Method of treating a metal surface to increase polymer adhesion

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Reexamination Certificate

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Reexamination Certificate

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06441838

ABSTRACT:

BACKGROUND OF THE INVENTION
The subject invention generally relates to ink jet printing, and more particularly to thin film ink jet printheads for ink jet cartridges and methods for manufacturing such printheads.
The art of ink jet printing is relatively well developed. Commercial products such as computer printers, graphics plotters, and facsimile machines have been implemented with ink jet technology for producing printed media. The contributions of Hewlett-Packard Company to ink jet technology are described, for example, in various articles in the
Hewlett
-
Packard Journal
, Vol. 36, No. 5 (May 1985); Vol. 39, No. 5 (October 1988); Vol. 43, No. 4 (August 1992); Vol. 43, No. 6 (December 1992); and Vol. 45, No. 1 (February 1994); all incorporated herein by reference.
Generally, an ink jet image is formed pursuant to precise placement on a print medium of ink drops emitted by an ink drop generating device known as an ink jet printhead. Typically, an ink jet printhead is supported on a movable carriage that traverses over the surface of the print medium and is controlled to eject drops of ink at appropriate times pursuant to command of a microcomputer or other controller, wherein the timing of the application of the ink drops is intended to correspond to a pattern of pixels of the image being printed.
A typical Hewlett-Packard ink jet printhead includes an array of precisely formed nozzles in an orifice plate that is attached to an ink barrier layer which in turn is attached to a thin film substructure that implements ink firing heater resistors and apparatus for enabling the resistors. The ink barrier layer defines ink channels including ink chambers disposed over associated ink firing resistors, and the nozzles in the orifice plate are aligned with associated ink chambers. Ink drop generator regions are formed by the ink chambers and portions of the thin film substructure and the orifice plate that are adjacent to the ink chambers.
The thin film substructure is typically comprised of a substrate such as silicon on which are formed various thin film layers that form thin film ink firing resistors, apparatus for enabling the resistors, and also intercon- nections to bonding pads that are provided for external electrical connections to the printhead. The thin film substructure more particularly includes a top thin film layer of tantalum disposed over the resistors as a thermomechanical passivation layer.
The ink barrier layer is typically a polymer material that is laminated as a dry film to the thin film substructure, and is designed to be photodefinable and both UV and thermally curable.
An example of the physical arrangement of the orifice plate, ink barrier layer, and thin film substructure is illustrated at page 44 of the
Hewlett
-
Packard Journal
of February 1994, cited above. Further examples of ink jet printheads are set forth in commonly assigned U.S. Pat. No. 4,719,477 and U.S. Pat. No. 5,317,346, both of which are incorporated herein by reference.
A consideration with the foregoing ink jet printhead architecture includes delamination of the ink barrier layer from the thin film substructure. Delamination principally occurs from environmental moisture and the ink itself which is in continual contact with the edges of the thin film substructure/barrier interface in the drop generator regions.
It has been determined that the tantalum thermomechanical passivation layer offers the additional functionality of improving adhesion to the ink barrier layer. However, while the barrier adhesion to tantalum has proven to be sufficient for printheads that are incorporated into disposable ink jet cartridges, barrier adhesion to tantalum is not sufficiently robust for semi-permanent ink jet printheads which are not replaced as frequently. Moreover, new developments in ink chemistry have resulted in formulations that more aggressively debond the interface between the thin film substructure and the barrier layer, as well as the interface between the barrier layer and the orifice plate.
In particular, water from the ink enters the thin film substructure/barrier interface by penetration through the bulk of the barrier and penetration along the thin film substructure/barrier interface, causing debonding of the interfaces through a chemical mechanism such as hydrolysis.
The problem with tantalum as a bonding surface is due to the fact that while the tantalum layer is pure tantalum when it is first formed in a sputtering apparatus, a tantalum oxide layer forms as soon as the tantalum layer is exposed to an oxygen containing atmosphere. The chemical bond between an oxide and a polymer film tends to be easily degraded by water, since the water forms a hydrogen bond with the oxide that competes with and replaces the original polymer to oxide bond, and thus ink formulations, particularly the more aggressive ones, debond an interface between a metal oxide and a polymer barrier.
SUMMARY OF THE INVENTION
It would therefore be an advantage to provide an improved ink jet printhead that reduces delamination of the interface between the thin film substructure and the ink barrier layer.
A further advantage would be to provide in a ink jet printhead a bonding surface that provides bonding sites to which a polymer barrier layer can form a stable chemical bond.
The invention is generally employed in an ink jet printhead that includes a thin film substrate including a plurality of thin film layers, a plurality of ink firing heater resistors defined in the plurality of thin film layers, a barrier adhesion layer disposed on the plurality of thin film layers, an ink barrier layer disposed on the barrier adhesion layer, and respective ink chambers formed in the ink barrier layer over respective thin film resistors, each chamber formed by a chamber opening in barrier layer.
In accordance with one aspect of the invention, the barrier adhesion layer comprises a deposited transition layer which after exposure to air contains tantalum, carbon, fluorine, and oxygen, and which is formed pursuant to exposure of the patterned tantalum layer to a plasma that includes a fluorinated hydrocarbon such as carbon tetrafluoride (CF
4
), fluoroform (CHF
3
), hexafluoroethane (C
2
F6), difluoromethane (CH
2
F
2
), pentafluoroethane (C
2
HF
5
), tetrafluoroethane (C
2
H
2
F
4
), or octafluorobutene (C
4
F
8
).
In accordance with a further aspect of the invention the ink barrier adhesion layer comprises a tantalum nitride layer.


REFERENCES:
patent: 4169032 (1979-09-01), Haase et al.
patent: 4474642 (1984-10-01), Nakane et al.
patent: 4535343 (1985-08-01), Wright et al.
patent: 4719477 (1988-01-01), Hess
patent: 4824716 (1989-04-01), Yerman
patent: 5278584 (1994-01-01), Keefe et al.
patent: 5317346 (1994-05-01), Garcia
patent: 5469199 (1995-11-01), Allen et al.
patent: 5812158 (1998-09-01), Murthy et al.
patent: 5983829 (1999-11-01), Suzuki
patent: 6037664 (2000-03-01), Zhao et al.
“Plasma Polymerization of Fluorocarbons,” d'Agostino, Cramarossa, Fracassi & Illuzzi, Chapter 2 of Plasma Deposition, Treatment, and Etching of Polymers, Riccardo d'Agostino, Ed., Academic Press, Inc., San Diego, 1990, pp. 95-162.
“Development of the Thin-Film Structure for the ThinkJet Printhead,” Bhaskar & Aden, Hewlett-Packard Journal, vol. 36, No. 5, May 1985, pp. 27-33.
“Development of a High-Resolution Thermal Inkjet Printhead,” Buskirk, Hackleman, Hall, Kanarek, Low, Trueba, Van de Poll, Hewlett-Packard Journal, vol. 39, No. 5, Oct. 1988, pp. 55-61.
“The Third-Generation HP Thermal InkJet Printhead,” Aden, Bohorquez, Collins, Crook, Garcia & Hess, Hewlett-Packard Journal, vol. 45, No. 1, Feb. 1994, pp. 41-45.

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