Printhead having a thin film membrane with a floating section

Information

  • Patent Grant
  • 6626523
  • Patent Number
    6,626,523
  • Date Filed
    Wednesday, October 31, 2001
    23 years ago
  • Date Issued
    Tuesday, September 30, 2003
    21 years ago
Abstract
A printhead including a printhead substrate having at least one opening formed in a first surface to provide a fluid path through the substrate. The printhead further includes a thin film membrane formed on a second surface of the substrate. The thin film membrane includes a plurality of fluid ejection elements and has a floating section and a cantilevered section, which are detached and separated from one another by a gap.
Description




FIELD OF THE INVENTION




Embodiments of the present invention relate to printers and, more particularly to a printhead for a printer.




BACKGROUND OF THE INVENTION




Printers typically have a printhead mounted on a carriage that scans back and forth across the width of a sheet of paper, as the paper is fed through the printer. Fluid from a fluid reservoir, either on-board the carriage or external to the carriage, is fed to fluid ejection chambers on the printhead. Each fluid ejection chamber contains a fluid ejection element, such as a heater resistor or a piezoelectric element, which is independently addressable. Energizing a fluid ejection element causes a droplet of fluid to be ejected through a nozzle to create a small dot on the paper. The pattern of dots created forms an image or text.




Hewlett-Packard is developing printheads that are formed using integrated circuit techniques. A thin film membrane, composed of various thin film layers, including a resistive layer, is formed on a top surface of a silicon substrate, and an orifice layer is formed on top of the thin film membrane. The various thin film layers of the thin film membrane are etched to provide conductive leads to fluid ejection elements, which may be heater resistor or piezoelectric elements. Fluid feed holes are also formed in the thin film layers. The fluid feed holes control the flow of fluid to the fluid ejection elements. The fluid flows from the fluid reservoir, across a bottom surface of the silicon substrate, into a trench formed in the silicon substrate, through the fluid feed holes, and into fluid ejection chambers where the fluid ejection elements are located.




The trench is etched in the bottom surface of the silicon substrate so that fluid can flow into the trench and into each fluid ejection chamber through the fluid feed holes formed in the thin film membrane. The trench completely etches away portions of the substrate near the fluid feed holes, so that the thin film membrane forms a shelf in the vicinity of the fluid feed holes.




One problem faced during development of these printheads is that the thin film membrane and the orifice layer form a composite, which when subjected to stress can crack. When the composite is placed under stress, the thin film membrane, which is the stiffer of the two components, bears the majority of the stress. Thus, when the printhead is flexed or otherwise stressed, either during assembly or operation, the thin film membrane, particularly, in the shelf portion which overlies the trench, can crack. Cracking in the thin film membrane causes reliability problems with these printheads. The problem of flexure and stresses is exacerbated in longer printheads, which typically have larger trenches.




SUMMARY




Described herein is a printhead having a printhead substrate and a thin film membrane. The printhead substrate has at least one opening formed in a first surface to provide a fluid path through the substrate. The thin film membrane is formed on a second surface of the substrate and includes a plurality of fluid ejection elements. The thin film membrane has a floating and cantilevered section, which are detached and separated from each other by a gap formed in the thin film membrane. The floating section is located over the opening of the substrate, while the cantilevered section is substantially supported by the substrate.











BRIEF DESCRIPTION OF THE DRAWINGS




Embodiments of the present invention may be better understood, and its features and advantages made apparent to those skilled in the art, by referencing the accompanying drawings, wherein like reference numerals are used for like parts in the various drawings.





FIG. 1

is a perspective view of one embodiment of a print cartridge that may incorporate the printhead described herein.





FIG. 2

is a perspective cutaway view, taken generally along line


2





2


in

FIG. 1

, of a portion of a printhead.





FIG. 3

is a perspective view of the underside of the printhead shown in FIG.


2


.





FIG. 4

is a cross-sectional view taken generally along line


4





4


in FIG.


3


.





FIG. 5

is a top-down view of the printhead of

FIG. 2

with a transparent orifice layer.





FIGS. 6A-6C

are cross sectional views of one embodiment of the printhead during various stages of a manufacturing process for securing the thin film membrane of the printhead to the orifice layer.





FIG. 7

is a cross-sectional view of an embodiment of a printhead without fluid feed holes.





FIG. 8

is a perspective view of a conventional printer, into which the various embodiments of printheads may be installed for printing on a medium.











DETAILED DESCRIPTION





FIG. 1

is a perspective view of one type of print cartridge


10


that may incorporate the printhead structure of the present invention. Print cartridge


10


is of the type that contains a substantial quantity of fluid within its body


12


, but another suitable print cartridge may be the type that receives fluid from an external fluid supply either mounted on the printhead or connected to the printhead via a tube.




The fluid is supplied to a printhead


14


. Printhead


14


, to be described in detail later, channels the fluid into fluid ejection chambers, each chamber containing a fluid ejection element. Electrical signals are provided to contacts


16


to individually energize the fluid ejection elements to eject a droplet of fluid through an associated nozzle


18


. The structure and operation of conventional print cartridges are very well known.




Embodiments of the present invention relate to the printhead portion of a print cartridge, or a printhead that can be permanently installed in a printer, and, thus, is independent of the fluid delivery system that provides fluid to the printhead. The invention is also independent of the particular printer, into which the printhead is incorporated.





FIG. 2

is a cross-sectional view of a portion of the printhead of

FIG. 1

taken generally along line


2





2


in FIG.


1


. Although a printhead may have 300 or more nozzles and associated fluid ejection chambers, detail of only a single fluid ejection chamber need be described in order to understand the invention. It should also be understood by those skilled in the art that many printheads are formed on a single silicon wafer and then separated from one another using conventional techniques.




In

FIG. 2

, a silicon substrate


20


has an opening or trench


22


formed in a bottom surface thereof. Trench


22


provides a path for fluid to flow along the bottom surface and through substrate


20


.




Formed on top of silicon substrate


20


is a thin film membrane


24


. Thin film membrane


24


is composed of various thin film layers, to be described in detail later. The thin film layers include a resistive layer for forming fluid ejection elements or resistors


26


. Other thin film layers perform various functions, such as providing electrical insulation from substrate


20


, providing a thermally conductive path from the heater resistor elements to substrate


20


, and providing electrical conductors to the resistor elements. One electrical conductor


28


is shown leading to one end of a resistor


26


. A similar conductor leads to the other end of resistor


26


. In an actual embodiment, the resistors and conductors in a chamber would be obscured by overlying layers.




Thin film membrane


24


includes fluid feed holes


30


that are formed completely through thin film membrane


24


. In addition, thin film membrane


24


is divided into a cantilevered section


32


and a floating section


34


. Cantilevered section


32


is substantially supported by substrate


20


, while floating section


34


is suspended over trench


22


formed in substrate


20


. Floating section


34


is separated on all sides from cantilevered section


32


by a gap


36


formed in thin film membrane


24


. Each gap


36


has a width of approximately 0.1 microns. One of ordinary skill in the art will appreciate that the width of gaps


36


may be optimized to control the flow of fluid through printhead


14


. The advantages of dividing thin film membrane


24


into cantilevered and floating sections


32


and


34


, respectively, is described in greater detail below.




In another embodiment, floating section


34


is not separated on all sides from the remainder of the thin film layers but is only separated on one or both long sides to relieve stress.




An orifice layer


38


is deposited over the surface of thin film membrane


24


. Orifice layer


38


is adhered to the top surface of thin film membrane


24


, such that the two form a composite. The adhesion between thin film membrane


24


and orifice layer


38


is sufficient for orifice layer


38


to suspend floating section


34


of thin film membrane


24


over trench


22


in substrate


20


, however, additional structures, as described below, may be used to further secure the two together.




Orifice layer


38


is etched to form fluid ejection chambers


40


, one chamber per resistor


26


. A manifold


42


is also formed in orifice layer


38


for providing a common fluid channel for a row of fluid ejection chambers


40


. The inside edge of manifold


42


is shown by a dashed line


44


. Nozzles


46


may be formed by laser ablation using a mask and conventional photolithography techniques.




Trench


22


in silicon substrate


20


extends along the length of the row of fluid feed holes


30


so that fluid


48


from a fluid reservoir may enter fluid feed holes


30


and supply fluid to fluid ejection chambers


40


.




In one embodiment, each printhead is approximately one-half inch long and contains two offset rows of nozzles, each row containing 150 nozzles for a total of 300 nozzles per printhead. The printhead can thus print at a single pass resolution of 600 dots per inch (dpi) along the direction of the nozzle rows or print at a greater resolution in multiple passes. Greater resolutions may also be printed along the scan direction of the printhead. Resolutions of 1200 dpi or greater may be obtained using the present invention.




In operation, an electrical signal is provided to heater resistor


26


, which vaporizes a portion of the fluid to form a bubble within a fluid ejection chamber


40


. The bubble propels a fluid droplet through an associated nozzle


46


onto a medium. The fluid ejection chamber is then refilled by capillary action.





FIG. 3

is a perspective view of the underside of the printhead of

FIG. 2

showing trench


22


in substrate


20


, gaps


36


separating floating section


34


of thin film membrane


24


from cantilevered section


32


, and fluid feed holes


30


in floating section


34


. In the particular embodiment of

FIG. 3

, a single trench


22


provides access to two rows of fluid feed holes


30


. Trench


22


also provides access to gaps


36


such that fluid may flow through gaps


36


and into fluid ejection chambers


40


. Floating section


34


, which is suspended over trench


22


, preferably has dimensions smaller than that those of trench


22


.




In one embodiment, the size of each fluid feed hole


30


is smaller than the size of a nozzle


46


, so that particles in the fluid will be filtered by fluid feed holes


30


and will not clog nozzle


46


. The clogging of a fluid feed hole will have little effect on the refill speed of a chamber, since there are multiple fluid feed holes supplying fluid to each chamber


40


. In another embodiment, there are more fluid feed holes


30


than fluid ejection chambers


40


.





FIG. 4

is a cross-sectional view taken generally along line


4





4


in FIG.


2


.

FIG. 4

shows the individual thin film layers which comprise thin film membrane


24


. In the particular embodiment of

FIG. 4

, the portion of silicon substrate


20


shown is approximately 30 microns thick. This portion is referred to as the bridge. The bulk silicon is approximately 675 microns thick.




A field oxide layer


50


, having a thickness of 1.2 microns, is formed over silicon substrate


20


using conventional techniques. A tetraethyl orthosilicate (TEOS) layer


52


, having a thickness of 1.0 microns, is then applied over the layer of oxide


50


. A boron TEOS (BTEOS) layer may be used instead.




A resistive layer of, for example, tantalum aluminum (TaAl), having a thickness of 0.1 microns, is then formed over TEOS layer


52


. Other known resistive layers can also be used.




A patterned metal layer, such as an aluminum-copper alloy, having a thickness of 0.5 microns, overlies the resistive layer for providing an electrical connection to the resistors. The conductive AlCu traces are etched to reveal portions of the TaAl layer to define a first resistor dimension (e.g., a width). A second resistor dimension (e.g., a length) is defined by etching the AlCu layer to cause a resistive portion to be contacted by AlCu traces at two ends. This technique of forming resistors


26


and electrical conductors is well known in the art.




TEOS layer


52


and field oxide layer


50


provide electrical insulation between resistors


26


and substrate


20


, as well as an etch stop when etching substrate


20


. In addition, TEOS layer


52


and field oxide layer


50


provide a mechanical support for an overhang portion


54


of cantilevered section


32


and for floating section


34


. The TEOS and field oxide layers also insulate polysilicon gates of transistors (not shown) used to couple energization signals to the resistors


26


.




Referring back to

FIG. 4

, over the resistors


26


and AlCu metal layer is formed a silicon nitride (Si


3


N


4


) layer


56


, having a thickness of 0.25 microns. This layer provides insulation and passivation. Prior to nitride layer


56


being deposited, the resistive and patterned metal layers are etched to pull back both layers from fluid feed holes


30


so as not to be in contact with any fluid. This is because the resistive and patterned metal layers are vulnerable to certain fluids and the etchant used to form trench


22


. Etching back a layer to protect the layer from fluid may also apply to the polysilicon layer in the printhead.




Over the nitride layer


56


is formed a layer


58


of silicon carbide (SiC), having a thickness of 0.125 microns, to provide additional insulation and passivation. Other dielectric layers may be used instead of nitride and carbide.




Carbide layer


58


and nitride layer


56


are also etched to expose portions of the AlCu traces for contact to subsequently formed ground lines (out of the field of FIG.


4


).




On top of carbide layer


58


is formed an adhesive layer


60


of tantalum (Ta), having a thickness of 0.3 microns. The tantalum also functions as a bubble cavitation barrier over the resistor elements. This layer


60


contacts the AlCu conductive traces through the openings in the nitride/carbide layers.




Gold (not shown) is deposited over tantalum layer


60


and etched to form ground lines electrically connected to certain ones of the AlCu traces. Such conductors may be conventional.




The AlCu and gold conductors may be coupled to transistors formed on the substrate surface. Such transistors are described in U.S. Pat. No. 5,648,806, assigned to the present assignee and incorporated herein by reference. The conductors may terminate at electrodes along edges of substrate


20


.




A flexible circuit (not shown) has conductors, which are bonded to the electrodes on substrate


20


and which terminate in contact pads


16


(

FIG. 1

) for electrical connection to the printer.




Fluid feed holes


30


and gaps


36


are formed by etching through the layers that form thin film membrane


24


. In one embodiment, a single feed hole and gap mask is used. In another embodiment, several masking and etching steps are used as the various thin film layers are formed.




Orifice layer


38


is then deposited and formed, followed by the etching of the trench


22


. In another embodiment, the trench etch is conducted before the orifice layer fabrication. Orifice layer


38


may be formed of a spun-on epoxy called SU-8. Orifice layer


38


in one embodiment is approximately 30 microns.




A backside metal may be deposited, if necessary, to better conduct heat from substrate


20


to the fluid.





FIG. 5

is a top-down view of the structure of FIG.


2


. The dimensions of the elements may be as follows: fluid feed holes


30


are 10 microns×20 microns; fluid ejection chambers


40


are 25 microns×25 microns; nozzles


46


have a diameter of 16 microns; heater resistors


26


are 20 microns×20 microns; and manifold


42


has a width of approximately 20 microns. The dimensions will vary depending on the fluid used, operating temperature, printing speed, desired resolution, and other factors.




The present invention provides a printhead with improved reliability. Since the composite formed by thin film membrane


24


and orifice layer


38


is not continuous throughout, due to gaps


36


in thin film membrane


24


, it is less sensitive to the loads imposed by flexure of printhead


14


. When flexure occurs, gaps


36


stop the propagation of stress through thin film membrane


24


and allow the lower modulus SU-8 material of orifice layer to bear the imposed load. Thus, by isolating floating section


34


of thin film membrane


24


from loads created by flexure of the die, the thin film membrane can remain over trench


22


in substrate, thereby taking advantage of the smaller features and tighter tolerances offered by integrated circuit techniques. Adjusting the width of gaps


36


also provides a way to control fluid refill other than through barrier architecture or through shelf length. In addition, the present invention requires no additional process steps, as gaps


36


may be formed simultaneously with fluid feed holes


30


. Finally, the present invention enables the use of the thin film membrane in larger printheads that have a greater potential for flexure.




As discussed above, adhesion between the top layer of thin film membrane


24


and orifice layer


38


enables orifice layer


38


to suspend floating section


34


of thin film membrane


24


over trench


22


in substrate


20


. Orifice layer


38


may also be further secured to thin film membrane


24


.

FIGS. 6A-6C

illustrate a method of forming rivet-like structures to secure orifice layer


38


to thin film membrane


24


. These structures may be formed, as needed, in floating section


34


of thin film membrane


24


. In

FIG. 6A

, thin film membrane


24


is etched to form one or more openings


62


at desired locations for the rivets. Thin film membrane


24


is then used as a mask, and silicon substrate


20


is exposed to an anisotrophic etchant, such as TMAH. The etchant attacks the exposed silicon and undercuts the thin film membrane, as illustrated in FIG.


6


B. Next, SU-8, the epoxy which forms orifice layer


38


, is spun on. The epoxy material flows into the cavity created by the etchant, as illustrated in FIG.


6


C. The SU-8 is then exposed and baked to cure, and the rivet is complete.





FIG. 7

is a cross-sectional view of an embodiment of the invention without fluid feed holes. The layers of thin film membrane


24


are similar to those in FIG.


4


. Unlike

FIG. 4

, there is no fluid feed hole


30


. Rather, fluid flows through gaps


36


.





FIG. 8

illustrates one embodiment of a printer


70


that can incorporate various embodiments of printheads. Numerous other designs of printers may also be used. More detail of a printer is found in U.S. Pat. No. 5,582,459, to Norman Pawlowski et al., incorporated herein by reference.




Printer


70


includes an input tray


72


containing sheets of paper


74


, which are forwarded through a print zone


76


using rollers


78


for being printed upon. Paper


74


is then forwarded to an output tray


80


. A moveable carriage


82


holds print cartridges


82


,


84


,


86


and


99


, which respectively print cyan (C), black (K), magenta (M), and yellow (Y) fluid.




In one embodiment, fluids in replaceable fluid cartridges


92


are supplied to their associated print cartridges via flexible fluid tubes


94


. The print cartridges may also be the type that hold a substantial supply of fluid and may be refillable or non-refillable. In another embodiment, the fluid supplies are separate from the printhead portions and are removably mounted on the printheads in carriage


82


.




Carriage


82


is moved along a scan axis by a conventional belt and pulley system and slides along a slide rod


96


. In another embodiment, the carriage is stationary, and an array of stationary print cartridges print on a moving sheet of paper.




Printing signals from a conventional external computer (e.g., a PC) are processed by printer


70


to generate a bitmap of the dots to be printed. The bitmap is then converted into firing signals for the printheads. The position of the carriage


82


as it traverses back and forth along the scan axis while printing is determined from an optical encoder strip


98


, detected by a photoelectric element on carriage


82


, to cause the various fluid ejection elements on each print cartridge to be selectively fired at the appropriate time during a carriage scan.




The printhead may use resistive, piezoelectric, or other types of fluid ejection elements.




As the print cartridges in carriage


82


scan across a sheet of paper, the swaths printed by the print cartridges overlap. After one or more scans, the sheet of paper


74


is shifted in a direction towards output tray


80


, and carriage


82


resumes scanning.




The present invention is equally applicable to alternative printing systems (not shown) that utilize alternative media and/or printhead moving mechanisms, such as those incorporating grit wheel, roll feed, or drum or vacuum belt technology to support and move the print media relative to the printhead assemblies. With a grit wheel design, a grit wheel and pinch roller move the media back and forth along one axis while a carriage carrying one or more printhead assemblies scan past the media along an orthogonal axis. With a drum printer design, the media is mounted to a rotating drum that is rotated along one axis while a carriage carrying one or more printhead assemblies scans past the medial along an orthogonal axis. In either the drum or grit wheel designs, the scanning is typically not done in a back and forth manner as is the case for the system depicted in FIG.


8


.




Multiple printheads may be formed on a single substrate. Further, an array of printheads may extend across the entire width of a page so that no scanning of the printheads is needed; only the paper is shifted perpendicular to the array.




Additional print cartridges in the carriage may include other colors or fixers.




While particular embodiments of the present invention have been shown and described, it will be obvious to those skilled in the art that changes and modifications may be made without departing from this invention in its broader aspects and, therefore, the appended claims are to encompass within their scope all such changes and modifications as fall within the true spirit and scope of this invention.



Claims
  • 1. A printhead comprising:a printhead substrate having at least one opening formed in a first substrate, the at least one opening providing a fluid path through the substrate; and a thin film membrane formed on a second surface of the substrate, the thin film membrane including a plurality of fluid ejection elements, the thin film membrane having a cantilevered section and a floating section, the floating section being at least partially detached from the cantilevered section and separated by an elongated gap formed in the thin film membrane, the floating section being located over the at least one opening in the substrate, the cantilevered section being substantially supported by the substrate.
  • 2. The printhead of claim 1, wherein the gap separating the cantilevered and floating sections of the thin film membrane is in fluid communication with the fluid path.
  • 3. The printhead of claim 1, wherein the floating section of the thin film membrane has a plurality of fluid feed holes formed therein, the fluid feed holes being in fluid communication with the fluid path.
  • 4. The printhead of claim 1, wherein the floating section of the thin film membrane is substantially rectangular in shape.
  • 5. The printhead of claim 1, wherein a portion of the cantilevered section of the thin film membrane extends over the at least one opening in the substrate.
  • 6. The printhead of claim 1, wherein each of the fluid ejection elements overlies the substrate.
  • 7. The printhead of claim 1, further comprising a printer supporting the printhead.
  • 8. The printhead of claim 1, wherein the floating section of the thin film membrane comprises a field oxide layer and a protective layer, the protective layer overlying the field oxide layer.
  • 9. The printhead of claim 8, wherein the at least one opening in the substrate forms a trench, and wherein the field oxide layer acts as an etch stop when etching the trench.
  • 10. The printhead of claim 1, further comprising an orifice layer formed on the thin film membrane, the orifice layer supporting the floating section over the at least one opening in the substrate.
  • 11. The printhead of claim 10, wherein the orifice layer is mechanically coupled to the floating section of the thin film membrane.
  • 12. The printhead of claim 10, wherein the orifice layer defines a plurality of fluid ejection chambers, each chamber housing an associated fluid ejection element, the orifice layer further defining a nozzle for each fluid ejection chamber.
  • 13. A fluid ejector comprising:a substrate having at least one opening formed in a first substrate, the at least one opening providing a fluid path through the substrate; and a thin film membrane formed on a second surface of the substrate, the thin film membrane including a plurality of fluid ejection elements, the thin film membrane having a cantilevered section and a floating section, the floating section being at least partially detached from the cantilevered section and separated by an elongated gap formed in the thin film membrane, the floating section being located over the at least one opening in the substrate, the cantilevered section being substantially supported by the substrate.
  • 14. A printhead comprising:a printhead substrate having at least one opening formed in a first substrate, the at least one opening providing a fluid path through the substrate; and a thin film membrane formed on a second surface of the substrate, the thin film membrane including a plurality of fluid ejection elements, the thin film membrane having a cantilevered section and a floating section, the floating section being at least partially detached from the cantilevered section and separated by a gap formed in the thin film membrane, the floating section being located over the at least one opening in the substrate, the cantilevered section being substantially supported by the substrate; wherein the floating section of the thin film membrane has a plurality of fluid feed holes formed therein, the fluid feed holes being in fluid communication with the fluid path.
  • 15. A printhead comprising:a printhead substrate having at least one opening formed in a first substrate, the at least one opening providing a fluid path through the substrate; and a thin film membrane formed on a second surface of the substrate, the thin film membrane including a plurality of fluid ejection elements, the thin film membrane having a cantilevered section and a floating section, the floating section being at least partially detached from the cantilevered section and separated by a gap formed in the thin film membrane, the floating section being located over the at least one opening in the substrate, the cantilevered section being substantially supported by the substrate; wherein each of the fluid ejection elements overlies the substrate.
  • 16. A printhead comprising:a printhead substrate having at least one opening formed in a first substrate, the at least one opening providing a fluid path through the substrate; and a thin film membrane formed on a second surface of the substrate, the thin film membrane including a plurality of fluid ejection elements, the thin film membrane having a cantilevered section and a floating section, the floating section being at least partially detached from the cantilevered section and separated by a gap formed in the thin film membrane, the floating section being located over the at least one opening in the substrate, the cantilevered section being substantially supported by the substrate; wherein the floating section of the thin film membrane comprises a field oxide layer and a protective layer, the protective layer overlying the field oxide layer.
  • 17. The printhead of claim 16, wherein the at least one opening in the substrate forms a trench, and wherein the field oxide layer acts as an etch stop when etching the trench.
  • 18. A printhead comprising:a printhead substrate having at least one opening formed in a first substrate, the at least one opening providing a fluid path through the substrate; and a thin film membrane formed on a second surface of the substrate, the thin film membrane including a plurality of fluid ejection elements, the thin film membrane having a cantilevered section and a floating section, the floating section being at least partially detached from the cantilevered section and separated by a gap formed in the thin film membrane, the opening being in fluid communication with a plurality of fluid ejection chambers through the gap, the floating section being located over the at least one opening in the substrate, the cantilevered section being substantially supported by the substrate.
  • 19. A printhead comprising:a printhead substrate having at least one opening formed in a first substrate, the at least one opening providing a fluid path through the substrate; and a thin film membrane formed on a second surface of the substrate, the thin film membrane including a plurality of fluid ejection elements, the thin film membrane having a cantilevered section and a floating section, the floating section being at least partially detached from the cantilevered section and separated along at least one long side by an elongated gap formed in the thin film membrane, the floating section being located over the at least one opening in the substrate, the cantilevered section being substantially supported by the substrate.
US Referenced Citations (2)
Number Name Date Kind
4894664 Tsung Pan Jan 1990 A
6000787 Weber et al. Dec 1999 A