1. Field of the Invention
The present invention relates to methods of manufacturing micromachinable, pico- to nanoliter-volume, hermetic packaging that incorporates reliable electrical feedthroughs, and sensors configured utilizing the same, all of which are intended to perform reliably in harsh and biological environments.
2. Description of the Prior Art
Over the past 20 years, advances in the field of microelectronics have enabled the realization of microelectromechanical systems (MEMS) and corresponding batch fabrication techniques. These developments have allowed the creation of sensors and actuators with micrometer-scale features. With the advent of the above-described capability, heretofore implausible applications for sensors and actuators are now significantly closer to commercial realization.
In parallel, much work has been done in the development of pressure sensors. Pressure sensors are disclosed, for example, in U.S. Pat. No. 6,855,115, issued Feb. 15, 2005; U.S. patent application Ser. No. 10/054,671, filed Jan. 22, 2002; U.S. patent application Ser. No. 10/215,377, filed Aug. 7, 2002; U.S. patent application Ser. No. 10/215,379, filed Aug. 7, 2002; U.S. patent application Ser. No. 10/943,772, filed Sep. 16, 2004; and U.S. patent application Ser. No. 11/157,375, filed Jun. 21, 2005, all of which are incorporated herein by reference.
In particular, absolute pressure sensors, in which the pressure external to the sensor is read with respect to an internal pressure reference, are of interest. The internal pressure reference is a volume within the sensor, sealed, which typically contains a number of moles of gas (the number can also be zero, i.e. the pressure reference can be a vacuum, which can be of interest to reduce temperature sensitivity of the pressure reference as known in the art). The external pressure is then read relative to this constant and known internal pressure reference, resulting in measurement of the external absolute pressure. For stability of the pressure reference and assuming the temperature and volume of the reference are invariant or substantially invariant, it is desirable that the number of moles of fluid inside the reference does not change. One method to approach this condition is for the reference volume to be hermetic.
The term hermetic is generally defined as meaning “being airtight or impervious to air.” In reality, however, all materials are, to a greater or lesser extent, permeable, and hence specifications must define acceptable levels of hermeticity. An acceptable level of hermeticity is therefore a rate of fluid ingress or egress that changes the pressure in the internal reference volume (a.k.a. pressure chamber) by an amount preferably less than 10 percent of the external pressure being sensed, more preferably less than 5 percent, and most preferably less than 1 percent over the accumulated time over which the measurements will be taken. In many biological applications, an acceptable pressure change in the pressure chamber is on the order of 1.5 mm Hg/year.
The pressure reference is typically interfaced with a sensing means that can sense deflections of boundaries of the pressure reference when the pressure external to the reference changes. A typical example would be bounding at least one side of the pressure reference with a deflectable diaphragm or plate and measuring the deflection of the diaphragm or plate by use of, among other techniques, a piezoresistive or a capacitance measurement. If the deflection of the diaphragm or plate is sufficiently small, the volume change of the pressure reference does not substantially offset the pressure in the pressure reference.
These approaches may require an electrical feedthrough to the hermetic environment (e.g., to contact electrodes inside the hermetic pressure reference), for connection to outside electronics to buffer or transmit the signal. Alternatively, electronics may be incorporated within the reference cavity, requiring power to be conducted into the hermetic environment. To maintain stability of the pressure reference, these seals should also be hermetic, resulting in the necessity to develop a feedthrough technology for contacts through the cavity walls. As is known in the art, such feedthrough points are typically sites for failure of hermeticity. This problem is further exacerbated when miniaturizing the sensor, since the total volume of material available for hermetic sealing shrinks proportionally and the reliability of the feedthrough is also greatly reduced. In the limit of ultraminiaturized sensors, such as those producible using microelectromechanical systems (MEMS) technology, one of the major challenges to enabling the use of such devices in applications where they are physically connected to other devices has been the creation of reliable hermetic packaging that provides feedthroughs that enable exchange of power and information with external electronics.
Design criteria for ultraminiature packaging that overcomes the aforementioned shortcomings are as follows: The packaging must exhibit long term hermeticity (on the order of the life of the sensor, which in some cases can exceed tens of years). Feedthroughs must be provided through the hermetic package that do not introduce new or unnecessary potential modes of failure. The feedthroughs will constitute a necessary material interface, but all other interfaces can and should be eliminated. In other words, the number and area of material interfaces should be minimized to reduce the potential for breach of hermeticity. The materials selected must be compatible with the processes used to fabricate the package as well as sufficiently robust to resist deleterious corrosion and biocompatible to minimize the body's immune response. Finally, the packaging should be amenable to batch fabrication.
In the past, many methods for creating such hermetic packages have been proposed. One approach used in the past to create the pressure cavity is anodic bonding to create a silicon-to-glass seal. A borosilicate glass is required for this method. Another technique utilized in the creation of hermetic packages is eutectic bonding to create a silicon to metal hermetic seal, e.g. Au to Si. Both of these bonding methods used to create the pressure cavity introduce a large area along the perimeter of the material interface of the pressure cavity package which presents opportunity for failure, e.g. through corrosion. These methods for creating the pressure cavity do not minimize the area of the material interface as is desirable. A desirable improvement to the construction of the pressure cavity would minimize the material interface to the hermetic electrical feedthroughs, and, even further, minimize the number and area of material interfaces in those feedthroughs.
Previous attempts to create hermetic feedthroughs also fall short of the above-stated requirements. Many prior art hermetic feedthroughs are too large and not amenable to the required miniaturization for pico to nanoliter volume packaging achievable by MEMS or similar approaches. Furthermore, earlier attempts to create feedthroughs in pico to nanoliter packaging are prone to corrosion because of the materials used in construction or are sufficiently complicated that they introduce more material interfaces than are necessary. A representative feedthrough approach, known as a “buried” feedthrough, is illustrated in
This prior art buried feedthrough suffers a number of disadvantages. First, there are numerous material interfaces: an interface 30 between the lower substrate 12 and the metal 10; an interface 32 between the metal 12 and the insulating layer 14, an interface 34 between the insulating layer 14 and the gold 24; and an interface 36 between the gold 24 and the upper substrate 20, all of which create potential paths for infusion into or effusion out of the hermetic chamber 22. The creation of this buried feedthrough also introduces increased processing steps. Further, the insulating layer material is cited as being prone to corrosion in certain environments, e.g. the human body. Corrosion issues may be further exacerbated by the application of electrical bias to metal 10 which may be required in certain applications. Thus prior art hermetic feedthroughs fall short of meeting the constraints outlined above.
Also, many prior art attempts to provide pressure sensors utilize silicon as a substrate material. If the package is implanted in vivo, silicon is not an optimal material choice. Silicon invokes an undesirable immune response over other, more inert materials such as fused silica. If silicon is used, a coating must be applied to ensure biocompatibility. Such a coating increases the package size, thereby decreasing the benefits of miniaturization, and introduces an undesirable additional processing step in the manufacture of the package.
Additionally, prior art devices commonly employ the use of borosilicate glass as part of the pressure cavity. The ions in borosilicate glass constitute an impurity in the glass. The barrier to diffusion of water decreases as the purity of glass decreases. This makes use of impure glass undesirable in such applications.
Thus a need exists for hermetic pico to nanoliter packaging with electrical feedthroughs for use in biological environments, such packaging being constructed of high-purity materials and having a reduced number and area of material interfaces.
The present invention comprises a method of manufacturing a micromachinable, hermetic, pico to nanoliter-volume pressure cavity. Such a pressure cavity utilizes high-purity materials and provides reliable electrical feedthroughs. The pressure cavity is preferably constructed of two or more substrates of a ceramic material, and the layers are optionally fused together so that there is no interface of material where the two substrates have been joined to create a cavity. Furthermore, feedthroughs establishing electrical communication within the cavity are formed in at least one of the substrates. The feedthroughs themselves are configured in such a way that the number and area of material interfaces is minimized. Such feedthroughs constitute the only site for material interface in the sensor package, thereby decreasing the number of potential leak sites in and increasing the reliability of the hermetic package. Pressure cavities and sensors of the disclosed embodiments are manufactured using microelectromechanical systems (MEMS) fabrication techniques, which allow creation of a device that is small, accurate, precise, durable, robust, biocompatible, and insensitive to changes in body chemistry or biology.
In another aspect the present invention comprises a sensor that can be incorporated into harsh and biological environments. One example of such an environment is a medical lead or catheter implanted, acutely or chronically, into the human body. The sensor is configured to measure one or more physical properties such as pressure or temperature. Communication between the sensor and another device can be established by, e.g., using wires fixed to bonding pads on the exterior of the sensor packaging that are configured so that they are in electrical contact with the hermetic feedthroughs. As another example, the hermetic electrical feedthrough can have a wire extending from the feedthrough, and contact with the pressure cavity can be accomplished via connection with this wire. Devices in electrical communication with sensors according to the present invention may be either implanted or external to the body. Sensors of this invention are sufficiently small to allow for incorporation into medical leads or catheters that are twelve French or smaller, preferably six French or smaller, without causing abrupt changes in geometry of the lead or catheter, and require minimal power to perform their intended function.
In one embodiment of the invention, a wired sensor ascending to the present invention comprises a hermetic pressure cavity. The pressure cavity further comprises a capacitor configured so that the characteristic capacitance value of the capacitor varies in response to a physical property, or changes in a physical property, of a patient. The electrodes of the capacitor are substantially planar and are arranged substantially parallel to and spaced apart from one another. The pressure cavity has at least one deflectable region in mechanical communication with at least one of the capacitor electrodes. Additionally, electrical feedthroughs are formed through the substrate defining the pressure cavity and allow for the sensor to receive power and signals, and return information to either implanted or extracorporeal external electronics.
In another embodiment of the invention, a wired sensor according to the present invention comprises a hermetic pressure cavity. The pressure cavity further comprises a Wheatstone bridge configured so that the resistance value of the bridge varies in response to a physical property, or changes in a physical property, of a patient. The pressure cavity has at least one deflectable region in mechanical communication with at least one of the resistors comprising the bridge. Additionally, electrical feedthroughs are formed through the substrate and allow for the sensor to receive power and signals, and return information to external electronics. It is a further aspect of this invention that only a portion of the Wheatstone bridge be located within the pressure cavity, the other portion being contained within external electronics.
In yet another embodiment, a wired sensor further comprises on-board (i.e., within the sensor package) electronics, e.g., a silicon chip bearing electronics. The variable capacitive or resistive element and the on-board electronics can be maintained in separate cavities in electrical communication with one another by hermetic feedthroughs formed through a middle substrate. Feedthroughs establishing electrical communication with the sensor exterior may be configured so that moisture does not affect the electronics over the life of the sensor and, optionally, are also hermetic. This configuration offers the advantage that the feedthroughs to the on-board electronics act as a redundant barrier to any potential breach of the hermeticity of the pressure cavity. Alternatively, the capacitor and on-board electronics can be contained within a single hermetic cavity. This configuration offers the advantage of decreased manufacturing steps, thereby lowering the overall cost to produce the sensor. In either case, electrical feedthroughs, which are themselves optionally hermetic, formed through the substrates comprising the external walls allow for the sensor to receive power and return information to external electronics.
Referring now to the drawings, in which like numerals indicate like elements throughout the several views,
A capacitor comprises a pair of lower electrodes 56, 57 located on a first wall 58 of the chamber 52. The two lower electrodes 56, 57 are electrically isolated from one another. A third electrode 60 is disposed on an opposite wall 62 of the pressure cavity 52 in parallel, spaced apart relation to the lower electrodes 56, 57. The upper electrode 60 is mechanically coupled to the deflectable region 54. As ambient pressure increases, the deflectable region 54 moves inward, displacing the upper electrode 60 toward the lower electrodes 56, 57, thereby changing the characteristic capacitance value of the capacitor.
The capacitor configuration depicted here is one example where the lower capacitor electrode consists of two electrically isolated regions, 56 and 57, although other configurations are possible and obvious to one skilled in the art.
The lower portion of the pressure cavity 52 comprises passages 64, 65 that traverse the hermetic pressure cavity body 51 and are in contact with the electrodes 56, 57. As shown in
It is a preferred embodiment of this invention that the metal-fused silica interface between the lower electrodes 56, 57 and the interior surface of the pressure cavity body 51 be hermetic. The electrical contact pads 66, 67 can occupy either all or part of the passages 64, 65. A variety of metal deposition techniques can be used (e.g., electroplating, use of molten metal, or PVD) depending on the choice of metal and desired material properties. In the case of a partially-filled feedthrough passage 64, 65, a void inside the feedthrough passages and above the electrical contact pads 66, 67 will remain. In order to fill these voids and to enhance the strength of the feedthroughs 70, 71, any remaining space in the passages 64, 65 can be filled with a ceramic material. Glass frit is one example of a ceramic material that can be used to fill the remaining space and heated sufficiently that the material flows, thereby eliminating any voids in the ceramic material. In the case of metal-filled feedthrough cavities, the pads 66, 67 on the exterior of the package are formed by, e.g., fusion bonding, low pressure plasma spray, laser welding, electroplating or PVD, depending on the choice of metal and the desired material properties. The electrical contact pads 66, 67 provide a site to connect to external electronics.
Suitable non-refractory metals for the electrical feedthroughs include gold, platinum, nickel, and silver and alloys thereof. Suitable refractory metals include niobium, titanium, tungsten, tantalum, molybdenum, chromium, and a platinum/iridium alloy and alloys thereof. If refractory metals are used to construct the feedthroughs, either alternating or direct current may be used to bias the sensors by external electronics. If any other metals are used, the sensors should be biased under AC power to prevent the onset of bias-induced corrosion.
The pressure cavity 52 is hermetic for the following reasons. First, the pressure cavity body 51 is formed of a hermetic material and is a unitary structure, meaning there are no seams or bi-material joints that can form a potential path for gas or fluid intrusion into the pressure chamber other than the passages 64, 65, which themselves are hermetically sealed. One reason for the hermeticity of the passages 64, 65 is that the electrodes 56, 57 are hermetically imposed onto the wall 58 over the feedthroughs. The electrodes 56, 57 (along with any other metallic structure fixed to the ceramic substrate) optionally form an intermetallic compound. An intermetallic compound is formed between a metal and a substrate when chemical reactions take place that result in the formation of covalent bonds between two or more elements, with at least one of the elements coming from the substrate and one from the metal. Optionally, the material 68 filling the passages 64, 65 is itself capable of hermetic sealing such that the interface between the material 68 and the material defining the feedthrough passages is also hermetic. Thus gas or fluid would have to pass through or around the material 68 in the passages 64, 65 and pass through or around the electrodes 56, 57 before it could enter the pressure chamber and compromise its integrity. And finally, the passages 64, 65 are small, thereby minimizing the area of interface and reducing the probability of flaw creation and propagation. In the disclosed embodiments, the passages have cross-sectional areas ranging from 10−6 to 10−9 square meters.
A disclosed method of fabricating the sensor 50 depicted in
The laser cutting operation fuses the substrates, hermetically sealing the sensor and trapping air or any other desirable gas in the hermetic cavity of the sensor, or creating a vacuum within the hermetic cavity of the sensor. In one example, a CO2 laser operating at a peak wavelength of ten microns is used to hermetically seal and to reduce the sensor to its final size. The laser energy is confined to a precise heat effect zone where the substrates are fused, eliminating any material interface between the original substrates.
The resulting hermetic package presents electrical feedthroughs 70, 71 created in the sensor body 51 that allow for communication between components inside the hermetically-sealed sensor 50 and external electrical components. The feedthroughs 70, 71 are small, thereby minimizing the area of interface. Such feedthroughs interface with the substrate at areas ranging from 10−6 to 10−9 square meters.
The manufacturing of the sensor 50 depicted in
The lower substrate is processed to create a recessed region in its surface and thin film electrodes at the bottom surface of each recessed region. Creation of a recessed region with known geometry comprises the steps of (i) depositing and patterning a mask at the surface of the wafer, (ii) etching the wafer material through openings in the mask, and (iii) removal of the mask.
One method for creating the desired recessed region is depicted in
As can be seen in
Referring now to
A glass etchant is now used to etch the portion of the upper surface of the substrate 102 that is exposed through the mask 108. To accomplish this, the substrate 102 is placed in a fixture that prevents the etchant from contacting the un-masked back side of the substrate and is then submerged in a solution containing hydro-fluoric acid, resulting in etching of the masked substrate only where the fused silica is exposed. The substrate 102 is removed from the acid when the substrate has been etched to the desired depth, usually on the order of 1-3 micrometers. The resulting etched substrate 112 with rectangular recessed region 114 is shown in
The etched substrate 112 is now primed for creation of electrodes at the bottom of the recessed region 114. As shown in
Referring now to
Next, the portions of the metal layer 120 exposed through the mask 126 are etched away, as illustrated in
At this point, as depicted in
An optional step involving creation of an intermetallic compound can be performed, e.g., at this step and serves to increase the hermeticity of the metal-substrate interface. An intermetallic compound is created by annealing a metal deposited onto a ceramic substrate at a temperature sufficient to initiate covalent bonding across the substrates. It may be necessary to protect the surface of the metal from oxidation by providing a protective layer to the exposed metal or by performing the annealing step in an inert environment (e.g., vacuum, N2). One example of an intermetallic compound is the Ti—O—Si system, where titanium is deposited onto a SiO2 substrate. The exposed Ti surfaces are protected from oxidation by a layer of silicon nitride. The metal and underlying ceramic substrate are heated at a ramp rate of, e.g., 4-10 degrees C./minute to between substantially 700 and substantially 1100 degrees C. in order to drive the fusion reaction. The temperature is gradually increased and decreased in order to obviate any potential problems with CTE mismatch between the metal and the substrate. If necessary, the protective layer is then removed. In this Ti—O—Si system, either the Ti dissolves significant amounts of oxygen prior to oxide formation enabling the oxygen to react with Si diffusing to the interface, or the stable oxide evolves from TiO to SiO2 in the presence of the Ti-rich phases. Other configurations of metals and substrates can be used to achieve the same effect, e.g., W—Si—O, Mo—Si—O, Ta—Si—O, and Ti—Si—N. To carry out this annealing step, one skilled in the art need only reference the ternary phase diagram to determine sufficient annealing temperatures and to discern the relevant properties of the intermetallic compound.
Referring now to
As an optional preparatory step for the upper substrate 150, a blanket etch can be performed on the back side using hydrofluoric acid or any other suitable etchant to form the recess 54 such that overall thickness of the substrate 150 is reduced to a known thickness that lies in the range of 30-100 micrometers. This step serves to increase sensitivity of the deflectable region of the pressure cavity body 51 (
The substrates 112, 150 are then aligned, subjected to bonding, and reduced to the final overall dimension of the sensor as shown in
With further reference to
At some point, the feedthrough passages 64, 65 are created by removing material on the lower surface of the pressure cavity body 51 to expose the back side of the capacitor electrodes 56, 57, establishing electrical communication through this location as pictured in
It is a further aspect of this invention to provide for a hermetic sensor that incorporates a pressure cavity and additional electrical components that incorporate the above described advantages, with additional functionality and advantages being provided. A sensor according to the invention, along with desirable modifications, is depicted in
Also mounted to the intermediate wall 208 within the lower hermetic chamber 210 is a fourth electrode 224. A fifth electrode 226 is located on the intermediate wall 208 within the upper chamber 212, which is, optionally, hermetic. A sixth electrode 225 is behind and in-plane with the fifth electrode 226 and is thus not visible in
Electrical contact pads 230, 231 are formed on the intermediate wall 208 within the upper hermetic chamber. A first pad 230 is located opposite a portion of the second electrode 216. A second pad 231 is located opposite a portion of the third electrode 217 and is behind and in plane with the first pad 230 and thus not visible in
To provide electrical access to the interior of the sensor, fifth and sixth feedthrough passages 240, 241 are provided. The passage 240 extends from the exterior of the sensor body to the upper chamber 212. The passage 241 also extends from the exterior of the sensor body to the upper chamber 212 but is behind and in plane with the electrical feedthrough 240 and thus not visible in
The upper chamber 212 contains one or more electrical components such as a silicon chip 250 bearing electronics that can act to buffer, to linearize, or otherwise to manipulate the electronic signal from the transducer. The silicon chip 250 is placed in electrical communication with the electrodes and with an external source by way of the conductive pads 230, 231, 242, and 243. In one embodiment (not shown), the electronics comprises an A/D converter placed in series with an additional silicon chip bearing electronics. In this case, an additional set of electrical contact pads are provided that allow electrical communication between the A/D converter and the additional electronics.
The fabrication of the sensor depicted in
Conductive pads 230, 231, 242, and 243 on the top surface of the second substrate can be formed during the feedthrough fabrication sequence. The silicon chip 250 is then connected to the conductive pads 230, 231, 242, and 243 that were formed during the feedthrough fabrication sequence. A third substrate that has a recess sufficiently deep to contain the silicon chip 250 and to make contact to the second substrate is added to the assembly. A laser is then used to remove material around the sensor periphery to reduce the sensor to final dimensions. In the disclosed embodiment, the sensor is 750 micrometers wide by 4-5 mm long and 0.6 mm tall. Passages 240 and 241 are then created to allow for conductive communication with external electronics.
In an alternative example, a piezoresistive transduction scheme can be utilized to measure changes in the position of the deflectable region in the pressure cavity. One or more piezoresistive elements translate mechanical strain into changes in electrical resistance. The piezoresistor is made of, e.g., polysilicon and formed on the interior of the pressure cavity in lieu of the electrodes in previous examples. The resistance modulation is, e.g., detected through a fully active Wheatstone bridge, as is known in the art. Optimally, the Wheatstone bridge configuration used is one where only one leg of the bridge is fixed to the deflectable region of the pressure cavity. This design reduces the number of feedthroughs to two.
One proposed transduction scheme capable of measuring changes in the position of the deflectable region in the pressure cavity is illustrated in
As previously indicated, various capacitor configurations are possible.
A capacitor comprises a single lower electrode 356 located on a first wall 358 of the chamber 352. A second electrode 360 is disposed on an opposite wall 362 of the pressure cavity 352 in parallel, spaced apart relation to the lower electrode 356. The upper electrode 360 is mechanically coupled to the deflectable region 354.
The lower portion of the pressure cavity 352 contains a pair of passages 364, 365 that traverse the hermetic pressure cavity body 351. The first passage 364 is in contact with the lower electrode 356. The second passage 365 is in contact with the upper electrode 360 by way of an electrode in the form of an electrically conductive post 357 disposed within the pressure cavity 352. Electrical contact pads 366, 367 are formed within the passages 364, 365 on the back side of the electrodes 356, 357 and extend to the exterior of the housing 351, thereby providing a region on the exterior of the sensor 350 configured with sufficient dimensions so as to allow for a means for connection with external electronics.
While the invention as been illustrated in the context of a biological device, it will be appreciated that the hermetic chamber herein described can be adapted to non-biological applications, for example, industrial applications in which a harsh environment is encountered.
Specific embodiments have been described herein, by way of example and for clarity of understanding, and variations and modifications to the present invention may be possible given the disclosure above. Hence the scope of the present invention is limited solely by the appended claims.
This application is entitled to the filing dates of provisional U.S. Patent Application Ser. No. 60/651,670, filed Feb. 10, 2005, and provisional U.S. Patent Application Ser. No. 60/653,868, filed Feb. 17, 2005.
Number | Name | Date | Kind |
---|---|---|---|
2796863 | Von Wittern | Jun 1957 | A |
3867950 | Fischell | Feb 1975 | A |
3942382 | Hok | Mar 1976 | A |
3958558 | Dunphy et al. | May 1976 | A |
4026276 | Chubbuck | May 1977 | A |
4127110 | Bullara | Nov 1978 | A |
4206762 | Cosman | Jun 1980 | A |
4207604 | Bell | Jun 1980 | A |
4207903 | O'Neill | Jun 1980 | A |
RE30366 | Rasor | Aug 1980 | E |
4237900 | Schulman et al. | Dec 1980 | A |
4354506 | Sakaguchi et al. | Oct 1982 | A |
4378809 | Cosman | Apr 1983 | A |
4485813 | Anderson et al. | Dec 1984 | A |
4494950 | Fischell | Jan 1985 | A |
4521684 | Gilby et al. | Jun 1985 | A |
4596563 | Pande | Jun 1986 | A |
4617606 | Shak et al. | Oct 1986 | A |
4701826 | Mikkor | Oct 1987 | A |
4713540 | Gibly et al. | Dec 1987 | A |
4718425 | Tanaka et al. | Jan 1988 | A |
4773972 | Mikkor | Sep 1988 | A |
4796641 | Mills et al. | Jan 1989 | A |
4815472 | Wise et al. | Mar 1989 | A |
4846191 | Brockway et al. | Jul 1989 | A |
4890623 | Cook et al. | Jan 1990 | A |
4899752 | Cohen | Feb 1990 | A |
4913147 | Fahlstrom et al. | Apr 1990 | A |
4924172 | Holmgren | May 1990 | A |
4934369 | Maxwell | Jun 1990 | A |
4987897 | Funke | Jan 1991 | A |
5036854 | Schollmeyer et al. | Aug 1991 | A |
5113868 | Wise et al. | May 1992 | A |
5115128 | Cook | May 1992 | A |
5129394 | Mehra | Jul 1992 | A |
5165289 | Tilmans | Nov 1992 | A |
5173836 | Tomase et al. | Dec 1992 | A |
5181423 | Philipps et al. | Jan 1993 | A |
5192314 | Daskalakis | Mar 1993 | A |
5207103 | Wise et al. | May 1993 | A |
5265606 | Kujawski | Nov 1993 | A |
5277068 | Fukiura et al. | Jan 1994 | A |
5353800 | Pohndorf et al. | Oct 1994 | A |
5355714 | Suzuki et al. | Oct 1994 | A |
5373852 | Harrison et al. | Dec 1994 | A |
5400535 | Schomaker | Mar 1995 | A |
5411535 | Fujii et al. | May 1995 | A |
5411551 | Winston et al. | May 1995 | A |
5431171 | Harrison et al. | Jul 1995 | A |
5440300 | Spillman, Jr. | Aug 1995 | A |
5487760 | Villafana | Jan 1996 | A |
5497099 | Walton | Mar 1996 | A |
5515041 | Spillman, Jr. | May 1996 | A |
5535752 | Halperin et al. | Jul 1996 | A |
5538005 | Harrison et al. | Jul 1996 | A |
5551427 | Altman | Sep 1996 | A |
5554139 | Okajima | Sep 1996 | A |
5566676 | Rosenfeldt et al. | Oct 1996 | A |
5593430 | Renger | Jan 1997 | A |
5600245 | Yamamoto et al. | Feb 1997 | A |
5626630 | Markowitz et al. | May 1997 | A |
5686841 | Stolarczyk et al. | Nov 1997 | A |
5695155 | Macdonald et al. | Dec 1997 | A |
5702427 | Ecker et al. | Dec 1997 | A |
5703576 | Spillman, Jr. et al. | Dec 1997 | A |
5713917 | Leonhardt et al. | Feb 1998 | A |
5722414 | Archibald et al. | Mar 1998 | A |
5723791 | Koch et al. | Mar 1998 | A |
5740594 | Lukasiewicz et al. | Apr 1998 | A |
5743267 | Nikolic et al. | Apr 1998 | A |
5750926 | Schulman et al. | May 1998 | A |
5796827 | Coppersmith et al. | Aug 1998 | A |
5807265 | Itoigawa et al. | Sep 1998 | A |
5836886 | Itoigawa et al. | Nov 1998 | A |
5860938 | Lafontaine et al. | Jan 1999 | A |
5899927 | Ecker et al. | May 1999 | A |
5935084 | Southworth | Aug 1999 | A |
5942991 | Gaudreau et al. | Aug 1999 | A |
5967986 | Cimochowski et al. | Oct 1999 | A |
5974894 | Delatorre | Nov 1999 | A |
6015386 | Kensey et al. | Jan 2000 | A |
6015387 | Schwartz et al. | Jan 2000 | A |
6019729 | Itoigawa et al. | Feb 2000 | A |
6024704 | Meador et al. | Feb 2000 | A |
6025725 | Gershenfeld et al. | Feb 2000 | A |
6030413 | Lazarus | Feb 2000 | A |
6033366 | Brockway et al. | Mar 2000 | A |
6053873 | Govari et al. | Apr 2000 | A |
6076016 | Geierbach | Jun 2000 | A |
6111520 | Allen et al. | Aug 2000 | A |
6113553 | Chubbuck | Sep 2000 | A |
6134461 | Say et al. | Oct 2000 | A |
6140740 | Porat et al. | Oct 2000 | A |
6159156 | Van Bockel | Dec 2000 | A |
6198965 | Penner et al. | Mar 2001 | B1 |
6201980 | Darrow et al. | Mar 2001 | B1 |
6206835 | Spillman, Jr. et al. | Mar 2001 | B1 |
6212056 | Gammel et al. | Apr 2001 | B1 |
6237398 | Porat et al. | May 2001 | B1 |
6239724 | Doron et al. | May 2001 | B1 |
6252481 | Iwao et al. | Jun 2001 | B1 |
6277078 | Porat et al. | Aug 2001 | B1 |
6278379 | Allen et al. | Aug 2001 | B1 |
6287253 | Ortega et al. | Sep 2001 | B1 |
6291343 | Tseng et al. | Sep 2001 | B1 |
6338284 | Najafi et al. | Jan 2002 | B1 |
6373264 | Matsumoto et al. | Apr 2002 | B1 |
6383144 | Mooney et al. | May 2002 | B1 |
6409674 | Brockway et al. | Jun 2002 | B1 |
6416474 | Penner et al. | Jul 2002 | B1 |
6442413 | Silver | Aug 2002 | B1 |
6454720 | Clerc et al. | Sep 2002 | B1 |
6645143 | Van Tessel et al. | Nov 2003 | B2 |
6667725 | Simmons et al. | Dec 2003 | B1 |
6678458 | Ellis et al. | Jan 2004 | B2 |
6689056 | Kilcoyne et al. | Feb 2004 | B1 |
6765493 | Lonsdale et al. | Jul 2004 | B2 |
6812404 | Martinez | Nov 2004 | B1 |
6855115 | Fonseca et al. | Feb 2005 | B2 |
6923769 | Nishii et al. | Aug 2005 | B2 |
6926670 | Rich et al. | Aug 2005 | B2 |
6939299 | Petersen et al. | Sep 2005 | B1 |
6989493 | Hipwell et al. | Jan 2006 | B2 |
7119552 | Morimoto et al. | Oct 2006 | B2 |
7147604 | Allen et al. | Dec 2006 | B1 |
20010001311 | Park et al. | May 2001 | A1 |
20020013994 | Ahn | Feb 2002 | A1 |
20020151816 | Rich et al. | Oct 2002 | A1 |
20020170897 | Hall | Nov 2002 | A1 |
20020188207 | Richter | Dec 2002 | A1 |
20030031587 | Hu et al. | Feb 2003 | A1 |
20030125790 | Fastovsky et al. | Jul 2003 | A1 |
20030136417 | Fonseca et al. | Jul 2003 | A1 |
20030139677 | Fonseca et al. | Jul 2003 | A1 |
20030143775 | Brady | Jul 2003 | A1 |
20030219220 | Ellis et al. | Nov 2003 | A1 |
20040059348 | Geske et al. | Mar 2004 | A1 |
20040073137 | Lloyd et al. | Apr 2004 | A1 |
20040077117 | Ding et al. | Apr 2004 | A1 |
20040122494 | Eggers et al. | Jun 2004 | A1 |
20040157367 | Wong et al. | Aug 2004 | A1 |
20040176672 | Silver et al. | Sep 2004 | A1 |
20050075697 | Olson et al. | Apr 2005 | A1 |
20050085703 | Behm | Apr 2005 | A1 |
20050154321 | Wolinsky et al. | Jul 2005 | A1 |
20050187482 | O'Brien et al. | Aug 2005 | A1 |
20050194174 | Hipwell et al. | Sep 2005 | A1 |
20050229710 | O'Dowd et al. | Oct 2005 | A1 |
20060129056 | Leuthardt et al. | Jun 2006 | A1 |
20060174712 | O'Brien et al. | Aug 2006 | A1 |
20060241354 | Allen | Oct 2006 | A1 |
20060283007 | Cros et al. | Dec 2006 | A1 |
20060287602 | O'Brien et al. | Dec 2006 | A1 |
20060287700 | White et al. | Dec 2006 | A1 |
20070107524 | O'Brien et al. | May 2007 | A1 |
20070199385 | O'Brien et al. | Aug 2007 | A1 |
20070261497 | O'Brien et al. | Nov 2007 | A1 |
20080060834 | Eck et al. | Mar 2008 | A1 |
20080060844 | Teske et al. | Mar 2008 | A1 |
Number | Date | Country |
---|---|---|
1158061 | Jun 1983 | CA |
19644858.5 | Oct 1996 | DE |
10052053 | Apr 2002 | DE |
101 35 568 | Feb 2003 | DE |
9006723 | Jun 1990 | EP |
0337035 | Nov 1993 | EP |
0646365 | Apr 1995 | EP |
WO 8303348 | Oct 1983 | WO |
WO 9308871 | May 1993 | WO |
WO 9533517 | Dec 1995 | WO |
WO 9709926 | Mar 1997 | WO |
WO 9732518 | Sep 1997 | WO |
WO 9732519 | Sep 1997 | WO |
WO 9733513 | Sep 1997 | WO |
WO 9847727 | Oct 1998 | WO |
WO 9934731 | Jul 1999 | WO |
WO 0100089 | Jan 2001 | WO |
WO 0187137 | Nov 2001 | WO |
WO 0197908 | Dec 2001 | WO |
WO 0016686 | Mar 2003 | WO |
WO 03061504 | Jul 2003 | WO |
WO 03106952 | Dec 2003 | WO |
WO 2004014456 | Feb 2004 | WO |
WO 04098701 | Nov 2004 | WO |
WO 2005019785 | Mar 2005 | WO |
WO-2005027998 | Mar 2005 | WO |
WO 2007002224 | Jan 2007 | WO |
WO 2007002225 | Jan 2007 | WO |
WO 20007002185 | Jan 2007 | WO |
2007047571 | Apr 2007 | WO |
2007047794 | Apr 2007 | WO |
WO 2006086114 | May 2007 | WO |
WO 2006086113 | Nov 2007 | WO |
Number | Date | Country | |
---|---|---|---|
20060177956 A1 | Aug 2006 | US |
Number | Date | Country | |
---|---|---|---|
60653868 | Feb 2005 | US | |
60651670 | Feb 2005 | US |