Thinning and dicing of semiconductor wafers using dry etch, and obtaining semiconductor chips with rounded bottom edges and corners

Information

  • Patent Grant
  • 6498074
  • Patent Number
    6,498,074
  • Date Filed
    Wednesday, June 6, 2001
    23 years ago
  • Date Issued
    Tuesday, December 24, 2002
    21 years ago
Abstract
A semiconductor wafer is diced before thinning. The wafer is diced only part of the way through, to form grooves which are at least as deep as the final thickness of each chip to be obtained from the wafer. Then the wafer backside is etched with a dry etch, for example, atmospheric pressure plasma etch. The wafer is thinned until the grooves are exposed from the backside. The dry etch leaves the chip's backside smooth. After the grooves have been exposed, the dry etch is continued to remove damage from the chip sidewalls and to round the chips' bottom edges and corners. The grooves' aspect ratio is large to reduce the lateral etch rate of the chip sidewalls and thus allow more area for on-chip circuitry.
Description




BACKGROUND OF THE INVENTION




The present invention relates to thinning and dicing of semiconductor wafers using a dry etch.




In many semiconductor fabrication processes, when circuitry has been fabricated in a semiconductor wafer, the wafer is thinned and then diced into chips. The thinning is typically performed with mechanical lapping. Dicing is performed with a diamond saw or a laser. The diamond saw or the laser can be used to cut the wafer all the way through along scribe lines. Alternatively, the wafer is cut part of the way through, and then broken.




The thinning and dicing processes can damage the wafer. It is desirable to provide alternative processes that reduce wafer damage and prolong the lifetime of chips obtained from the wafer.




SUMMARY




Some embodiments of the present invention reduce or eliminate wafer damage and prolong the chip lifetime by dicing the wafer part of the way through and then thinning the wafer with a dry etch. The chip lifetime is prolonged because the dry etch removes damage from chip surfaces and rounds the chip's edges and corners.




More particularly, as illustrated in

FIG. 1

, a chip


110


obtained by prior art thinning and dicing techniques may have uneven, damaged surfaces


110


B,


110


S, with sharp bottom corners and edges. Surface


110


B is the chip's backside, and surfaces


110


S are sidewalls. The wafer has been thinned from backside


110


B by mechanical lapping, and then diced along sidewalls


110


S with a diamond saw or a laser apparatus. These thinning and dicing processes damage the backside


110


B and sidewalls


110


S. The damage may include chipped, jagged surfaces, and microcracks. When the chip


110


is later packaged and put into use, the chip is subjected to heating and cooling cycles. These cycles cause the chip's packaging material (not shown) to exert stresses on the chip. Additional stresses can be developed inside the chip due to the thermal cycles, chip handling, or the presence of different materials or other non-uniformities inside the chip. Because the chip surfaces


110


B,


110


S are damaged, and because they intersect at sharp edges and corners, the stresses concentrate at isolated points on the chip surface. Further, microcracks weaken the chip's resistance to stress. As a result, the chip becomes less reliable. Cracks formed or extended by stresses in the chip can reach and damage the chip circuitry (not shown).




Dry etch provides smoother chip surfaces and rounded edges and corners. Damage is reduced or eliminated. The chip reliability is therefore improved.




In some embodiments of the present invention, the wafer is processed as follows. The wafer is diced to form grooves in the face side of the wafer. The grooves are at least as deep as the final thickness of each chip to be obtained from the wafer. Dicing can be performed with a diamond saw or a laser. The grooves' sidewalls can be damaged.




Then the wafer backside is etched with the dry etch until the grooves are exposed from the backside. The dry etch leaves the chips' backside smooth. In some embodiments, the dry etch continues after the grooves have been exposed from the backside. The etchant gets into the grooves and smoothens the chip sidewalls, removing at least some of the sidewall damage. The etchant also rounds the bottom corners and edges of the chips.




Suitable etches include atmospheric pressure plasma etches described, for example, in the aforementioned U.S. Pat. No. 6,184,060. These etches are fairly fast. Silicon can be etched at 10 μm/min.




In some embodiments, the dry etch is a blanket uniform etch of the wafer's flat backside surface. No masking layers are used on the backside surface.




The invention is not limited to the embodiments described above. In some embodiments, one or more openings are formed in a first surface of a semiconductor wafer along a boundary of one or more chips. The openings do not go through the wafer. The wafer is thinned with a dry etch until the openings are exposed on a second side.




Other features of the invention are described below. The invention is defined by the appended claims.











BRIEF DESCRIPTION OF THE DRAWINGS





FIG. 1

is a side view of a prior art semiconductor chip.





FIG. 2A

is a top view of a wafer being processed according to an embodiment of the present invention.





FIG. 2B

shows a cross-section of the wafer of

FIG. 2A

along the lines II—II.





FIGS. 3 and 4

are cross-sections illustration of a wafer and processing equipment during wafer thinning according to an embodiment of the present invention.





FIG. 5

is a perspective view of a chip processed according to an embodiment of the present invention.





FIG. 6

is a side view of a packaged chip processed according to an embodiment of the present invention.





FIGS. 7 through 11

are cross-section illustrations of wafers being processed according to embodiments of the present invention.











DESCRIPTION OF SOME EMBODIMENTS





FIG. 2A

is a top view of a semiconductor wafer


210


shown before the wafer is thinned with a dry etch.

FIG. 2B

is a cross sectional view of the wafer along the lines II—II in FIG.


2


A. Circuitry has been fabricated in the wafer, and the wafer must now be divided into chips


110


. The circuitry may include transistors, diodes, and other devices (not shown) manufactured in and over an active layer


220


(

FIG. 2B

) adjacent to the wafer top surface


210


F (the surface shown in FIG.


2


A). Optional conductive bumps


216


have been manufactured on contact pads on top surface


210


F of chips


110


. The bumps will be used to connect the chips to wiring substrates (not shown), e.g., printed circuit boards.




The wafer thickness


240


has been sufficiently large to achieve suitable mechanical strength and heat dissipation during fabrication of the wafer circuitry. 720 μm is suitable for some silicon wafer fabrication processes. The wafer will now to be thinned to its final thickness Hf. In some embodiments, the final thickness is 10-450 μm. These thickness figures are illustrative and not limiting.




After the circuitry and the bumps


216


were manufactured, grooves


260


were formed in the wafer top surface along scribe lines and, in particular, along the boundary of chips


110


. The grooves could be formed by conventional dicing techniques, e.g. with a diamond saw or a laser. Other processes, e.g., a masked etch, could also be used. The grooves do not go through the wafer. The grooves are at least as deep as the final chip thickness Hf. In some embodiments, the groove depth is 10-450 μm. The grooves will be exposed from the bottom during wafer thinning when the wafer back side


110


B is etched, as described below.




The groove sidewall and bottom surfaces


270


can be damaged by dicing, as schematically shown by uneven lines in

FIGS. 2A

,


2


B.




Wafer


210


is placed in a non-contact wafer holder


510


(FIG.


3


). Holder


510


includes one or more vortex chucks


520


having outlets in the holder's surface


524


. Surface


524


faces the top surface of the wafer. Gas supplied under pressure through a conduit


522


enter chucks


520


through respective passages


523


. Each passage is tangential to the chuck's cylindrical chamber when viewed from the top. A gas vortex


525


emitted by each chuck towards the wafer generates a low pressure zone near the chuck's vertical axis. In this zone, the wafer is drawn towards the chuck. At the same time, the gas vortices do not allow the wafer to touch the holder surface


524


. Such wafer holders are described, for example, in U.S. patent application Ser. No. 09/456,135 “Non-Contact Workpiece Holder” filed by O. Siniaguine et al. on Dec. 7, 1999 and incorporated herein by reference. Other suitable holders are described in PCT publication WO 99/46805 (TruSi Technologies, LLC, Sep. 16, 1999) incorporated herein by reference. Other holders, for example, Bernoulli type holders, electrostatic holders, mechanical clamps, or vacuum chucks, can also be used.




Wafer holder


510


is called “non-contact” because the top surface of the wafer does not contact the holder surface


524


. However, the edge of the wafer can contact the holder's limitors


526


which extend around the wafer to restrict the wafer lateral motion. In some embodiments, holder


510


is mounted on a rotating carousel (not shown). The carousel rotation develops a centrifugal force that presses the wafer against one or more limitors


526


. See PCT publication WO 99/26796 (TruSi Technologies, LLC, Jun. 3, 1999).




The wafer backside surface


110


B is etched with a dry etch. In

FIG. 3

, the etch is a blanket (unmasked) uniform etch of the wafer's flat semiconductor backside surface (e.g., silicon surface). The etch is atmospheric pressure plasma etch. Plasma generator


530


generates plasma


540


into which suitable reagents are injected. If the wafer is made of silicon, a CF4 etch can be used. See PCT publication WO 98/19337 (TruSi Technologies, LLC, May 7, 1998) incorporated herein by reference. A suitable etcher is type Tru-Etch 3000 (trademark) available from TruSi Technologies, LLC, of Sunnyvale, Calif. The dry etch thins the wafer until the grooves


260


are exposed from the bottom. When the grooves are exposed, the plasma enters the grooves and etches the groove sidewalls


270


. The sidewalls become smoother as a result. The dicing damage becomes partially or completely removed from the sidewalls. The bottom corners and edges of chips


110


become rounded.




Advantageously, some atmospheric pressure plasma etching processes described in WO 98/19337 are fast. Silicon can be etched at the rate of about 10 μm/min. Other kinds of etches can also be used. The dry etch can be preceded by mechanical lapping of the wafer bottom surface


110


B.




In some embodiments, before the backside etch, the groove depth Hg (

FIG. 2B

) exceeds the final chip thickness by an amount needed to obtain the rounded edges and corners and smooth sidewalls for chips


110


. The more the groove depth exceeds the final chip thickness, the longer the duration of the backside etch after the grooves have been exposed from the bottom. The bottom corners and edges become more rounded, and more time is allowed for sidewall damage removal. In some embodiments, the radius of the rounded corners is roughly 1.5 times the thickness of the material removed from the wafer backside after the grooves are exposed. The depth of the grooves also takes into account possible wafer non-uniformity, the non-uniformity of the dicing process that creates the grooves, and the non-uniformity of the backside etch. If mechanical lapping or any other process is used to remove material from the wafer backside before the dry etch illustrated in

FIG. 5

, the non-uniformity of such processes can also be taken into account. In some embodiments, the groove depth Hg exceeds the final chip thickness Hf by 10 μm or more.




When the grooves


260


become exposed during the thinning etch of

FIG. 3

, chips


110


become separated from each other, but the chips are held in holder


510


by the vacuum forces developed by the gas vortices. The vortex chucks


520


are positioned close to each other to insure that each chip


110


will be adjacent to a low pressure zone developed by at least one chuck


520


. In

FIG. 4

, “L” denotes the greatest lateral dimension of each chip


110


. “P” is the distance between the centers of the adjacent chucks


520


. “D” is the diameter of each chuck. “P” and “D” can vary for different chucks


520


in the same wafer holder. The diameter D of each vortex chuck should be small enough to prevent a chip from being sucked into the chuck. The chip should be balanced at a predetermined distance from the wafer holder surface


524


by the vacuum forces drawing the chip towards the holder and the opposite-direction forces generated between the chucks by the gas flowing away from the chucks. In some embodiments, D<L/2 and P<L/2 for all the chucks.




In some embodiments, each of P and D is less than one half of the shortest side of each rectangular chip


110


.




In some embodiments, the distance between the adjacent chucks and the diameter of each chuck take into account the peripheral wafer portions


320


(FIG.


2


A). Each of P and D is less than one half of the greatest lateral dimension, or of the longest or shortest side, of each portion


320


.





FIG. 5

is a perspective view of a chip


110


after the etch. The chip is shown bottom side up. The chip's sidewalls


110


S and bottom surface


110


B are smooth. The edges


110


E at which the sidewalls


110


S meet with each other and with the bottom surface


110


B are rounded, and so are the bottom corners


110


C. The smooth surfaces and the rounded edges and corners prolong the chip's lifetime and improve the chip's reliability.




In

FIG. 6

, chip


110


has been mounted on a printed circuit board


610


using flip chip technology. Bumps


216


are soldered to the printed circuit board. Encapsulant


620


(suitable plastic) is deposited over the chip for protective purposes. The chip's smooth surfaces and rounded edges and corners prolong the chip's lifetime. Similar advantages are achieved with non-flip-chip packaging.




In

FIG. 7

, the etch uniformity is improved by depositing a layer


310


over grooves


260


and wafer portions adjacent to the grooves. Layer


310


is deposited before the backside etch of the wafer. When chips


110


and peripheral portions


320


become separated during the backside etch, the layer


310


holds the chips and the portions


320


in the same position relative to each other. Therefore, the gaps between the chips


110


and the peripheral portions


320


remain uniform, and hence the chip sidewalls (the sidewalls of grooves


260


) are etched uniformly. If some chips


110


were too close to each other or to peripheral portions


320


, the chips' sidewalls could be etched too slowly, and less damage would be removed than desirable. Other sidewalls, farther from adjacent chips


110


or portions


320


, could be undesirably overetched.




Layer


310


also relaxes the requirements for the distance between adjacent vortex chucks


520


and the diameter of each chuck since the chips


110


and peripheral portions


320


are held in position by layer


310


throughout the backside etch.




Layer


310


can be a sticky material which adheres to the wafer without additional adhesive. Alternatively, adhesives can be used. In some embodiments, layer


310


is polyimide. Polyimide is chosen because it does not react with etchants utilized in some thinning processes (e.g., CF4). The thickness of polyimide layer


310


is 1 μm to 200 μm in some embodiments. Other materials and thicknesses can also be used. In some embodiments, layer


310


is an adhesive tape such as described in U.S. Pat. No. 5,888,883 issued on Mar. 30, 1999 to Sasaki et al.




Layer


310


does not cover the middle portions of chips


110


, including the bumps


216


. The bumps, and any other uneven features of the chip top surface


210


F, are believed to be capable of impeding adhesion of layer


310


to the wafer.




In some embodiments, layer


310


is pre-manufactured as a continuous sheet. Then openings are cut out in layer


310


at the location of the middle portions of chips


110


. Then layer


310


is deposited.




Layer


310


can be deposited using known techniques. In some embodiments, layer


310


is deposited at atmospheric pressure using a roller to remove air bubbles. Alternatively, layer


310


can be laminated on the wafer in vacuum, with or without a roller.




In some embodiments, layer


310


covers peripheral portions


320


. In

FIG. 8

, layer


310


covers the entire wafer. In some embodiments, the top surface of chips


110


is even, bumps


216


are absent.




The invention is not limited to layer


310


covering or exposing any particular features of the wafer.




Layer


310


prevents the plasma from going through the grooves


260


and damaging the circuitry at the top surface of the wafer. Gas emitted by chucks


520


flows down around the wafer as shown at


550


in

FIG. 3

, and impedes the plasma from flowing up around the wafer and reaching the wafer top surface. As indicated in the aforementioned U.S. patent application Ser. No. 09/456,135, the chuck density can be made high at the edge of wafer holder


510


to prevent the plasma from flowing up around the wafer. Gas can be made to flow down at all points around the wafer.




In

FIG. 9

, layer


310


has been deposited by a spin-on or spraying technique. Layer


310


fills grooves


260


. (In contrast, in

FIGS. 7 and 8

, the grooves are not filled.) Layer


310


in

FIG. 9

can be polymer or some other material.





FIG. 10

shows the structure after the backside etch for FIG.


9


. In the embodiment of

FIG. 10

, when layer


310


is exposed from the bottom, layer


310


is etched faster than the wafer substrate. Therefore, the bottom surface of layer


310


is higher than the bottom surface of chips


110


and peripheral portions


320


. The bottom corners and edges of chips


110


have been exposed to the etchant, and have been rounded.





FIG. 11

illustrates an embodiment in which the layer


310


is etched slower than the wafer substrate. This is the case if layer


310


is polyimide, the wafer is a silicon wafer, and the etch is a CF4 plasma etch. Layer


310


is etched slowly, but the microloading effect causes the chips


110


to be etched faster at the bottom edges adjacent to layer


310


. As a result, the bottom edges and corners of chips


110


are rounded.




After the etch of

FIG. 10

or


11


, layer


310


is removed. In some embodiments, polyimide layer


310


is removed by oxygen plasma.




In some embodiments, when the wafer is etched from the bottom and the grooves


260


are exposed, it is desirable to reduce the horizontal etch rate of the grooves' sidewalls


270


. Excessive etching of the sidewalls reduces the area available for the on-chip circuitry. In some embodiments, the lateral (horizontal) etch rate is reduced by controlling the grooves' aspect ratio A


1


=Hg/Wg, where Wg is the width of groove


260


.




When A


1


is high, the sidewall etch rate is reduced while the vertical etch rate at the bottom of the wafer remains the same. A high vertical etch rate is desirable because it reduces the dicing time and also reduces the time needed to remove jagged edges protruding from the grooves' sidewalls. In some embodiments in which Wg is measured at the top of the wafer, the aspect ratio A


1


is chosen to be at least 0.5, or at least 1, or at least 1.2, or at least 2, or at least 3, or at least 4, or at least 5, or at least some other number.




In an exemplary embodiment, the wafer is diced with a saw, and the groove width Wg is 25 to 30 μm (depending on the saw). In another embodiment, the wafer is diced with a laser apparatus, and the groove width Wg is about 100 μm. In still another embodiment, the wafer is diced with a dry etch (for example, RIE), and the groove width is 5 μm. The groove width Wg is measured at the top of the wafer. (If the wafer is diced with a dry etch, the groove sidewalls are not necessarily vertical, and the groove width may vary with depth.) The wafer is diced while being attached to tape


310


(

FIGS. 7

,


8


). In these exemplary embodiments, the final wafer thickness Hf is 100 μm, and the groove depth Hg is slightly higher, for example, 110 μm. These values are exemplary and not limiting. Other values are used in other embodiments. For example, Hg can be 30 μm or some other value.




In some embodiments, a lower bound is placed on the parameter A


2


=Hf/Wf where Wf is the final distance between the chips


110


(FIG.


8


). Wf can be measured at the top of the chips. A


2


represents the aspect ratio at the end of the backside etch. Lower bounds can also be placed on parameters A


3


=Hg/Wf, A


4


=Hf/Wg. Appropriate bound values for A


2


, A


3


, A


4


include 0.5, 1, 1.2, 2, 3, 4, 5, or other values.




The invention is not limited by any particular mathematical formula for defining a lower bound for A


1


, A


2


, A


3


, or A


4


. For example, defining a lower bound for Hf/Wf has the same effect as defining an upper bound for Wf/Hf. Also, Hg≧Hf, so if Hg/Wg≧LB (some lower bound), then Hf/Wg≧LB. Other mathematical dependencies can also be explored to define a limitation on the horizontal etch rate of the grooves' sidewalls.




The invention is not limited to isotropic backside etches. In some embodiments, an anisotropic etch is used, e.g., vacuum plasma RIE (reactive ion etching). The etchant's ions are reflected from tape


310


which is made, for example, from an organic compound resistant to the echant. These reflected ions hit the grooves' sidewalls, so the sidewalls are etched horizontally. A high aspect ratio of the grooves retards horizontal etching.




In some embodiments, each of the parameters Hg, Wg, Hf, Wf has the same value throughout the wafer, but the invention is not limited to such embodiments. For example, different grooves may have different widths Wg in the same wafer.




In some embodiments, the grooves between adjacent chips


110


have the same depth and width as the grooves separating the chips


110


from the peripheral portions


320


, but this is not necessary.




The above embodiments illustrate but do not limit the invention. The invention is not limited to silicon wafers or any packaging technology. The invention is not limited to plasma etching, or to any particular etch chemistry or type of etcher. In some embodiments, the lateral etch rate at the groove sidewalls is reduced by a suitable choice of etching parameters. For example, in a vacuum plasma etch, the wafer can be held at a suitable potential to steer ions vertically towards the wafer and not laterally. Such potential may be tens or hundreds of volts, for example. The invention is not limited to wafers containing multiple chips. In some embodiments, only one chip has been fabricated in the wafer. The chip is extracted and the wafer peripheral portions


320


are discarded. The invention is not limited to unmasked or uniform backside etches. Other embodiments and variations are within the scope of the invention, as defined by the appended claims.



Claims
  • 1. A method for obtaining one or more chips from a semiconductor wafer, the method comprising:forming an opening in a first surface of the semiconductor wafer on a boundary of the one or more chips, the first surface being on a first side of the semiconductor wafer, wherein the opening does not go through the wafer; and thinning the wafer with a dry etch to remove material from an entire second side of the wafer at least until the opening becomes exposed on the second side, wherein the dry etch rounds one or more of the edges and/or corners obtained on the second side of the wafer at a location of the opening when the opening becomes exposed.
  • 2. The method of claim 1 wherein at least a portion of the opening is elongated and for at least said portion, a ratio H1/W1≧0.5, wherein H1 is a depth of the opening at said portion, the depth being measured before the opening is exposed on the second side, and W1 is a width of the opening at said portion, the width being measured at the first surface.
  • 3. The method of claim 2 wherein W1 is at most 100 μm.
  • 4. The method of claim 2 wherein W1 is at most 30 μm.
  • 5. The method of claim 2 wherein W1 is at most 5 μm.
  • 6. The method of claim 2 wherein the opening extends along an entire boundary of at least one chip.
  • 7. The method of claim 1 wherein at least a portion of the opening is elongated, and for at least said portion, a ratio H2/W1≧0.5, wherein H2 is a final thickness of the wafer and W1 is a width of the opening at said portion, the width being measured at the first surface.
  • 8. The method of claim 7 wherein W1 is at most 100 μm.
  • 9. The method of claim 7 wherein W1 is at most 30 μm.
  • 10. The method of claim 7 wherein W1 is at most 5 μm.
  • 11. The method of claim 7 wherein the opening extends along an entire boundary of at least one chip.
  • 12. The method of claim 1 wherein at least a portion of the opening is elongated, and for at least said portion, a ratio H1/W2≧0.5, wherein H1 is a depth of the opening at said portion, the depth being measured before the opening is exposed on the second side, and W2 is a minimal distance between a chip obtained from the wafer and an adjacent portion of the wafer at an end of the dry etch.
  • 13. The method of claim 12 wherein the opening extends along an entire boundary of at least one chip.
  • 14. The method of claim 1 wherein a ratio H2/W2≧0.5, wherein H2 is a final thickness of the wafer and W2 is a minimal distance between a chip obtained from the wafer and an adjacent portion of the wafer at an end of the dry etch.
  • 15. The method of claim 14 wherein the opening extends along an entire boundary of at least one chip.
  • 16. The method of claim 1 wherein the semiconductor wafer comprises circuitry made at the first side of the wafer, the second side is a backside opposite to the first side, and the opening runs along a scribe line on the first side.
  • 17. The method of claim 15 wherein the opening extends along an entire boundary of at least one chip.
CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a continuation in part of U.S. patent application Ser. No. 09/752,802, filed Dec. 28, 2000, which is a division of U.S. patent application Ser. No. 09/491,456, filed Jan. 26, 2000, which is a continuation in part of U.S. patent application Ser. No. 09/083,927 filed May 22, 1998, now U.S. Pat. No. 6,184,060, incorporated herein by reference, which is a continuation of PCT application PCT/US97/18979 (WO 98/19337), having an international filing date of Oct. 27, 1997, incorporated herein by reference, which claims priority of U.S. provisional application No. 60/030,425 filed Oct. 29, 1996, incorporated herein by reference.

US Referenced Citations (76)
Number Name Date Kind
3739463 Aird et al. Jun 1973 A
3761782 Youmans Sep 1973 A
3810129 Behman et al. May 1974 A
3811117 Anderson, Jr. et al. May 1974 A
3838501 Umbaugh Oct 1974 A
3881884 Cook et al. May 1975 A
3991296 Kojima et al. Nov 1976 A
3993917 Kalter Nov 1976 A
4139401 McWilliams et al. Feb 1979 A
4141135 Henry et al. Feb 1979 A
4368106 Anthony Jan 1983 A
4394712 Anthony Jul 1983 A
4463336 Black et al. Jul 1984 A
4467518 Bansal et al. Aug 1984 A
4603341 Bertin et al. Jul 1986 A
4612083 Yasumoto et al. Sep 1986 A
4628174 Anthony Dec 1986 A
4722130 Kimura et al. Feb 1988 A
4729971 Coleman Mar 1988 A
4769738 Nakamura et al. Sep 1988 A
4807021 Okumura Feb 1989 A
4822755 Hawkins et al. Apr 1989 A
4842699 Hua et al. Jun 1989 A
4897708 Clements Jan 1990 A
4978639 Hua et al. Dec 1990 A
4996587 Hinrichsmeyer et al. Feb 1991 A
5024970 Mori Jun 1991 A
5160987 Pricer et al. Nov 1992 A
5191405 Tomita et al. Mar 1993 A
5229647 Gnadinger Jul 1993 A
5259924 Mathews et al. Nov 1993 A
5268326 Lesk et al. Dec 1993 A
5270261 Bertin et al. Dec 1993 A
5307942 Quelfeter et al. May 1994 A
5309318 Beilstein, Jr. et al. May 1994 A
5313097 Haj-Ali-Ahmadi et al. May 1994 A
5314844 Imamura May 1994 A
5414637 Bertin et al. May 1995 A
5426566 Beilstein, Jr. et al. Jun 1995 A
5466634 Beilstein, Jr. et al. Nov 1995 A
5467305 Bertin et al. Nov 1995 A
5468663 Bertin et al. Nov 1995 A
5478781 Bertin et al. Dec 1995 A
5502333 Bertin et al. Mar 1996 A
5502667 Bertin et al. Mar 1996 A
5506753 Bertin et al. Apr 1996 A
5517057 Beilstein, Jr. et al. May 1996 A
5517754 Beilstein, Jr. et al. May 1996 A
5532519 Bertin et al. Jul 1996 A
5561622 Bertin et al. Oct 1996 A
5563086 Bertin et al. Oct 1996 A
5567653 Bertin et al. Oct 1996 A
5567654 Beilstein, Jr. et al. Oct 1996 A
5571754 Bertin et al. Nov 1996 A
5596226 Beilstein, Jr. et al. Jan 1997 A
5646067 Gaul Jul 1997 A
5656553 Leas et al. Aug 1997 A
5691248 Cronin et al. Nov 1997 A
5707485 Rolfson et al. Jan 1998 A
5824595 Igel et al. Oct 1998 A
5843844 Miyanaga Dec 1998 A
5846879 Winnerl et al. Dec 1998 A
5851845 Wood et al. Dec 1998 A
5858256 Minne et al. Jan 1999 A
5888882 Igel et al. Mar 1999 A
5888883 Sasaki et al. Mar 1999 A
5979475 Satoh et al. Nov 1999 A
5998292 Black et al. Dec 1999 A
6004867 Kim et al. Dec 1999 A
6036872 Wood et al. Mar 2000 A
6083811 Riding et al. Jul 2000 A
6121119 Richards et al. Sep 2000 A
6162701 Usami et al. Dec 2000 A
6176966 Tsujimoto et al. Jan 2001 B1
6184060 Siniaguine Feb 2001 B1
9752802 Siniaguine et al. May 2001
Foreign Referenced Citations (10)
Number Date Country
19707887 Sep 1998 DE
0 807964 Apr 1995 EP
0 698 288 Feb 1996 EP
0 757431 Jul 1996 EP
WO 9203848 Mar 1992 WO
WO 9409513 Apr 1994 WO
WO 9425981 Nov 1994 WO
WO 9621943 Jul 1996 WO
WO 9745856 Dec 1997 WO
WO 9745862 Dec 1997 WO
Provisional Applications (1)
Number Date Country
60/030425 Oct 1996 US
Continuations (1)
Number Date Country
Parent PCT/US97/18979 Oct 1997 US
Child 09/083927 US
Continuation in Parts (2)
Number Date Country
Parent 09/752802 Dec 2000 US
Child 09/876888 US
Parent 09/083927 May 1998 US
Child 09/491456 US