Patent Grant
7585398
This application relates to chambers, systems, and methods for electrochemically processing microfeature workpieces having a plurality of microdevices integrated in and/or on the workpiece. The microdevices can include submicron features. Particular aspects of the present invention are directed toward electrochemical deposition chambers having nonporous barriers to separate a first processing fluid and a second processing fluid. Additional aspects of this application are directed toward electrochemical deposition chambers having (a) a barrier between a first processing fluid and a second processing fluid, and (b) a plurality of independently operable electrodes in the second processing fluid.
Microelectronic devices, such as semiconductor devices, imagers, and displays, are generally fabricated on and/or in microelectronic workpieces using several different types of machines (“tools”). Many such processing machines have a single processing station that performs one or more procedures on the workpieces. Other processing machines have a plurality of processing stations that perform a series of different procedures on individual workpieces or batches of workpieces. In a typical fabrication process, one or more layers of conductive materials are formed on the workpieces during deposition stages. The workpieces are then typically subject to etching and/or polishing procedures (i.e., planarization) to remove a portion of the deposited conductive layers for forming electrically isolated contacts and/or conductive lines.
Tools that plate metals or other materials on the workpieces are becoming an increasingly useful type of processing machine. Electroplating and electroless plating techniques can be used to deposit copper, solder, permalloy, gold, silver, platinum, electrophoretic resist and other materials onto workpieces for forming blanket layers or patterned layers. A typical copper plating process involves depositing a copper seed layer onto the surface of the workpiece using chemical vapor deposition (CVD), physical vapor deposition (PVD), electroless plating processes, or other suitable methods. After forming the seed layer, a blanket layer or patterned layer of copper is plated onto the workpiece by applying an appropriate electrical potential between the seed layer and an anode in the presence of an electroprocessing solution. The workpiece is then cleaned, etched and/or annealed in subsequent procedures before transferring the workpiece to another processing machine.
The plating machines used in fabricating microelectronic devices must meet many specific performance criteria. For example, many plating processes must be able to form small contacts in vias or trenches that are less than 0.5 μm wide, and often less than 0.1 μm wide. A combination of organic additives such as “accelerators,” “suppressors,” and “levelers” can be added to the electroplating solution to improve the plating process within the trenches so that the plating metal fills the trenches from the bottom up. As such, maintaining the proper concentration of organic additives in the electroplating solution is important to properly fill very small features.
One drawback of conventional plating processes is that the organic additives decompose and break down proximate to the surface of the anode. Also, as the organic additives decompose, it is difficult to control the concentration of organic additives and their associated breakdown products in the plating solution, which can result in poor feature filling and nonuniform layers. Moreover, the decomposition of organic additives produces by-products that can cause defects or other nonuniformities. To reduce the rate at which organic additives decompose near the anode, other anodes such as copper-phosphorous anodes can be used.
Another drawback of conventional plating processes is that organic additives and/or chloride ions in the electroplating solution can alter pure copper anodes. This can alter the electrical field, which can result in inconsistent processes and nonuniform layers. Thus, there is a need to improve the plating process to reduce the adverse effects of the organic additives.
Still another drawback of electroplating is providing a desired electrical field at the surface of the workpiece. The distribution of electrical current in the plating solution is a function of the uniformity of the seed layer across the contact surface, the configuration/condition of the anode, the configuration of the chamber, and other factors. However, the current density profile on the plating surface can change during a plating cycle. For example, the current density profile typically changes during a plating cycle as material plates onto the seed layer. The current density profile can also change over a longer period of time because (a) the shape of consumable anodes changes as they erode, and (b) the concentration of constituents in the plating solution can change. Therefore, it can be difficult to maintain a desired current density at the surface of the workpiece.
The present invention is directed, in part, toward electrochemical deposition chambers with nonporous barriers to separate processing fluids. The chambers are divided into two distinct systems that interact with each other to electroplate a material onto the workpiece while controlling migration of selected elements in the processing fluids (e.g., organic additives) from crossing the barrier to avoid the problems caused when organic additives are proximate to the anode and when bubbles or other matter get into the processing fluid.
The chambers include a processing unit to provide a first processing fluid to a workpiece (i.e., working electrode), an electrode unit for conveying a flow of a second processing fluid different than the first processing fluid, and an electrode (i.e., counter electrode) in the electrode unit. The chambers also include a nonporous barrier between the first processing fluid and the second processing fluid. The nonporous barrier allows ions to pass through the barrier but inhibits nonionic species from passing between the first and second processing fluids. As such, the nonporous barrier separates and isolates components of the first and second processing fluids from each other such that the first processing fluid can have different chemical characteristics than the second processing fluid. For example, the first processing fluid can be a catholyte having organic additives and the second processing fluid can be an anolyte without organic additives or a much lower concentration of such additives.
The nonporous barrier provides several advantages by substantially preventing the organic additives in the catholyte from migrating to the anolyte. First, because the organic additives are prevented from being in the anolyte, they cannot flow past the anode and decompose into products that interfere with the plating process. Second, because the organic additives do not decompose at the anode, they are consumed at a much slower rate in the catholyte so that it is less expensive and easier to control the concentration of organic additives in the catholyte. Third, less expensive anodes, such as pure copper anodes, can be used in the anolyte because the risk of passivation is reduced or eliminated.
The present invention is also directed toward electrochemical deposition chambers with (a) a porous and/or nonporous barrier between processing fluids to mitigate or eliminate the problems caused by organic additives, and (b) multiple independently operable electrodes to provide and maintain a desired current density at the surface of the workpiece. These chambers are also divided into two distinct systems that interact with each other to electroplate a material onto the workpiece while controlling migration of selected elements in the processing fluids (e.g., organic additives) from crossing the barrier to avoid the problems caused by the interaction between the organic additives and the anode and by bubbles or particulates in the processing fluid. Additionally, the independently operable electrodes provide better control of the electrical field at the surface of the workpiece compared to systems that have only a single electrode.
The chambers include a processing unit to provide a first processing fluid to a workpiece (i.e., working electrode), an electrode unit for conveying a flow of a second processing fluid different than the first processing fluid, and a plurality of electrodes (i.e., counter electrodes) in the electrode unit. The chambers also include a barrier between the first processing fluid and the second processing fluid. The barrier can be a porous, permeable member that permits fluid and small molecules to flow through the barrier between the first and second processing fluids. Alternatively, the barrier can be a nonporous, semipermeable member that prevents fluid flow between the first and second processing fluids while allowing ions to pass between the fluids. The barrier may also comprise a member having porous areas and nonporous areas. The barrier of these embodiments separates and/or isolates components of the first and second processing fluids from each other such that the first processing fluid can have different chemical characteristics than the second processing fluid. For example, the first processing fluid can be a catholyte having organic additives and the second processing fluid can be an anolyte without organic additives or with a much lower concentration of such additives.
The multiple electrodes in this aspect of the invention can be controlled independently of one another to tailor the electrical field to the workpiece. Each electrode can have a current level such that the electrical field generated by all of the electrodes provides the desired plating profile at the surface of the workpiece. Additionally, the current applied to each electrode can be independently varied throughout a plating cycle to compensate for differences that occur at the surface of the workpiece as the thickness of the plated layer increases.
The combination of having multiple electrodes to control the electrical field and a barrier in the chamber will provide a system that is significantly more efficient and produces significantly better quality products. The system is more efficient because using one processing fluid for the workpiece and another processing fluid for the electrodes allows the processing fluids to be tailored to the best use in each area without having to compromise to mitigate the adverse effects of using only a single processing solution. As such, the tool does not need to be shut down as often to adjust the fluids and it consumes less constituents. The system produces better quality products because (a) using two different processing fluids allows better control of the concentration of important constituents in each processing fluid, and (b) using multiple electrodes provides better control of the current density at the surface of the workpiece.
As used herein, the terms “microfeature workpiece” or “workpiece” refer to substrates on and/or in which microdevices are formed. Typical microdevices include microelectronic circuits or components, thin-film recording heads, data storage elements, microfluidic devices, and other products. Micromachines or micromechanical devices are included within this definition because they are manufactured using much of the same technology as used in the fabrication of integrated circuits. The substrates can be semiconductive pieces (e.g., silicon wafers or gallium arsenide wafers), nonconductive pieces (e.g., various ceramic substrates), or conductive pieces (e.g., doped wafers). Also, the term electrochemical processing or deposition includes electroplating, electro-etching, anodization, and/or electroless plating.
Several embodiments of electrochemical deposition chambers for processing microfeature workpieces are particularly useful for electrolytically depositing metals or electrophoretic resist in or on structures of a workpiece. The electrochemical deposition chambers in accordance with the invention can accordingly be used in systems with wet chemical processing chambers for etching, rinsing, or other types of wet chemical processes in the fabrication of microfeatures in and/or on semiconductor substrates or other types of workpieces. Several embodiments of electrochemical deposition chambers and integrated tools in accordance with the invention are set forth in
The illustrated vessel 110 includes a processing unit 120 (shown schematically), an electrode unit 180 (shown schematically), and a nonporous barrier 170 (shown schematically) between the processing and electrode units 120 and 180. The processing unit 120 is configured to contain a first processing fluid for processing the microfeature workpiece W. The electrode unit 180 is configured to contain an electrode 190 and a second processing fluid at least proximate to the electrode 190. The second processing fluid is generally different than the first processing fluid, but they can be the same in some applications. In general, the first and second processing fluids have some ions in common. The first processing fluid in the processing unit 120 is a catholyte and the second processing fluid in the electrode unit 180 is an anolyte when the workpiece is cathodic. In electropolishing or other deposition processes, however, the first processing fluid can be an anolyte and the second processing fluid can be a catholyte.
The system 100 further includes a first flow system 112 that stores and circulates the first processing fluid and a second flow system 192 that stores and circulates the second processing fluid. The first flow system 112 may include a first processing fluid reservoir 113, a plurality of fluid conduits 114 to convey a flow of the first processing fluid between the first processing fluid reservoir 113 and the processing unit 120, and a plurality of components 115 (shown schematically) in the processing unit 120 to convey a flow of the first processing fluid between the processing site and the nonporous barrier 170. The second flow system 192 may include a second processing fluid reservoir 193, a plurality of fluid conduits 185 to convey the flow of the second processing fluid between the second processing fluid reservoir 193 and the electrode unit 180, and a plurality of components 184 (shown schematically) in the electrode unit 180 to convey the flow of the second processing fluid between the electrode 190 and the nonporous barrier 170. The concentrations of individual constituents of the first and second processing fluids can be controlled separately in the first and second processing fluid reservoirs 113 and 193, respectively. For example, metals, such as copper, can be added to the first and/or second processing fluid in the respective reservoir 113 or 193. Additionally, the temperature of the first and second processing fluids and/or removal of undesirable materials or bubbles can be controlled separately in the first and second flow systems 112 and 192.
The nonporous barrier 170 is positioned between the first and second processing fluids in the region of the interface between the processing unit 120 and the electrode unit 180 to separate and/or isolate the first processing fluid from the second processing fluid. For example, the nonporous barrier 170 inhibits fluid flow between the first and second flow systems 112 and 192 while selectively allowing ions, such as cations and/or anions, to pass through the barrier 170 between the first and second processing fluids. As such, an electrical field, a charge imbalance between the processing fluids, and/or differences in the concentration of substances in the processing fluids can drive ions across the nonporous barrier 170 as described in detail below.
In contrast to porous barriers, such as filter media, expanded Teflon (Goretex), and fritted materials (glass, quartz, ceramic, etc.), the nonporous barrier 170 inhibits nonionic species, including small molecules and fluids, from passing through the barrier 170. For example, the nonporous barrier 170 can be substantially free of open area. Consequently, fluid is inhibited from passing through the nonporous barrier 170 when the first and second flow systems 112 and 192 operate at typical pressures. Water, however, can be transported through the nonporous barrier 170 via osmosis and/or electro-osmosis. Osmosis can occur when the molar concentrations in the first and second processing fluids are substantially different. Electro-osmosis can occur as water is carried through the nonporous barrier 170 with current carrying ions in the form of a hydration sphere. When the first and second processing fluids have similar molar concentrations and no electrical current is passed through the processing fluids, fluid flow between the first and second processing fluids is substantially prevented.
Moreover, the nonporous barrier 170 can be hydrophilic so that bubbles in the processing fluids do not cause portions of the barrier 170 to dry, which reduces conductivity through the barrier 170. Suitable nonporous barriers 170 include NAFION membranes manufactured by DuPont®, Ionac® membranes manufactured by Sybron Chemicals Inc., and NeoSepta membranes manufactured by Tokuyuma.
When the system 100 is used for electrochemical processing, an electrical potential can be applied to the electrode 190 and the workpiece W such that the electrode 190 is an anode and the workpiece W is a cathode. The first and second processing fluids are accordingly a catholyte and an anolyte, respectively, and each fluid can include a solution of metal ions to be plated onto the workpiece W. The electrical field between the electrode 190 and the workpiece W may drive positive ions through the nonporous barrier 170 from the anolyte to the catholyte, or drive negative ions in the opposite direction. In plating applications, an electrochemical reaction occurs at the microfeature workpiece W in which metal ions are reduced to form a solid layer of metal on the microfeature workpiece W. In electrochemical etching and other electrochemical applications, the electrical field may drive ions the opposite direction.
One feature of the system 100 illustrated in
The system 100 illustrated in
To control the concentration of metal ions in the first processing solution in some electroplating applications, the system 100 illustrated in
The illustrated vessel 110a includes a processing unit 120a (shown schematically), an electrode unit 180a (shown schematically), and a barrier 170a (shown schematically) between the processing and electrode units 120a and 180a. The processing unit 120a of the illustrated embodiment includes a dielectric divider 142 projecting from the barrier 170a toward the processing site and a plurality of chambers 130 (identified individually as 130a-b) defined by the dielectric divider 142. The chambers 130a-b can be arranged concentrically and have corresponding openings 144a-b proximate to the processing site. The chambers 130a-b are configured to convey a first processing fluid to/from the microfeature workpiece W. The processing unit 120a, however, may not include the dielectric divider 142 and the chambers 130, or the dielectric divider 142 and the chambers 130 may have other configurations.
The electrode unit 180a includes a dielectric divider 186, a plurality of compartments 184a-b defined by the dielectric divider 186, and a plurality of electrodes 190a and 190b disposed within corresponding compartments 184a-b. The compartments 184a-b can be arranged concentrically and configured to convey a second processing fluid at least proximate to the electrodes 190a-b. As noted above, the second processing fluid is generally different than the first processing fluid, but they can be the same in some applications. In general, the first and second processing fluids have some ions in common. The first processing fluid in the processing unit 120a is a catholyte and the second processing fluid in the electrode unit 180a is an anolyte when the workpiece is cathodic. In electropolishing or other deposition processes, however, the first processing fluid can be an anolyte and the second processing fluid can be a catholyte. Although the system 100a shown in
The system 100a further includes a first flow system 112a that stores and circulates the first processing fluid and a second flow system 192a that stores and circulates the second processing fluid. The first flow system 112a may include (a) the first processing fluid reservoir 113, (b) the plurality of fluid conduits 114 to convey the flow of the first processing fluid between the first processing fluid reservoir 113 and the processing unit 120a, and (c) the chambers 130a-b to convey the flow of the first processing fluid between the processing site and the barrier 170a. The second flow system 192a may include (a) the second processing fluid reservoir 193, (b) the plurality of fluid conduits 185 to convey the flow of the second processing fluid between the second processing fluid reservoir 193 and the electrode unit 180a, and (c) the compartments 184a-b to convey the flow of the second processing fluid between the electrodes 190a-b and the barrier 170a. The concentrations of individual constituents of the first and second processing fluids can be controlled separately in the first and second processing fluid reservoirs 113 and 193, respectively. For example, metals, such as copper, can be added to the first and/or second processing fluid in the respective reservoir 113 or 193. Additionally, the temperature of the first and second processing fluids and/or removal of undesirable materials or bubbles can be controlled separately in the first and second flow systems 112a and 192a.
The barrier 170a is positioned between the first and second processing fluids in the region of the interface between the processing unit 120a and the electrode unit 180a to separate and/or isolate the first processing fluid from the second processing fluid. For example, the barrier 170a can be a porous, permeable membrane that permits fluid and small molecules to flow through the barrier 170a between the first and second processing fluids. Alternatively, the barrier 170a can be a nonporous, semipermeable membrane that prevents fluid flow between the first and second flow systems 112 and 192 while selectively allowing ions, such as cations and/or anions, to pass through the barrier 170a between the first and second processing fluids, as described above with respect to the nonporous barrier 170 shown in
When the system 100a is used for electrochemical processing, an electrical potential can be applied to the electrodes 190a-b and the workpiece W such that the electrodes 190a-b are anodes and the workpiece W is a cathode. The first and second processing fluids are accordingly a catholyte and an anolyte, respectively, and each fluid can include a solution of metal ions to be plated onto the workpiece W. The electrical field between the electrodes 190a-b and the workpiece W may drive positive ions through the barrier 170a from the anolyte to the catholyte, or drive negative ions in the opposite direction. In plating applications, an electrochemical reaction occurs at the microfeature workpiece W in which metal ions are reduced to form a solid layer of metal on the microfeature workpiece W. In electrochemical etching and other electrochemical applications, the electrical field may drive ions the opposite direction.
The first electrode 190a provides an electrical field to the workpiece W at the processing site through the portion of the second processing fluid in the first compartment 184a of the electrode unit 180a and the portion of the first processing fluid in the first chamber 130a of the processing unit 120a. Accordingly, the first electrode 190a provides an electrical field that is effectively exposed to the processing site via the first opening 144a. The first opening 144a shapes the electrical field of the first electrode 190a to create a “virtual electrode” at the top of the first opening 144a. This is a “virtual electrode” because the dielectric divider 142 shapes the electrical field of the first electrode 190a so that the effect is as if the first electrode 190a were placed in the first opening 144a. Virtual electrodes are described in detail in U.S. patent application Ser. No. 09/872,151, incorporated by reference above. Similarly, the second electrode 190b provides an electrical field to the workpiece W through the portion of the second processing fluid in the second compartment 184b of the electrode unit 180a and the portion of the first processing fluid in the second chamber 130b of the processing unit 120a. Accordingly, the second electrode 190b provides an electrical field that is effectively exposed to the processing site via the second opening 144b to create another “virtual electrode.”
In operation, a first current is applied to the first electrode 190a and a second current is applied to the second electrode 190b. The first and second electrical currents are controlled independently of each other such that they can be the same or different than each other at any given time. Additionally, the first and second electrical currents can be dynamically varied throughout a plating cycle. The first and second electrodes accordingly provide a highly controlled electrical field to compensate for inconsistent or non-uniform seed layers as well as changes in the plated layer during a plating cycle.
In addition to the benefits of having multiple independently operable electrodes, the system 100a is expected to have similar benefits as the system 100 described above with respect to separating the first processing fluid from the second processing fluid. As explained above, for example, the lack of organic additives in the anolyte provides the following advantages: (a) reduces by-products of decomposed organics in the catholyte; (b) reduces consumption of the organic additives; (c) reduces passivation of the anode; and (d) enables efficient use of pure copper anodes. The system 100a illustrated in
The foregoing operation of the system 100 shown in
In other embodiments, the nonporous barrier can be anionic and the electrode can be an inert anode (i.e. platinum or iridium oxide) to prevent the accumulation of sulfate ions in the first processing fluid. In this embodiment, the acid concentration or pH in the first and second processing fluids can be similar. Alternatively, the second processing fluid may have a higher concentration of acid to increase the conductivity of the fluid. Copper salt (copper sulfate) can be added to the first processing fluid to replenish the copper in the fluid. Electrical current can be carried through the barrier by the passage of sulfate anions from the first processing fluid to the second processing fluid. Therefore, sulfate ions are less likely to accumulate in the first processing fluid where they can adversely affect the deposited film.
In other embodiments, the system can electrochemically etch copper from the workpiece. In these embodiments, the first processing solution (the anolyte) contains an electrolyte that may include copper ions. During electrochemical etching, a potential can be applied to the electrode and/or the workpiece. An anionic nonporous barrier can be used to prevent positive ions (such as copper) from passing into the second processing fluid (catholyte). Consequently, the current is carried by anions, and copper ions are inhibited from flowing proximate to and being deposited on the electrode.
The foregoing operation of the illustrated system 100 also occurs by selecting suitable volumes of anolyte and catholyte. Referring back to
The illustrated vessel 210 includes a processing unit 220, a barrier unit 260 coupled to the processing unit 220, and an electrode unit 280 coupled to the barrier unit 260. The processing unit 220, the barrier unit 260, and the electrode unit 280 need not be separate units, but rather they can be sections or components of a single unit. The processing unit 220 includes a chassis 228 having a first portion of the first flow system 212a to direct the flow of the first processing fluid through the chassis 228. The first portion of the first flow system 212a can include a separate component attached to the chassis 228 and/or a plurality of fluid passageways in the chassis 228. In this embodiment, the first portion of the first flow system 212a includes a conduit 215, a first flow guide 216 having a plurality of slots 217, and an antechamber 218. The slots 217 in the first flow guide 216 distribute the flow radially to the antechamber 218.
The first portion of the first flow system 212a further includes a second flow guide 219 that receives the flow from the antechamber 218. The second flow guide 219 can include a sidewall 221 having a plurality of openings 222 and a flow projector 224 having a plurality of apertures 225. The openings 222 can be vertical slots arranged radially around the sidewall 221 to provide a plurality of flow components projecting radially inwardly toward the flow projector 224. The apertures 225 in the flow projector 224 can be a plurality of elongated slots or other openings that are inclined upwardly and radially inwardly. The flow projector 224 receives the radial flow components from the openings 222 and redirects the flow through the apertures 225. It will be appreciated that the openings 222 and the apertures 225 can have several different configurations. For example, the apertures 225 can project the flow radially inwardly without being canted upwardly, or the apertures 225 can be canted upwardly at a greater angle than the angle shown in
The processing unit 220 can also include a field shaping module 240 for shaping the electrical field(s) and directing the flow of the first processing fluid at the processing site. In this embodiment, the field shaping module 240 has a first partition 242a with a first rim 243a, a second partition 242b with a second rim 243b, and a third partition 242c with a third rim 243c. The first rim 243a defines a first opening 244a, the first rim 243a and the second rim 243b define a second opening 244b, and the second rim 243b and the third rim 243c define a third opening 244c. The processing unit 220 can further include a weir 245 having a rim 246 over which the first processing fluid can flow into a recovery channel 247. The third rim 243c and the weir 245 define a fourth opening 244d. The field shaping module 240 and the weir 245 are attached to the processing unit 220 by a plurality of bolts or screws, and a number of seals 249 are positioned between the chassis 228 and the field shaping module 240.
The vessel 210 is not limited to having the field shaping unit 240 shown in
In the illustrated embodiment, the first portion of the first flow system 212a in the processing unit 220 further includes a first channel 230a in fluid communication with the antechamber 218, a second channel 230b in fluid communication with the second opening 244b, a third channel 230c in fluid communication with the third opening 244c, and a fourth channel 230d in fluid communication with the fourth opening 244d. The first portion of the first flow system 212a can accordingly convey the first processing fluid to the processing site to provide a desired fluid flow profile at the processing site.
In this particular processing unit 220, the first processing fluid enters through an inlet 214 and passes through the conduit 215 and the first flow guide 216. The first processing fluid flow then bifurcates with a portion of the fluid flowing up through the second flow guide 219 via the antechamber 218 and another portion of the fluid flowing down through the first channel 230a of the processing unit 220 and into the barrier unit 260. The upward flow through the second flow guide 219 passes through the flow projector 224 and the first opening 244a. A portion of the first processing fluid flow passes upwardly over the rim 243a, through the processing site proximate to the workpiece, and then flows over the rim 246 of the weir 245. Other portions of the first processing fluid flow downwardly through each of the channels 230b-d of the processing unit 220 and into the barrier unit 260.
The electrode unit 280 of the illustrated vessel 210 includes a container 282 that houses an electrode assembly and a first portion of the second flow system 292a. The illustrated container 282 includes a plurality of dividers or walls 286 that define a plurality of compartments 284 (identified individually as 284a-d). The walls 286 of this container 282 are concentric annular dividers that define annular compartments 284. However, in other embodiments, the walls can have different configurations to create nonannular compartments and/or each compartment can be further divided into cells. The specific embodiment shown in
The vessel 210 can further include at least one electrode disposed in the electrode unit 280. The vessel 210 shown in
In this embodiment, the electrodes 290 are coupled to an electrical connector system 291 that extends through the container 282 of the electrode unit 280 to couple the electrodes 290 to a power supply. The electrodes 290 can provide a constant current throughout a plating cycle, or the current through one or more of the electrodes 290 can be changed during a plating cycle according to the particular parameters of the workpiece. Moreover, each electrode 290 can have a unique current that is different than the current of the other electrodes 290. The electrodes 290 can be operated in DC, pulsed, and pulse reverse waveforms. Suitable processes for operating the electrodes are set forth in U.S. patent application Ser. Nos. 09/849,505; 09/866,391; and 09/866,463, all of which are hereby incorporated by reference in their entirety.
The first portion of the second flow system 292a conveys the second processing fluid through the electrode unit 280. More specifically, the second processing fluid enters the electrode unit 280 through an inlet 285 and then the flow is divided as portions of the second processing fluid flow into each of the compartments 284. The portions of the second processing fluid flow across corresponding electrodes 290 as the fluid flows through the compartments 284 and into the barrier unit 260.
The illustrated barrier unit 260 is between the processing unit 220 and the electrode unit 280 to separate the first processing fluid from the second processing fluid while allowing individual electrical fields from the electrodes 290 to act through the openings 244a-d. The barrier unit 260 includes a second portion of the first flow system 212b, a second portion of the second flow system 292b, and a nonporous barrier 270 separating the first processing fluid in the first flow system 212 from the second processing fluid in the second flow system 292. The second portion of the first flow system 212b is in fluid communication with the first portion of the first flow system 212a in the processing unit 220. The second portion of the first flow system 212b includes a plurality of annular openings 265 (identified individually as 265a-d): adjacent to the nonporous barrier 270, a plurality of channels 264 (identified individually as 264a-d) extending between corresponding annular openings 265 and corresponding channels 230 in the processing unit 220, and a plurality of passageways 272 extending between corresponding annular openings 265 and a first outlet 273. As such, the first processing fluid flows from the channels 230a-d of the processing unit 220 to corresponding channels 264a-d of the barrier unit 260. After flowing through the channels 264a-d in the barrier unit 260, the first processing fluid flows in a direction generally parallel to the nonporous barrier 270 through the corresponding annular openings 265 to corresponding passageways 272. The first processing fluid flows through the passageways 272 and exits the vessel 210 via the first outlet 273.
The second portion of the second flow system 292b is in fluid communication with the first portion of the second flow system 292a in the electrode unit 280. The second portion of the second flow system 292b includes a plurality of channels 266 (identified individually as 266a-d) extending between the barrier 270 and corresponding compartments 284 in the electrode unit 280 and a plurality of passageways 274 extending between the nonporous barrier 270 and a second outlet 275. As such, the second processing fluid flows from the compartments 284a-d to corresponding channels 266a-d and against the nonporous barrier 270. The second processing fluid flow flexes the nonporous barrier 270 toward the processing unit 220 so that the fluid can flow in a direction generally parallel to the barrier 270 between the barrier 270 and a surface 263 of the barrier unit 260 to the corresponding passageways 274. The second processing fluid flows through the passageways 274 and exits the vessel 210 via the second outlet 275.
The nonporous barrier 270 is disposed between the second portion of the first flow system 212b and the second portion of the second flow system 292b to separate the first and second processing fluids. The nonporous barrier 270 can be a semipermeable membrane to inhibit fluid flow between the first and second flow systems 212 and 292 while allowing ions to pass through the barrier 270 between the first and second processing fluids. As explained above, the nonporous barrier 270 can also be cation or anion selective and accordingly permit only the selected ions to pass through the barrier 270. Because fluids are inhibited from flowing through the nonporous barrier 270, the barrier 270 is not subject to clogging.
Electrical current can flow through the nonporous barrier 270 in either direction in the presence of an electrolyte. For example, electrical current can flow from the second processing fluid in the channels 266 to the first processing fluid in the annular openings 265. Furthermore, the nonporous barrier 270 can be hydrophilic so that bubbles in the processing fluids do not cause portions of the barrier 270 to become dry and block electrical current. The nonporous barrier 270 shown in
The vessel 210 also controls bubbles that are formed at the electrodes 290 or elsewhere in the system. For example, the nonporous barrier 270, a lower portion of the barrier unit 260, and the electrode unit 280 are canted relative to the processing unit 220 to prevent bubbles in the second processing fluid from becoming trapped against the barrier 270. As bubbles in the second processing fluid move upward through the compartments 284 and the channels 266, the angled orientation of the nonporous barrier 270 and the bow of the barrier 270 above each channel 266 causes the bubbles to move laterally under the barrier 270 toward the upper side of the surface 263 corresponding to each channel 266. The passageways 274 carry the bubbles out to the second outlet 275 for removal. The illustrated nonporous barrier 270 is oriented at an angle α of approximately 5°. In additional embodiments, the barrier 270 can be oriented at an angle greater than or less than 5° that is sufficient to remove bubbles. The angle α, accordingly, is not limited to 5°. In general, the angle α should be large enough to cause bubbles to migrate to the high side, but not so large that it adversely affects the electrical field.
An advantage of the illustrated barrier unit 260 is that the angle α of the nonporous barrier 270 prevents bubbles from being trapped against portions of the barrier 270 and creating dielectric areas on the barrier 270, which would adversely affect the electrical field. In other embodiments, other devices can be used to degas the processing fluids in lieu of or in addition to canting the barrier 270. As such, the nonporous barrier 270 need not be canted relative to the processing unit 220 in all applications.
The spacing between the electrodes 290 and the nonporous barrier 270 is another design criteria for the vessel 210. In the illustrated vessel 210, the distance between the nonporous barrier 270 and each electrode 290 is approximately the same. For example, the distance between the nonporous barrier 270 and the first electrode 290a is approximately the same as the distance between the nonporous barrier 270 and the second electrode 290b. Alternatively, the distance between the nonporous barrier 270 and each electrode 290 can be different. In either case, the distance between the nonporous barrier 270 and each arcuate section of a single electrode 290 is approximately the same. The uniform spacing between each section of a single electrode 290 and the nonporous barrier 270 is expected to provide more accurate control over the electrical field compared to having different spacings between sections of an electrode 290 and the barrier 270. Because the second processing fluid has less acid, and is thus less conductive, a difference in the distance between the nonporous barrier 270 and separate sections of an individual electrode 290 has a greater affect on the electrical field at the workpiece than a difference in the distance between the workpiece and the barrier 270.
In operation, the processing unit 220, the barrier unit 260, and the electrode unit 280 operate together to provide a desired electrical field profile (e.g., current density) at the workpiece. The first electrode 290a provides an electrical field to the workpiece through the portions of the first and second processing fluids that flow in the first channels 230a, 264a, and 266a, and the first compartment 284a. Accordingly, the first electrode 290a provides an electrical field that is effectively exposed to the processing site via the first opening 244a. The first opening 244a shapes the electrical field of the first electrode 290a according to the configuration of the rim 243a of the first partition 242a to create a “virtual electrode” at the top of the first opening 244a. This is a “virtual electrode” because the field shaping module 240 shapes the electrical field of the first electrode 290a so that the effect is as if the first electrode 290a were placed in the first opening 244a. Virtual electrodes are described in detail in U.S. patent application Ser. No. 09/872,151, which is hereby incorporated by reference. Similarly, the second, third, and fourth electrodes 290b-d provide electrical fields to the processing site through the portions of the first and second processing fluids that flow in the second channels 230b, 264b, and 266b, the third channels 230c, 264c, and 266c, and the fourth channels 230d, 264d, and 266d, respectively. Accordingly, the second, third, and fourth electrodes 290b-d provide electrical fields that are effectively exposed to the processing site via the second, third, and fourth openings 244b-d, respectively, to create corresponding virtual electrodes.
The illustrated vessel 210 further includes a first attachment assembly 254a for attaching the barrier unit 260 to the processing unit 220 and a second attachment assembly 254b for attaching the electrode unit 280 to the barrier unit 260. The first and second attachment assemblies 254a-b can be quick-release devices to securely hold the corresponding units together. For example, the first and second attachment assemblies 254a-b can include clamp rings 255a-b and latches 256a-b that move the clamp rings 255a-b between a first position and a second position. As the latches 256a-b move the clamp rings 255a-b from the first position to the second position, the diameter of the clamp rings 255a-b decreases to clamp the corresponding units together. Optionally, as the first and second attachment assemblies 254a-b move from the first position to the second position, the attachment assemblies 254a-b drive the corresponding units together to compress the interface elements 250 and 252 and properly position the units relative to each other. Suitable attachment assemblies of this type are disclosed in detail in U.S. Patent Application No. 60/476,881, filed Jun. 6, 2003, which is hereby incorporated by reference in its entirety. In other embodiments, the attachment assemblies 254a-b may not be quick-release devices and can include a plurality of clamp rings, a plurality of latches, a plurality of bolts, or other types of fasteners.
One advantage of the vessel 210 illustrated in
An alternate embodiment of the barrier unit 260 can include a porous barrier instead of the nonporous barrier 270 shown and described above with reference to
Unlike the vessel 210, the vessel 310 does not include a separate barrier unit but rather the barrier 370 is attached directly between the processing unit 320 and the electrode unit 380. The barrier 370 otherwise separates the first processing fluid in the processing unit 320 and the second processing fluid in the electrode unit 380 in much the same manner as the nonporous barrier 270. Another difference with the vessel 210 is that the barrier 370 and the electrode unit 380 are not canted relative to the processing unit 320.
The first and second processing fluids can flow in the vessel 310 in a direction that is opposite to the flow direction described above with reference to the vessel 210 of
The frame 662 has a plurality of posts 663 and cross-bars 661 that are welded together in a manner known in the art. A plurality of outer panels and doors (not shown in
The mounting module 660 is a rigid, stable structure that maintains the relative positions between the wet chemical processing chambers 610, the workpiece supports 613, and the transport system 605. One aspect of the mounting module 660 is that it is much more rigid and has a significantly greater structural integrity compared to the frame 662 so that the relative positions between the wet chemical processing chambers 610, the workpiece supports 613, and the transport system 605 do not change over time. Another aspect of the mounting module 660 is that it includes a dimensionally stable deck 664 with positioning elements at precise locations for positioning the processing chambers 610 and the workpiece supports 613 at known locations on the deck 664. In one embodiment (not shown), the transport system 605 is mounted directly to the deck 664. In an arrangement shown in
The tool 600 is particularly suitable for applications that have demanding specifications which require frequent maintenance of the wet chemical processing chambers 610, the workpiece support 613, or the transport system 605. A wet chemical processing chamber 610 can be repaired or maintained by simply detaching the chamber from the processing deck 664 and replacing the chamber 610 with an interchangeable chamber having mounting hardware configured to interface with the positioning elements on the deck 664. Because the mounting module 660 is dimensionally stable and the mounting hardware of the replacement processing chamber 610 interfaces with the deck 664, the chambers 610 can be interchanged on the deck 664 without having to recalibrate the transport system 605. This is expected to significantly reduce the downtime associated with repairing or maintaining the processing chambers 610 so that the tool 600 can maintain a high throughput in applications that have stringent performance specifications.
The deck 664 further includes a plurality of positioning elements 668 and attachment elements 669 arranged in a precise pattern across the first panel 666a. The positioning elements 668 include holes machined in the first panel 666a at precise locations, and/or dowels or pins received in the holes. The dowels are also configured to interface with the wet chemical processing chambers 610 (
The mounting module 660 also includes exterior side plates 670a along longitudinal outer edges of the deck 664, interior side plates 670b along longitudinal inner edges of the deck 664, and endplates 670c attached to the ends of the deck 664. The transport platform 665 is attached to the interior side plates 670b and the end plates 670c. The transport platform 665 includes track positioning elements 668c for accurately positioning the track 604 (
The panels and bracing of the deck 664 can be made from stainless steel, other metal alloys, solid cast materials, or fiber-reinforced composites. For example, the panels and plates can be made from Nitronic 50 stainless steel, Hastelloy 625 steel alloys, or a solid cast epoxy filled with mica. The fiber-reinforced composites can include a carbon-fiber or Kevlar® mesh in a hardened resin. The material for the panels 666a and 666b should be highly rigid and compatible with the chemicals used in the wet chemical processes. Stainless steel is well-suited for many applications because it is strong but not affected by many of the electrolytic solutions or cleaning solutions used in wet chemical processes. In one embodiment, the panels and plates 666a-b and 670a-c are 0.125 to 0.375 inch thick stainless-steel, and more specifically they can be 0.250 inch thick stainless steel. The panels and plates, however, can have different thicknesses in other embodiments.
The bracing 671 can also be stainless steel, fiber-reinforced composite materials, other metal alloys, and/or solid cast materials. In one embodiment, the bracing can be 0.5 to 2.0 inch wide stainless steel joists, and more specifically 1.0 inch wide by 2.0 inches tall stainless steel joists. In other embodiments the bracing 671 can be a honey-comb core or other structures made from metal (e.g., stainless steel, aluminum, titanium, etc.), polymers, fiber glass or other materials.
The mounting module 660 is constructed by assembling the sections of the deck 664, and then welding or otherwise adhering the end plates 670c to the sections of the deck 664. The components of the deck 664 are generally secured together by the throughbolts 672 without welds. The outer side plates 670a and the interior side plates 670b are attached to the deck 664 and the end plates 670c using welds and/or fasteners. The platform 665 is then securely attached to the end plates 670c, and the interior side plates 670b. The order in which the mounting module 660 is assembled can be varied and is not limited to the procedure explained above.
The mounting module 660 provides a heavy-duty, dimensionally stable structure that maintains the relative positions between the positioning elements 668a-b on the deck 664 and the positioning elements 668c on the platform 665 within a range that does not require the transport system 605 to be recalibrated each time a replacement processing chamber 610 or workpiece support 613 is mounted to the deck 664. The mounting module 660 is generally a rigid structure that is sufficiently strong to maintain the relative positions between the positioning elements 668a-b and 668c when the wet chemical processing chambers 610, the workpiece supports 613, and the transport system 605 are mounted to the mounting module 660. In several embodiments, the mounting module 660 is configured to maintain the relative positions between the positioning elements 668a-b and 668c to within 0.025 inch. In other embodiments, the mounting module is configured to maintain the relative positions between the positioning elements 668a-b and 668c to within approximately 0.005 to 0.015 inch. As such, the deck 664 often maintains a uniformly flat surface to within approximately 0.025 inch, and in more specific embodiments to approximately 0.005-0.015 inch.
From the foregoing, it will be appreciated that specific embodiments of the invention have been described herein for purposes of illustration, but that various modifications may be made without deviating from the spirit and scope of the invention. For example, various aspects of any of the foregoing embodiments can be combined in different combinations, or features such as the sizes, material types, and/or fluid flows can be different. Accordingly, the invention is not limited except as by the appended claims.
This application is a continuation in part of U.S. Application numbers: (a) Ser. No. 10/729,349, filed on Dec. 5, 2003, now U.S. Pat. No. 7,351,314;(b) Ser. No. 10/729,357 filed on Dec. 5, 2003, now U.S. Pat. No. 7,351,315; and(c) Ser. No. 09/872,151, filed on May 31, 2001, now U.S. Pat. No. 7,264,698, which is a continuation-in-part of U.S. application Ser. No. 09/804,697, filed on Mar. 12, 2001, now U.S. Pat. No. 6,660,137, which is a continuation of International Patent Application No. PCT/US00/10120 filed on Apr. 13, 2000 and published in the English language, which claims the benefit of U.S. Application No. 60/129,055, filed on Apr. 13, 1999. All of the foregoing are incorporated herein by reference. This application is also a continuation in part of U.S. application Ser. No. 09/875,365, filed on Jun. 5, 2001, now U.S. Pat. No. 6,916,412.
| Number | Name | Date | Kind |
|---|---|---|---|
| 2256274 | Boedecker et al. | Sep 1941 | A |
| 3309263 | Grobe | Mar 1967 | A |
| 3616284 | Bodmer et al. | Oct 1971 | A |
| 3664933 | Clauss | May 1972 | A |
| 3706635 | Kowalski | Dec 1972 | A |
| 3706651 | Leland | Dec 1972 | A |
| 3716462 | Jensen | Feb 1973 | A |
| 3798003 | Ensley et al. | Mar 1974 | A |
| 3798033 | Yost, Jr. | Mar 1974 | A |
| 3878066 | Dettke et al. | Apr 1975 | A |
| 3930963 | Polichette et al. | Jan 1976 | A |
| 3968885 | Hassan et al. | Jul 1976 | A |
| 4000046 | Weaver | Dec 1976 | A |
| 4022679 | Koziol et al. | May 1977 | A |
| 4030015 | Herko et al. | Jun 1977 | A |
| 4046105 | Gomez | Sep 1977 | A |
| 4072557 | Schiel | Feb 1978 | A |
| 4082638 | Jumer | Apr 1978 | A |
| 4113577 | Ross et al. | Sep 1978 | A |
| 4134802 | Herr | Jan 1979 | A |
| 4137867 | Aigo | Feb 1979 | A |
| 4165252 | Gibbs | Aug 1979 | A |
| 4170959 | Aigo | Oct 1979 | A |
| 4222834 | Bacon et al. | Sep 1980 | A |
| 4238310 | Eckler et al. | Dec 1980 | A |
| 4246088 | Murphy et al. | Jan 1981 | A |
| 4259166 | Whitehurst | Mar 1981 | A |
| 4287029 | Shimamura | Sep 1981 | A |
| 4304641 | Grandia et al. | Dec 1981 | A |
| 4323433 | Loch | Apr 1982 | A |
| 4341629 | Uhlinger | Jul 1982 | A |
| 4360410 | Fletcher et al. | Nov 1982 | A |
| 4374007 | Barclay et al. | Feb 1983 | A |
| 4378283 | Seyffert et al. | Mar 1983 | A |
| 4384930 | Eckles | May 1983 | A |
| 4391694 | Runsten | Jul 1983 | A |
| 4422915 | Wielonski et al. | Dec 1983 | A |
| 4431361 | Bayne | Feb 1984 | A |
| 4437943 | Beck | Mar 1984 | A |
| 4440597 | Wells et al. | Apr 1984 | A |
| 4443117 | Muramoto et al. | Apr 1984 | A |
| 4449885 | Hertel | May 1984 | A |
| 4451197 | Lange | May 1984 | A |
| 4463503 | Applegate | Aug 1984 | A |
| 4466864 | Bacon | Aug 1984 | A |
| 4469564 | Okinaka et al. | Sep 1984 | A |
| 4469566 | Wray | Sep 1984 | A |
| 4475823 | Stone | Oct 1984 | A |
| 4480028 | Kato et al. | Oct 1984 | A |
| 4495153 | Midorikawa | Jan 1985 | A |
| 4495453 | Inaba | Jan 1985 | A |
| 4500394 | Rizzo | Feb 1985 | A |
| 4529480 | Trokhan | Jul 1985 | A |
| 4541895 | Albert | Sep 1985 | A |
| 4566847 | Maeda | Jan 1986 | A |
| 4576685 | Goffredo et al. | Mar 1986 | A |
| 4576689 | Makkaev | Mar 1986 | A |
| 4585539 | Edson | Apr 1986 | A |
| 4604177 | Sivilotti | Aug 1986 | A |
| 4604178 | Fiegener | Aug 1986 | A |
| 4634503 | Nogavich | Jan 1987 | A |
| 4639028 | Olson | Jan 1987 | A |
| 4648944 | George et al. | Mar 1987 | A |
| 4670126 | Messer et al. | Jun 1987 | A |
| 4685414 | DiRico | Aug 1987 | A |
| 4687552 | Early et al. | Aug 1987 | A |
| 4693017 | Oehler et al. | Sep 1987 | A |
| 4696729 | Santini | Sep 1987 | A |
| 4715934 | Tamminen | Dec 1987 | A |
| 4741624 | Barroyer | May 1988 | A |
| 4760671 | Ward | Aug 1988 | A |
| 4761214 | Hinman | Aug 1988 | A |
| 4770590 | Hugues et al. | Sep 1988 | A |
| 4781800 | Goldman | Nov 1988 | A |
| 4800818 | Kawaguchi et al. | Jan 1989 | A |
| 4828654 | Reed | May 1989 | A |
| 4849054 | Klowak | Jul 1989 | A |
| 4858539 | Schumann | Aug 1989 | A |
| 4864239 | Casarcia et al. | Sep 1989 | A |
| 4868992 | Crafts et al. | Sep 1989 | A |
| 4898647 | Luce et al. | Feb 1990 | A |
| 4902398 | Homstad | Feb 1990 | A |
| 4906341 | Yamakawa | Mar 1990 | A |
| 4913085 | Vohringer et al. | Apr 1990 | A |
| 4924890 | Giles et al. | May 1990 | A |
| 4944650 | Matsumoto | Jul 1990 | A |
| 4949671 | Davis et al. | Aug 1990 | A |
| 4951601 | Maydan et al. | Aug 1990 | A |
| 4959278 | Shimauch | Sep 1990 | A |
| 4962726 | Matsushita et al. | Oct 1990 | A |
| 4979464 | Kunze-Concewitz et al. | Dec 1990 | A |
| 4988533 | Freeman et al. | Jan 1991 | A |
| 5000827 | Schuster | Mar 1991 | A |
| 5024746 | Stierman et al. | Jun 1991 | A |
| 5026239 | Chiba | Jun 1991 | A |
| 5048589 | Cook et al. | Sep 1991 | A |
| 5054988 | Shiraiwa | Oct 1991 | A |
| 5055036 | Asano et al. | Oct 1991 | A |
| 5061144 | Akimoto | Oct 1991 | A |
| 5069548 | Boehnlein | Dec 1991 | A |
| 5078852 | Yee | Jan 1992 | A |
| 5083364 | Olbrich et al. | Jan 1992 | A |
| 5096550 | Mayer | Mar 1992 | A |
| 5110248 | Asano et al. | May 1992 | A |
| 5115430 | Hahne | May 1992 | A |
| 5125784 | Asano | Jun 1992 | A |
| 5128912 | Hug et al. | Jul 1992 | A |
| 5135636 | Yee et al. | Aug 1992 | A |
| 5138973 | Davis et al. | Aug 1992 | A |
| 5146136 | Ogura | Sep 1992 | A |
| 5151168 | Gilton | Sep 1992 | A |
| 5155336 | Gronet et al. | Oct 1992 | A |
| 5156174 | Thompson | Oct 1992 | A |
| 5156730 | Bhatt | Oct 1992 | A |
| 5162079 | Brown et al. | Nov 1992 | A |
| 5168886 | Thompson et al. | Dec 1992 | A |
| 5168887 | Thompson | Dec 1992 | A |
| 5169408 | Biggerstaff et al. | Dec 1992 | A |
| 5172803 | Lewin | Dec 1992 | A |
| 5174045 | Thompson et al. | Dec 1992 | A |
| 5178512 | Skrobak | Jan 1993 | A |
| 5178639 | Nishi | Jan 1993 | A |
| 5180273 | Salaya et al. | Jan 1993 | A |
| 5183377 | Becker et al. | Feb 1993 | A |
| 5186594 | Toshima et al. | Feb 1993 | A |
| 5209817 | Ahmad et al. | May 1993 | A |
| 5217586 | Datta | Jun 1993 | A |
| 5222310 | Thompson | Jun 1993 | A |
| 5227041 | Brogden | Jul 1993 | A |
| 5228232 | Miles | Jul 1993 | A |
| 5228966 | Murata | Jul 1993 | A |
| 5230371 | Lee | Jul 1993 | A |
| 5232511 | Bergman | Aug 1993 | A |
| 5235995 | Bergman et al. | Aug 1993 | A |
| 5238500 | Bergman | Aug 1993 | A |
| 5252137 | Tateyama et al. | Oct 1993 | A |
| 5252807 | Chizinsky | Oct 1993 | A |
| 5256262 | Blomsterberg | Oct 1993 | A |
| 5256274 | Poris | Oct 1993 | A |
| 5271953 | Litteral | Dec 1993 | A |
| 5271972 | Kwok et al. | Dec 1993 | A |
| 5301700 | Kamikawa et al. | Apr 1994 | A |
| 5302464 | Nomura et al. | Apr 1994 | A |
| 5306895 | Ushikoshi et al. | Apr 1994 | A |
| 5314294 | Taniguchi et al. | May 1994 | A |
| 5316642 | Young | May 1994 | A |
| 5326455 | Kubo et al. | Jul 1994 | A |
| 5330604 | Allum et al. | Jul 1994 | A |
| 5332271 | Grant et al. | Jul 1994 | A |
| 5332445 | Bergman | Jul 1994 | A |
| 5340456 | Mehler | Aug 1994 | A |
| 5344491 | Katou | Sep 1994 | A |
| 5348620 | Hermans et al. | Sep 1994 | A |
| 5364504 | Smurkoski et al. | Nov 1994 | A |
| 5366785 | Sawdai | Nov 1994 | A |
| 5366786 | Connor et al. | Nov 1994 | A |
| 5368711 | Poris | Nov 1994 | A |
| 5372848 | Blackwell | Dec 1994 | A |
| 5376176 | Kuriyama | Dec 1994 | A |
| 5377708 | Bergman | Jan 1995 | A |
| 5388945 | Garric et al. | Feb 1995 | A |
| 5391285 | Lytle | Feb 1995 | A |
| 5391517 | Gelatos et al. | Feb 1995 | A |
| 5405518 | Hsieh et al. | Apr 1995 | A |
| 5411076 | Matsunaga et al. | May 1995 | A |
| 5421987 | Tzanavaras et al. | Jun 1995 | A |
| 5427674 | Langenskiold et al. | Jun 1995 | A |
| 5429686 | Chiu et al. | Jul 1995 | A |
| 5429733 | Ishida | Jul 1995 | A |
| 5431803 | DiFranco et al. | Jul 1995 | A |
| 5437777 | Kishi | Aug 1995 | A |
| 5441629 | Kosaki | Aug 1995 | A |
| 5442416 | Tateyama et al. | Aug 1995 | A |
| 5443707 | Mori | Aug 1995 | A |
| 5445484 | Kato et al. | Aug 1995 | A |
| 5447615 | Ishida | Sep 1995 | A |
| 5454405 | Hawes | Oct 1995 | A |
| 5460478 | Akimoto et al. | Oct 1995 | A |
| 5464313 | Ohsawa | Nov 1995 | A |
| 5472502 | Batchelder | Dec 1995 | A |
| 5489341 | Bergman et al. | Feb 1996 | A |
| 5500081 | Bergman | Mar 1996 | A |
| 5501768 | Hermans et al. | Mar 1996 | A |
| 5508095 | Allum et al. | Apr 1996 | A |
| 5512319 | Cook et al. | Apr 1996 | A |
| 5514258 | Brinket et al. | May 1996 | A |
| 5516412 | Andricacos et al. | May 1996 | A |
| 5522975 | Andricacos et al. | Jun 1996 | A |
| 5527390 | Ono et al. | Jun 1996 | A |
| 5544421 | Thompson et al. | Aug 1996 | A |
| 5549808 | Farooq | Aug 1996 | A |
| 5567267 | Kazama et al. | Oct 1996 | A |
| 5571325 | Ueyama | Nov 1996 | A |
| 5575611 | Thompson et al. | Nov 1996 | A |
| 5584310 | Bergman | Dec 1996 | A |
| 5584971 | Komino | Dec 1996 | A |
| 5593545 | Rugowski et al. | Jan 1997 | A |
| 5597460 | Reynolds | Jan 1997 | A |
| 5597836 | Hackler et al. | Jan 1997 | A |
| 5600532 | Michiya et al. | Feb 1997 | A |
| 5609239 | Schlecker | Mar 1997 | A |
| 5620581 | Ang | Apr 1997 | A |
| 5639206 | Oda et al. | Jun 1997 | A |
| 5639316 | Cabral | Jun 1997 | A |
| 5641613 | Boff et al. | Jun 1997 | A |
| 5650082 | Anderson | Jul 1997 | A |
| 5651823 | Parodi et al. | Jul 1997 | A |
| 5658387 | Reardon | Aug 1997 | A |
| 5660472 | Peuse et al. | Aug 1997 | A |
| 5660517 | Thompson et al. | Aug 1997 | A |
| 5662788 | Sandhu | Sep 1997 | A |
| 5664337 | Davis et al. | Sep 1997 | A |
| 5670034 | Lowery | Sep 1997 | A |
| 5676337 | Giras et al. | Oct 1997 | A |
| 5677118 | Spara et al. | Oct 1997 | A |
| 5678320 | Thompson et al. | Oct 1997 | A |
| 5681392 | Swain | Oct 1997 | A |
| 5683564 | Reynolds | Nov 1997 | A |
| 5684654 | Searle et al. | Nov 1997 | A |
| 5684713 | Asada et al. | Nov 1997 | A |
| 5700127 | Harada | Dec 1997 | A |
| 5711646 | Ueda et al. | Jan 1998 | A |
| 5723028 | Poris | Mar 1998 | A |
| 5731678 | Zila et al. | Mar 1998 | A |
| 5744019 | Ang | Apr 1998 | A |
| 5746565 | Tepolt | May 1998 | A |
| 5747098 | Larson | May 1998 | A |
| 5754842 | Minagawa | May 1998 | A |
| 5755948 | Lazaro et al. | May 1998 | A |
| 5759006 | Miyamoto et al. | Jun 1998 | A |
| 5762751 | Bleck | Jun 1998 | A |
| 5765444 | Bacchi | Jun 1998 | A |
| 5765889 | Nam et al. | Jun 1998 | A |
| 5776327 | Botts et al. | Jul 1998 | A |
| 5785826 | Greenspan | Jul 1998 | A |
| 5788829 | Joshi et al. | Aug 1998 | A |
| 5802856 | Schaper et al. | Sep 1998 | A |
| 5829791 | Kotsubo et al. | Nov 1998 | A |
| 5843296 | Greenspan | Dec 1998 | A |
| 5871626 | Crafts | Feb 1999 | A |
| 5871805 | Lemelson | Feb 1999 | A |
| 5882498 | Dubin | Mar 1999 | A |
| 5883762 | Calhoun et al. | Mar 1999 | A |
| 5892207 | Kawamura et al. | Apr 1999 | A |
| 5904827 | Reynolds | May 1999 | A |
| 5908540 | Fanti | Jun 1999 | A |
| 5908543 | Matsunami | Jun 1999 | A |
| 5925227 | Kobayashi et al. | Jul 1999 | A |
| 5932077 | Reynolds | Aug 1999 | A |
| 5937142 | Moslehi et al. | Aug 1999 | A |
| 5957836 | Johnson | Sep 1999 | A |
| 5980706 | Bleck | Nov 1999 | A |
| 5985126 | Bleck | Nov 1999 | A |
| 5989397 | Laube et al. | Nov 1999 | A |
| 5989406 | Beetz | Nov 1999 | A |
| 5998123 | Tanaka et al. | Dec 1999 | A |
| 5999886 | Martin et al. | Dec 1999 | A |
| 6001235 | Arken et al. | Dec 1999 | A |
| 6004828 | Hanson | Dec 1999 | A |
| 6017820 | Ting et al. | Jan 2000 | A |
| 6027631 | Broadbent | Feb 2000 | A |
| 6028986 | Song | Feb 2000 | A |
| 6051284 | Byrne | Apr 2000 | A |
| 6053687 | Kirkpatrick | Apr 2000 | A |
| 6072160 | Bahl | Jun 2000 | A |
| 6072163 | Armstrong et al. | Jun 2000 | A |
| 6074544 | Reid | Jun 2000 | A |
| 6080288 | Schwartz et al. | Jun 2000 | A |
| 6080291 | Woodruff et al. | Jun 2000 | A |
| 6080691 | Lindsay et al. | Jun 2000 | A |
| 6086680 | Foster et al. | Jul 2000 | A |
| 6090260 | Inoue | Jul 2000 | A |
| 6091498 | Hanson | Jul 2000 | A |
| 6099702 | Reid | Aug 2000 | A |
| 6099712 | Ritzdorf | Aug 2000 | A |
| 6103085 | Woo et al. | Aug 2000 | A |
| 6107192 | Subrahmanyan et al. | Aug 2000 | A |
| 6108937 | Raaijmakers | Aug 2000 | A |
| 6110011 | Somekh | Aug 2000 | A |
| 6110346 | Reid | Aug 2000 | A |
| 6126798 | Reid et al. | Oct 2000 | A |
| 6130415 | Knoot | Oct 2000 | A |
| 6136163 | Cheung | Oct 2000 | A |
| 6139703 | Hanson et al. | Oct 2000 | A |
| 6139712 | Patton | Oct 2000 | A |
| 6140234 | Uzoh et al. | Oct 2000 | A |
| 6143147 | Jelinek | Nov 2000 | A |
| 6143155 | Adams | Nov 2000 | A |
| 6151532 | Barone et al. | Nov 2000 | A |
| 6156167 | Patton | Dec 2000 | A |
| 6157106 | Tietz et al. | Dec 2000 | A |
| 6159354 | Contolini | Dec 2000 | A |
| 6162344 | Reid | Dec 2000 | A |
| 6162488 | Gevelber et al. | Dec 2000 | A |
| 6168695 | Woodruff | Jan 2001 | B1 |
| 6174425 | Simpson | Jan 2001 | B1 |
| 6174796 | Takagi et al. | Jan 2001 | B1 |
| 6179983 | Reid | Jan 2001 | B1 |
| 6221230 | Takeuchi | Jan 2001 | B1 |
| 6184068 | Ohtani et al. | Feb 2001 | B1 |
| 6193859 | Contolini | Feb 2001 | B1 |
| 6199301 | Wallace | Mar 2001 | B1 |
| 6218097 | Bell et al. | Apr 2001 | B1 |
| 6228232 | Woodruff | May 2001 | B1 |
| 6234738 | Kimata | May 2001 | B1 |
| 6251238 | Kaufman et al. | Jun 2001 | B1 |
| 6251528 | Uzoh et al. | Jun 2001 | B1 |
| 6254742 | Hanson et al. | Jul 2001 | B1 |
| 6258220 | Dordi | Jul 2001 | B1 |
| 6261433 | Landau | Jul 2001 | B1 |
| 6270647 | Graham | Aug 2001 | B1 |
| 6277263 | Chen | Aug 2001 | B1 |
| 6278089 | Young et al. | Aug 2001 | B1 |
| 6280183 | Mayur et al. | Aug 2001 | B1 |
| 6280582 | Woodruff et al. | Aug 2001 | B1 |
| 6280583 | Woodruff et al. | Aug 2001 | B1 |
| 6623609 | Harris | Sep 2001 | B2 |
| 6297154 | Gross et al. | Oct 2001 | B1 |
| 6303010 | Woodruff et al. | Oct 2001 | B1 |
| 6309520 | Woodruff et al. | Oct 2001 | B1 |
| 6309524 | Woodruff et al. | Oct 2001 | B1 |
| 6318951 | Schmidt | Nov 2001 | B1 |
| 6322112 | Duncan | Nov 2001 | B1 |
| 6322677 | Woodruff | Nov 2001 | B1 |
| 6342137 | Woodruff | Jan 2002 | B1 |
| 6365729 | Tyagi et al. | Apr 2002 | B1 |
| 6391166 | Wang | May 2002 | B1 |
| 6402923 | Mayer | Jun 2002 | B1 |
| 6409892 | Woodruff et al. | Jun 2002 | B1 |
| 6428660 | Woodruff et al. | Aug 2002 | B2 |
| 6428662 | Woodruff et al. | Aug 2002 | B1 |
| 6436267 | Carl et al. | Aug 2002 | B1 |
| 6444101 | Stevens et al. | Sep 2002 | B1 |
| 6471913 | Weaver et al. | Oct 2002 | B1 |
| 6481956 | Hofmeister | Nov 2002 | B1 |
| 6491806 | Dubin | Dec 2002 | B1 |
| 6497801 | Woodruff | Dec 2002 | B1 |
| 6527920 | Mayer et al. | Mar 2003 | B1 |
| 6562421 | Sudo et al. | May 2003 | B2 |
| 6565729 | Chen et al. | May 2003 | B2 |
| 6569297 | Wilson et al. | May 2003 | B2 |
| 6599412 | Graham | Jul 2003 | B1 |
| 6632334 | Anderson et al. | Oct 2003 | B2 |
| 6654122 | Hanson | Nov 2003 | B1 |
| 6660137 | Wilson et al. | Dec 2003 | B2 |
| 6672820 | Hanson | Jan 2004 | B1 |
| 6678055 | Du-Nour et al. | Jan 2004 | B2 |
| 6699373 | Woodruff et al. | Mar 2004 | B2 |
| 6709562 | Andricacos et al. | Mar 2004 | B1 |
| 6749390 | Woodruff et al. | Jun 2004 | B2 |
| 6752584 | Woodruff et al. | Jun 2004 | B2 |
| 6755954 | Mayer et al. | Jun 2004 | B2 |
| 6773571 | Mayer | Aug 2004 | B1 |
| 6780374 | Weaver et al. | Aug 2004 | B2 |
| 6916412 | Woodruff et al. | Jul 2005 | B2 |
| 6921468 | Graham et al. | Jul 2005 | B2 |
| 20010024611 | Woodruff | Sep 2001 | A1 |
| 20010032788 | Woodruff et al. | Oct 2001 | A1 |
| 20010043856 | Woodruff | Nov 2001 | A1 |
| 20020008036 | Wang | Jan 2002 | A1 |
| 20020008037 | Wilson | Jan 2002 | A1 |
| 20020032499 | Wilson | Mar 2002 | A1 |
| 20020046952 | Graham | Apr 2002 | A1 |
| 20020053509 | Hanson et al. | May 2002 | A1 |
| 20020079215 | Wilson et al. | Jun 2002 | A1 |
| 20020096508 | Weaver et al. | Jul 2002 | A1 |
| 20020125141 | Wilson | Sep 2002 | A1 |
| 20020139678 | Wilson | Oct 2002 | A1 |
| 20020195351 | Lu et al. | Dec 2002 | A1 |
| 20030038035 | Wilson | Feb 2003 | A1 |
| 20030062258 | Woodruff | Apr 2003 | A1 |
| 20030070918 | Hanson | Apr 2003 | A1 |
| 20030127337 | Hanson | Jul 2003 | A1 |
| 20040031693 | Chen | Feb 2004 | A1 |
| 20040055877 | Wilson | Mar 2004 | A1 |
| 20040099533 | Wilson | May 2004 | A1 |
| 20040188259 | Wilson | Sep 2004 | A1 |
| 20050087439 | Hanson et al. | Apr 2005 | A1 |
| Number | Date | Country |
|---|---|---|
| 873651 | Jun 1971 | CA |
| 41 14 427 | Nov 1992 | DE |
| 195 25 666 | Oct 1996 | DE |
| 0 140 404 | Aug 1984 | EP |
| 0047132 | Jul 1985 | EP |
| 0 677 612 | Oct 1985 | EP |
| 0 257 670 | Mar 1988 | EP |
| 0 290 210 | Nov 1988 | EP |
| 0290210 | Nov 1988 | EP |
| 0 677 612 | Oct 1995 | EP |
| 0582019 | Oct 1995 | EP |
| 0544311 | May 1996 | EP |
| 0 881 673 | May 1998 | EP |
| 0 982 771 | Aug 1999 | EP |
| 1 069 213 | Jul 2000 | EP |
| 0452939 | Nov 2000 | EP |
| 2217107 | Mar 1989 | GB |
| 2 254 288 | Mar 1992 | GB |
| 2 279 372 | Jun 1994 | GB |
| 59-15094 | Aug 1984 | JP |
| 1048442 | Feb 1989 | JP |
| 220800 | Aug 1990 | JP |
| 4144150 | May 1992 | JP |
| 4311591 | Nov 1992 | JP |
| 5146984 | Jun 1993 | JP |
| 5195183 | Aug 1993 | JP |
| 5211224 | Aug 1993 | JP |
| 6017291 | Jan 1994 | JP |
| 6073598 | Mar 1994 | JP |
| 6224202 | Aug 1994 | JP |
| 7113159 | May 1995 | JP |
| 7197299 | Aug 1995 | JP |
| 7197299 | Aug 1995 | JP |
| 10-083960 | Mar 1998 | JP |
| 11036096 | Feb 1999 | JP |
| 11080993 | Mar 1999 | JP |
| 11-350185 | Dec 1999 | JP |
| 2000-087299 | Mar 2000 | JP |
| 2000-256896 | Sep 2000 | JP |
| 2001-64795 | Mar 2001 | JP |
| 2004-097856 | Apr 2004 | JP |
| WO-9000476 | Jan 1990 | WO |
| WO-9104213 | Apr 1991 | WO |
| WO-9506326 | Mar 1995 | WO |
| WO-9520064 | Jul 1995 | WO |
| WO-9916936 | Apr 1996 | WO |
| WO 9925902 | May 1999 | WO |
| WO-9925904 | May 1999 | WO |
| WO-9925905 | May 1999 | WO |
| WO-9940615 | Aug 1999 | WO |
| WO-9941434 | Aug 1999 | WO |
| WO-9945745 | Sep 1999 | WO |
| WO-0002675 | Jan 2000 | WO |
| WO-0002808 | Jan 2000 | WO |
| WO-0003072 | Jan 2000 | WO |
| WO-0202808 | Jan 2000 | WO |
| WO-0032835 | Jun 2000 | WO |
| WO-0061498 | Oct 2000 | WO |
| WO-0061837 | Oct 2000 | WO |
| WO-0146910 | Jun 2001 | WO |
| WO-0190434 | Nov 2001 | WO |
| WO-0191163 | Nov 2001 | WO |
| WO-0217203 | Feb 2002 | WO |
| WO-0245476 | Jun 2002 | WO |
| WO-02097165 | Dec 2002 | WO |
| WO-02099165 | Dec 2002 | WO |
| WO-03018874 | Mar 2003 | WO |
| WO-03072853 | Sep 2003 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20050087439 A1 | Apr 2005 | US | |
| 20090114533 A9 | May 2009 | US |
| Number | Date | Country | |
|---|---|---|---|
| 60129055 | Apr 1999 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/US00/10120 | Apr 2000 | US |
| Child | 09804697 | US | |
| Parent | 10861899 | US | |
| Child | 09804697 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 10729349 | Dec 2003 | US |
| Child | 10861899 | US | |
| Parent | 10729357 | Dec 2003 | US |
| Child | 10729349 | US | |
| Parent | 09872151 | May 2001 | US |
| Child | 10729357 | US | |
| Parent | 09804697 | Mar 2001 | US |
| Child | 09872151 | US | |
| Parent | 09875365 | Jun 2001 | US |
| Child | 10861899 | US |
