemical deposition process |
6921468, | Sep 30 1997 | Semitool, Inc. | Electroplating system having auxiliary electrode exterior to main reactor chamber for contact cleaning operations |
7025862, | Oct 22 2002 | Applied Materials | Plating uniformity control by contact ring shaping |
7087144, | Jan 31 2003 | Applied Materials, Inc.; Applied Materials, Inc | Contact ring with embedded flexible contacts |
20020022363, | |||
20050051436, | |||
JP407014811, | |||
JP4131395, | |||
JP4280993, | |||
JP58182823, | |||
JP6017291, | |||
JP63118093, | |||
WO32835, | |||
WO204715, | |||
WO9712079, | |||
WO9916936, | |||
WO9925902, | |||
WO9925903, | |||
WO9925904, | |||
WO9925905, | |||
WO9926275, |
Executed on | Assignor | Assignee | Conveyance | Frame | Reel | Doc |
Date | Maintenance Fee Events |
Jan 26 2009 | REM: Maintenance Fee Reminder Mailed. |
Jul 19 2009 | EXP: Patent Expired for Failure to Pay Maintenance Fees. |
Date | Maintenance Schedule |
Apr 08 2011 | 4 years fee payment window open |
Oct 08 2011 | 6 months grace period start (w surcharge) |
Apr 08 2012 | patent expiry (for year 4) |
Apr 08 2014 | 2 years to revive unintentionally abandoned end. (for year 4) |
Apr 08 2015 | 8 years fee payment window open |
Oct 08 2015 | 6 months grace period start (w surcharge) |
Apr 08 2016 | patent expiry (for year 8) |
Apr 08 2018 | 2 years to revive unintentionally abandoned end. (for year 8) |
Apr 08 2019 | 12 years fee payment window open |
Oct 08 2019 | 6 months grace period start (w surcharge) |
Apr 08 2020 | patent expiry (for year 12) |
Apr 08 2022 | 2 years to revive unintentionally abandoned end. (for year 12) |