WO2007041173A2 - Thick film layers and methods relating thereto - Google Patents
Thick film layers and methods relating thereto Download PDFInfo
- Publication number
- WO2007041173A2 WO2007041173A2 PCT/US2006/037727 US2006037727W WO2007041173A2 WO 2007041173 A2 WO2007041173 A2 WO 2007041173A2 US 2006037727 W US2006037727 W US 2006037727W WO 2007041173 A2 WO2007041173 A2 WO 2007041173A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- thick film
- film layer
- epoxy compound
- micro
- ejection head
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000012530 fluid Substances 0.000 claims abstract description 71
- 239000004593 Epoxy Substances 0.000 claims abstract description 51
- -1 aryl ketone Chemical class 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 230000002708 enhancing effect Effects 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 66
- 229920002120 photoresistant polymer Polymers 0.000 claims description 55
- 239000000758 substrate Substances 0.000 claims description 41
- 150000001875 compounds Chemical class 0.000 claims description 32
- 239000003623 enhancer Substances 0.000 claims description 11
- 238000003384 imaging method Methods 0.000 claims description 11
- 230000001965 increasing effect Effects 0.000 claims description 11
- 125000005410 aryl sulfonium group Chemical group 0.000 claims description 7
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 6
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000012955 diaryliodonium Substances 0.000 claims description 3
- 125000005520 diaryliodonium group Chemical group 0.000 claims 2
- 238000004528 spin coating Methods 0.000 claims 1
- 238000009472 formulation Methods 0.000 description 45
- 239000000463 material Substances 0.000 description 19
- 150000003839 salts Chemical class 0.000 description 12
- 230000005855 radiation Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 150000002118 epoxides Chemical class 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 125000002560 nitrile group Chemical group 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 2
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000708 deep reactive-ion etching Methods 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical class [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 2
- FODCFYIWOJIZQL-UHFFFAOYSA-N 1-methylsulfanyl-3,5-bis(trifluoromethyl)benzene Chemical compound CSC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 FODCFYIWOJIZQL-UHFFFAOYSA-N 0.000 description 1
- RAXMFFZNRKLKLH-UHFFFAOYSA-M 4-methylbenzenesulfonate;[4-[(2-methylpropan-2-yl)oxy]phenyl]-phenyliodanium Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.C1=CC(OC(C)(C)C)=CC=C1[I+]C1=CC=CC=C1 RAXMFFZNRKLKLH-UHFFFAOYSA-M 0.000 description 1
- AOYQDLJWKKUFEG-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]hept-4-ene-4-carboxylate Chemical compound C=1C2OC2CCC=1C(=O)OCC1CC2OC2CC1 AOYQDLJWKKUFEG-UHFFFAOYSA-N 0.000 description 1
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 1
- ADAHGVUHKDNLEB-UHFFFAOYSA-N Bis(2,3-epoxycyclopentyl)ether Chemical compound C1CC2OC2C1OC1CCC2OC21 ADAHGVUHKDNLEB-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- ISFXMNADAJKIEG-UHFFFAOYSA-M [4-[(2-methylpropan-2-yl)oxy]phenyl]-phenyliodanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC(OC(C)(C)C)=CC=C1[I+]C1=CC=CC=C1 ISFXMNADAJKIEG-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- LMMDJMWIHPEQSJ-UHFFFAOYSA-N bis[(3-methyl-7-oxabicyclo[4.1.0]heptan-4-yl)methyl] hexanedioate Chemical compound C1C2OC2CC(C)C1COC(=O)CCCCC(=O)OCC1CC2OC2CC1C LMMDJMWIHPEQSJ-UHFFFAOYSA-N 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- UMIKAXKFQJWKCV-UHFFFAOYSA-M diphenyliodanium;4-methylbenzenesulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.C=1C=CC=CC=1[I+]C1=CC=CC=C1 UMIKAXKFQJWKCV-UHFFFAOYSA-M 0.000 description 1
- SBQIJPBUMNWUKN-UHFFFAOYSA-M diphenyliodanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C=1C=CC=CC=1[I+]C1=CC=CC=C1 SBQIJPBUMNWUKN-UHFFFAOYSA-M 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical class [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/16—Production of nozzles
- B41J2/1601—Production of bubble jet print heads
- B41J2/1603—Production of bubble jet print heads of the front shooter type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/16—Production of nozzles
- B41J2/1621—Manufacturing processes
- B41J2/1631—Manufacturing processes photolithography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/16—Production of nozzles
- B41J2/1621—Manufacturing processes
- B41J2/164—Manufacturing processes thin film formation
- B41J2/1645—Manufacturing processes thin film formation thin film formation by spincoating
Definitions
- the invention relates to, for example, improved radiation curable resin formulations and to methods for attaching a nozzle member to a substrate for a micro- fluid ejection head having a thick film layer derived from the improved radiation curable resin formulation.
- Micro-fluid ejection devices such as ink jet printers continue to evolve as the technology for ink jet printing continues to improve to provide higher speed, higher quality printers. However, the improvement in speed and quality does not come without a price.
- the micro-fluid ejection heads are more costly to manufacture because of tighter alignment tolerances.
- micro-fluid ejection heads were made with nozzle members, such as nozzle plates, containing flow features. The nozzle plates were then aligned, and adhesively attached to a substrate.
- substrate is intended to include, but is not limited to, semiconductor substrates, silicon substrates, and/or ceramic substrates suitable for use in providing micro-fluid ejection heads.
- One advance in providing improved micro-fluid ejection heads is the use of a photoresist layer applied to a device surface of the substrate as a thick film layer.
- the thick film layer is imaged to provide flow features for the micro-fluid ejection heads.
- Use of the imaged thick film layer enables more accurate alignment between the flow features and ejection actuators on the device surface of the substrate.
- Conventional photoresist layers used for the thick film layer are derived from components that affect the properties and characteristics of the thick film layer once ;he layer is imaged and developed.
- conventional photoresist layers are subject to developing stress cracks, imperfections, and distortions that reduce idhesion between the thick film layer and the nozzle plate attached to the thick film iayer. Accordingly, there is a need for, for example, improved photoresist or photoimageable materials that provide enhanced characteristics and dimensional stability for use in micro-fluid ejection head structures.
- a thick BIm layer for a micro-fluid ejection head, a micro-fluid ejection head, and a method for making a micro-fluid ejection head.
- One such thick film layer includes a negative photoresist layer derived from a composition containing a multi-functional epoxy compound, a difunctional epoxy compound, a photoacid generator devoid of aryl sulfonium salts, an adhesion enhancer, and an aryl ketone solvent.
- the negative photoresist layer has increased planarity subsequent to photoimaging and developing the photoresist layer.
- a method for increasing the planarity of a surface of a thick film layer after photoimaging and developing flow features therein for a micro-fluid ejection head includes applying a negative photoresist layer adjacent (e.g., to) a device surface of a substrate.
- the negative photoresist layer is derived from a multi-functional epoxy compound, a difunctional epoxy compound, a photoacid generator devoid of aryl sulfonium salts, an adhesion enhancer, and an aryl ketone solvent.
- the photoresist layer is imaged and developed to provide the flow features therein, wherein the thick film layer has a substantially planar thick film layer surface.
- a micro-fluid ejection head including a substrate having a device surface.
- the ejection head has a photoimaged and developed thick film layer applied adjacent the device surface of the substrate.
- the thick film layer is a negative photoresist layer derived from a multi-functional epoxy compound, a difunctional epoxy compound, a photoacid generator devoid of aryl sulfonium salts, an adhesion enhancer, and an aryl ketone solvent.
- the negative photoresist layer Upon imaging and developing, the negative photoresist layer has increased planarity for use in the micro-fluid ejection head.
- a nozzle member is adjacent the imaged and developed thick film layer.
- a further embodiment of the disclosure provides a dimensionally stable thick film layer for a micro-fluid ejection head.
- the dimensionally stable thick film layer is derived from a difunctional epoxy component having a weight average molecular weight ranging from about 2500 to about 4000 Daltons, a photoacid generator, an aryl ketone solvent, and an adhesion enhancing component.
- the dimensionally stable thick film layer has a cross-link density upon curing that increases the dimensional stability of the thick film layer sufficient to provide flow features therein having substantially vertical walls.
- compositions and methods according to at least some of the exemplary embodiments of the disclosure is that the thick film layer may be made and processed with fewer imperfections. For example, stress cracking of the thick film layer may be reduced. Also, planarity of the thick film layer and resistance to various fluids may also significantly improved over conventional thick film layers. The improved planarity of the thick film layer is effective to provide improved adhesion between the nozzle member and the thick film layer thereby reducing the incidence of delamination that may occur.
- thick film layers made according to at least some of the exemplary embodiments of the disclosure may exhibit significantly increased dimensional stability during subsequent micro-fluid ejection head manufacturing steps.
- An increase in dimensional stability of the thick film layer may be achieved by increasing the cross-link density of the thick film layer to a predetermined level.
- the dimensional stability of the thick film layer may be determined, for example, by observing the amount of deformation of flow features formed in the thick film layer during a step of bonding a nozzle member to the thick film layer. Excessive shrinkage of the thick film layer, which may reduce adhesion of the thick film layer to a substrate, may result if the cross-link density is too high. Accordingly, the compositions described herein may provide suitable thick film layers that provide the desirable stability and adhesion characteristics required for micro-fluid ejection heads.
- difunctional epoxy means epoxy compounds and materials having only two epoxy functional groups in the molecule.
- Multifunctional epoxy means epoxy compounds and materials having more than two epoxy functional groups in the molecule.
- FIG. 1 is a cross-sectional view, not to scale, of a portion of a prior art micro- fluid ejection head
- FIG. 2 is a cross-sectional view, not to scale, of a portion of another micro- fluid ejection head containing a prior art thick film layer;
- FIG. 3 is a perspective view, not to scale, of a fluid cartridge containing a micro-fluid ejection head
- FIG. 4 is a perspective view, not to scale, of a micro-fluid ejection device
- FIG. 5 is a photomicrograph of a thick film layer made with a formulation according to one embodiment after imaging and developing;
- FIG. 6 is a photomicrograph of a thick film layer made with a formulation according to another embodiment after imaging and developing;
- FIGS. 7-8 are schematic views of a process for imaging a thick film layer according to an embodiment of the disclosure.
- FIG. 9 is a partial plan view of a thick film layer after imaging on a substrate.
- FIG. 10 cross-sectional view, not to scale, of a portion of a micro-fluid ejection head according to the disclosure containing a nozzle member laminated to a thick film layer.
- the micro-fluid ejection head 10 includes a substrate 12 having various insulative, conductive, resistive, and passivating layers providing a fluid ejector actuator 16.
- a nozzle plate 18 is attached as by an adhesive 20 to a device surface 22 of the substrate 12.
- the nozzle plate 18 is made out of a laser ablated material, such as polyimide.
- the polymiide material is laser ablated to provide a fluid chamber 24 in fluid flow communication with a fluid supply channel 26.
- fluid is expelled through a nozzle hole 28 that is also laser ablated in the polyimide material of the nozzle plate 18.
- the fluid chamber 24 and fluid supply channel 26 are collectively referred to as "flow features.”
- a fluid feed slot 30 is etched in the substrate 12 to provide fluid via the fluid supply channel 26 to the fluid chamber 24.
- the polyimide material is laser ablated from a flow feature side 32 thereof before the nozzle plate 18 is attached to the substrate 12. Accordingly, misalignment between the flow features in the nozzle plate 18 and the fluid ejector actuator 16 may be detrimental to the functioning of the micro-fluid ejection head 10.
- FIG. 2 Another prior art micro-fluid ejection head 34 is illustrated in FIG. 2.
- a thick film layer 36 provides the flow features, i.e., a fluid supply channel 38 and a fluid chamber 40 for providing fluid to the fluid ejector actuator 16.
- the thick film layer 36 is a photoresist material that is spin coated onto the device surface 22 of the substrate 12. The photoresist material is then imaged and developed using conventional photoimaging techniques to provide the flow features.
- a separate nozzle plate 42 containing only nozzles, such as nozzle 44 is then attached to the thick film layer 36 as by thermal compression bonding or by use of an adhesive.
- the nozzle plate 42 may be made of a laser ablated polyimide material.
- the microfluid ejection head 10 or 34 may be attached to a fluid supply reservoir 50 as illustrated in FIG. 3.
- the fluid reservoir 50 includes a flexible circuit 52 containing electrical contacts 54 thereon for providing control and actuation of the fluid ejector actuators 16 on the substrate 12 via conductive traces 56.
- One or more reservoirs 50 containing the ejection heads 10 or 34 may be used in a micro-fluid ejection device 60, such as an ink jet printer as shown in FIG. 4 to provide control and ejection of fluid from the ejection heads 10 or 34.
- conventional photoresist materials for providing the thick film layer 36 may develop cracks and/or imperfections such as non-planar areas 62 (FIG. 2) which may create gaps 64 or otherwise reduce adhesion between the nozzle plate 42 and the thick film layer 36. Such reduced adhesion may lead to delamination of the nozzle plate 42 from the thick film layer. Additionally, the gaps 64 caused by the raised areas 62 may cause misalignment or distortion of the nozzle holes 44 thereby resulting in poor performance of the ejection head 34.
- FIG. 5 is a photomicrograph of a portion of a thick film layer 66 made with a photoresist formulation according to one embodiment of the invention.
- imperfections 70 develop in the thick film layer 66.
- a thick film layer 72 made according to another embodiment of the disclosure is much improved in planarity and has much more well-defined flow features 74 without the imperfections 70 of the previous photoresist material.
- a photoresist formulation that provides the thick film layer 66 includes a difunctional epoxy component, a photoacid generator, a non-reactive solvent, and, optionally, an adhesion enhancing agent.
- a photoresist formulation that provides the improved thick film layer 72 further includes a multi-functional epoxy compound.
- the difunctional epoxy component may be selected from difunctional epoxy compounds which include diglycidyl ethers of bisphenol-A (e.g. those available under the trade designations "EPON 1007F”, “EPON 1007” and “EPON 1009F", available from Shell Chemical Company of Houston, Tex., "DER- 331", “DER-332”, and “DER-334", available from Dow Chemical Company of Midland, Mich., 3,4-epoxycyclohexylmethyl-3,4-epoxycyclo-hexene carboxylate (e.g.
- ERP-4221 available from Union Carbide Corporation of Danbury, Connecticut, 3,4- epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcy-clohexene carboxylate (e.g. "ERL-4201” available from Union Carbide Corporation), bis(3,4-epoxy-6- methylcyclohexylmethyl) adipate (e.g. "ERL-4289” available from Union Carbide Corporation), and bis(2,3-epoxycyclopentyl) ether (e.g. "ERL-0400” available from Union Carbide Corporation.
- An exemplary difunctional epoxy component is a bisphenol- A/epichlorohydrin epoxy resin available from Shell Chemical Company of Houston, Tex.
- EPON resin 1007F having an epoxide equivalent of greater than about 1000.
- An "epoxide equivalent” is the number of grams of resin containing 1 gram-equivalent of epoxide.
- the weight average molecular weight of the difunctional epoxy component is typically above 2500, e.g., from about 2800 to about 3500 weight average molecular weight in Daltons.
- the amount of difunctional epoxy component in the photoresist formulation may range from about 30 to about 95 percent by weight based on the weight of the cured resin.
- the photoresist formulation according to embodiments of the disclosure also includes a photoacid generator.
- the photoacid generator may be selected from a compound or mixture of compounds capable of generating a cation such as an aromatic complex salt which may be selected from onium salts of a Group VA element, onium salts of a Group VIA element, and aromatic halonium salts.
- Aromatic complex salts upon being exposed to ultraviolet radiation or electron beam irradiation, are capable of generating acid moieties which initiate reactions with epoxides.
- the photoacid generator may be present in the photoresist formulation in an amount ranging from about 0.5 to about 15 weight percent based on the weight of the cured resin.
- triaryl-substituted sulfonium complex salt photoinitiators which may be used in the formulations according to the first embodiment include, but are not limited to: triphenylsulfonium tetrafluoroborate triphenylsulfoniumhexafluorophosphate triphenylsulfonium hexafluoroantimonate tritolysulfonium hexafluorophosphate anisyldiphenylsulfonium hexafluoroantimonate
- an exemplary salt may be a mixture of triarylsulfonium hexafluoroantimonate salt, commercially available from Union Carbide Corporation under the trade name CYRACURE UVI-6974.
- suitable salts may include di- and triaryl-substituted iodonium salts which are substantially devoid of aryl sulfonium salts.
- aryl-substituted iodonium complex salt photoacid generates include, but are not limited to: diphenyliodonium trifluoromethanesulfonate,
- An exemplary iodonium salt for use as a photoacid generator for the formulations of the second embodiment described herein is a mixture of diaryliodonium hexafluoroantimonate salts, commercially available from the Polyset, Company of Mechanicsville, New York under the trade name PC-2506.
- the photoresist formulation also contains a multifunctional epoxy component.
- a suitable multifunctional epoxy component may be selected from aromatic epoxides such as glycidyl ethers of polyphenols.
- An exemplary multifunctional epoxy resin is a polyglycidyl ether of a phenolformaldehyde novolac resin such as a novolac epoxy resin having an epoxide gram equivalent weight ranging from about 190 to about 250 and a viscosity at 130° C. ranging from about 10 to about 60 poise, which is available from Resolution Performance Products of Houston, Texas under the trade name EPON RESIN SU-8.
- the multi-functional epoxy component of the photoresist formulation according to such an embodiment may have a weight average molecular weight of about 3,000 to about 5,000 as determined by gel permeation chromatography, and an average epoxide group functionality of greater than 3, such as from about 6 to about 10.
- the amount of multifunctional epoxy resin in the photoresist formulation according to the second embodiment ranges from about 30 to about 50 percent by weight based on the weight of the cured thick film layer 80.
- the photoresist formulations may optionally include an effective amount of an adhesion enhancing agent such as a silane compound.
- Silane compounds that are compatible with the components of the photoresist formulation typically have a functional group capable of reacting with at least one member selected from the group consisting of the multifunctional epoxy compound (in embodiments wherein the same is included in the photoresist formulation), the difunctional epoxy compound and the photoinitiator.
- an adhesion enhancing agent may be a silane with an epoxide functional group such as a glycidoxyalkyltrialkoxysilane, e.g., gamma- glycidoxypropyltrimethoxysilane.
- the adhesion enhancing agent is present in an amount ranging from about 0.5 to about 5 weight percent, such as from about 0.9 to about 4.5 weight percent based on total weight of the cured resin, including all ranges subsumed therein (including, e.g., an exemplary range of from about 1.0 to about 1.5).
- Adhesion enhancing agents are defined to include organic materials soluble in the photoresist composition which assist the film forming and adhesion characteristics of the thick film layer 80 adjacent the device surface 22 of the substrate 12.
- a suitable solvent is used.
- An exemplary solvent is a solvent which is non-photoreactive.
- Non-photoreactive solvents include, but are not limited to, gamma-butyrolactone, C 1-6 acetates, tetrahydrofuran, low molecular weight ketones, mixtures thereof and the like.
- An exemplary non-photoreactive solvent is acetophenone.
- the non-photoreactive solvent is present in the formulation mixtures used to provide the thick film layer 80 in an amount ranging of from about 20 to about 90 weight percent, such as from about 40 to about 60 weight percent, based on the total weight of the photoresist formulation.
- the non- photoreactive solvent does not remain in the cured thick film layer 80 and is thus is removed prior to or during the thick film layer 80 curing steps.
- a non-photoreactive solvent and a difunctional epoxy compound are mixed together in a suitable container, such as an amber bottle or flask and the mixture is put in a roller mill overnight at about 60° C. to assure suitable mixing of the components.
- a suitable container such as an amber bottle or flask
- the multifunctional epoxy compound if used, is added to the container and the resulting mixture is rolled for two hours on a roller mill at about 60° C.
- the other components such as the photoacid generator and/or the adhesion enhancing agent, are also added one at a time to the container and the container is rolled for about two hours at about 60° C. after adding all of the components to the container to provide a wafer coating mixture.
- the photoresist formulations and resulting thick film layer 80 described herein are substantially devoid of acrylate or methacylate polymers and nitrile groups. Without desiring to be bound by theory, it is believed that the higher molecular weight difunctional epoxy material contributes sufficient thermoplastic properties to the thick film layer 36 to enable use of a photocurrable formulation that is substantially devoid of acrylate or methacrylate polymers and nitrile rubber components. Additionally, a photoresist formulation, substantially devoid of acrylate or methacrylate polymers, may have an increased shelf life as compared to the same photoresist formulation containing acrylate or methacrylate polymers.
- a method for making the improved photoimaged thick film layer 80 will now be described with reference to FIGS. 7-9.
- a silicon substrate wafer is centered on an appropriate sized chuck of either a resist spinner or conventional wafer resist deposition track.
- the photoresist formulation mixture is either dispensed by hand or mechanically into the center of the wafer.
- the chuck holding the wafer is then rotated at a. predetermined number of revolutions per minute to evenly spread the mixture from the center of the wafer to the edge of the wafer.
- the rotational speed of the wafer may be adjusted or the viscosity of the coating mixture may be altered to vary the resulting resin film thickness. Rotational speeds of 2500 rpm or more may be used.
- the amount of photoresist formulation applied to device surface 22 should be sufficient to provide the thick film layer 80 having the desired thickness for flow features imaged therein. Accordingly, the thickness of layer 80 after curing may range from about 10 to about 25 microns or more.
- the resulting substrate wafer containing the thick film layer 80 is then removed from the chuck either manually or mechanically and placed on either a temperature controlled hotplate or in a temperature controlled oven at a temperature of about 90° C. for about 30 seconds to about 1 minute until the material is "soft" baked.
- This step removes at least a portion of the solvent from the thick film layer 80 resulting in a partially dried film adjacent the device surface 22 of the substrate 12.
- the wafer is removed from the heat source and allowed to cool to room temperature.
- the fluid feed slot 30 is formed in the substrate, such as by an etching process.
- An exemplary etching process is a dry etch process such as deep reactive ion etching or inductively coupled plasma etching. During the etching process, the photoresist layer 80 acts as an etch stop layer.
- the layer 80 is masked with a mask 86 containing substantially transparent areas 88 and substantially opaque areas 90 thereon. Areas of the thick film layer 80 masked by the opaque areas 90 of the mask 86 will be removed upon developing to provide the flow features described above.
- a radiation source provides actinic radiation indicated by arrows 92 to image the thick film layer 80.
- a suitable source of radiation emits actinic radiation at a wavelength within the ultraviolet and visible spectral regions.
- Exposure of the thick film layer 80 may be from less than about 1 second to 10 minutes or more, such as from about 5 seconds to about one minute, depending upon the amounts of particular epoxy materials and aromatic complex salts being used in the formulation and depending upon the radiation source, distance from the radiation source, and the thickness of the thick film layer 80.
- the thick film layer 80 may optionally be exposed to electron beam irradiation instead of ultraviolet radiation.
- the foregoing procedure is similar to a standard semiconductor lithographic process.
- the mask 86 is a clear, flat substrate usually glass or quartz with opaque areas 90 defining the areas to be removed from the layer 80 (i.e. a negative acting photoresist layer 80).
- the opaque areas 90 prevent the ultraviolet light from cross- linking the layer 80 masked beneath it.
- the exposed areas of the layer 80 provided by the substantially transparent areas 88 of the mask 86 are subsequently baked at a temperature of about 90° C. for about 30 seconds to about 10 minutes, such as from about 1 to about 5 minutes to complete the curing of the thick film layer 80.
- the non-imaged areas of the thick film layer 80 are then solubilized by a developer and the solubilized material is removed leaving the imaged and developed thick film layer 80 adjacent the device surface 22 of the substrate 12 as shown in FIG. 8 and in plan view in FIG. 9.
- the developer comes in contact with the substrate 12 and thick film layer 80 through either immersion and agitation in a tank-like setup or by spraying the developer on the substrate 12 and thick film layer 80. Either spray or immersion will adequately remove the non-imaged material.
- Illustrative developers include, for example, butyl cellosolve acetate, a xylene and butyl cellosolve acetate mixture, and C 1-6 acetates like butyl acetate.
- the substrate 12 having the layer 80 is optionally baked at a temperature ranging from about 150° C. to about 200° C, such as from about from about 170° C. to about 190° C. for about 1 minute to about 60 minutes, such as from about 15 to about 30 minutes.
- a formulation generally in accordance with the first embodiment, was used to make thick film layer 66. The formulation used was as follows:
- a formulation for comparison purposes, was used to make the thick film layer 72 (FIG. 6) and includes:
- the planarity of the thick film layer 66 may be significantly improved by use of the formulation in Table 2 as illustrated by the thick film layer 72 in FIG. 6.
- the thick film layer 72 made with the formulation of Table 2 provided substantially improved image resolution.
- such a thick film layer 72 had a resolution of greater than about 10 microns (e.g., 6 microns at 13 to 20 microns thickness), with an aspect ratio of less than about 2:1 (e.g., about 5:1).
- the increased resolution of the thick film layer 72 as compared to thick film layer 66 is believed to be the result of incorporating the multifunctional epoxy component (EPON SU-8) into the formulation.
- the EPON SU-8 component allows an increase in functionality by 2 per repeat units, which enables an increase in cross link density and a reduction in swelling during development.
- the Polyset photoacid generator has shown improvements in the rates of reaction and a larger energy window. The increase in the rate of reaction allows the progression of the cationic cure to propagate through the thickness of the thick film layer 72 at a faster rate insuring uniform distribution of cure as a function of depth.
- epoxies undergo shrinkage during the curing and cooling process which may result in internal stresses within the thick film layer 66 that may provide the imperfections 70 shown in FIG. 5.
- the stresses may manifest themselves in the form of interfacial delamination or stress cracks through the thick film layer 66.
- Such stress cracks may cause the surface of the thick film layer 66 to be non-planar which may lead to non uniform etching (pitting and over etching) of the substrate 12 when forming the fluid supply slot 30 by a deep reactive ion etching process.
- a technique to remove such stresses in the thick film layer 66 is the incorporation of a rubbery, flexible second phase within the epoxy.
- This rubbery phase forms soft, stress-relieving domains within the epoxy that will relieve some of the internal stresses and prevent the propagation of cracks.
- Most rubber phase materials are provided by nitrile groups. The nitrile groups on the rubber backbone enhance the interaction with the epoxy. However, the nitrile groups reduce the chemical resistance and decrease the cure rate of the thick film layer 66.
- Thick film layers made with formulations according to Table 3 are expected to exhibit increased dimensional stability over prior art formulations with respect to thermal bonding of components to the thick film layer. Such formulations may be used where higher image resolutions requirements are absent.
- a nozzle member such as plate 94, is laminated adjacent (e.g., to) the thick film layer 80.
- the nozzle plate 94 is substantially rectangular and is aligned with the substrate 12 and thick film layer 80 so that the nozzles 96 are in axial alignment with corresponding fluid ejector actuators 16 on the device surface 22 of the substrate 12 and with the fluid chambers 82 in the thick film layer 80.
- the nozzle plate 94 may be adhesively attached to the thick film layer 80.
- the nozzle plate 94 may be laminated to the thick film layer 80 using pressure and heat.
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Abstract
Thick film layers for a micro-fluid ejection head, micro-fluid ejection heads, and methods for making micro-fluid ejection head and thick film layers. One such thick film layer is derived from a difunctional epoxy component having a weight average molecular weight ranging from about 2500 to about 4000 Daltons, a photoacid generator, an aryl ketone solvent, and a adhesion enhancing component. One such thick film layer (80) has a cross-link density upon curing that increases the dimensional stability of the thick film layer sufficient to provide flow features therein having substantially vertical walls.
Description
THICK FILM LAYERS AND METHODS RELATING THERETO :ROSS-REFERENCE TO RELATED APPLICATION
This application claims the benefit of U.S. Provisional Application Serial No. 30/722,767, entitled "Thick-Film Layers for Micro-Fluid Ejection Heads, Micro-Fluid Ejection Heads and Methods Related Thereto", filed on September 30, 2005.
FIELD OF THE INVENTION
The invention relates to, for example, improved radiation curable resin formulations and to methods for attaching a nozzle member to a substrate for a micro- fluid ejection head having a thick film layer derived from the improved radiation curable resin formulation.
BACKGROUND AND SUMMARY
Micro-fluid ejection devices, such as ink jet printers continue to evolve as the technology for ink jet printing continues to improve to provide higher speed, higher quality printers. However, the improvement in speed and quality does not come without a price. The micro-fluid ejection heads are more costly to manufacture because of tighter alignment tolerances.
For example, micro-fluid ejection heads were made with nozzle members, such as nozzle plates, containing flow features. The nozzle plates were then aligned, and adhesively attached to a substrate. However, minor imperfections in the substrate or nozzle plate components of the ejection head or improper alignment of the parts may have a significant impact on the performance of the ejection heads. For the purposes of this disclosure, the term "substrate" is intended to include, but is not limited to, semiconductor substrates, silicon substrates, and/or ceramic substrates suitable for use in providing micro-fluid ejection heads.
One advance in providing improved micro-fluid ejection heads is the use of a photoresist layer applied to a device surface of the substrate as a thick film layer. The thick film layer is imaged to provide flow features for the micro-fluid ejection heads. Use of the imaged thick film layer enables more accurate alignment between the flow features and ejection actuators on the device surface of the substrate.
While the use of an imaged photoresist layer improves alignment of the flow features to the ejection actuators, there may still exist alignment problems associated with the nozzle plate. Misalignment between the ejection actuators and corresponding
lozzle (e.g., holes) in a nozzle plate attached to the thick film layer has a lisadvantageous effect on the accuracy of fluid droplets ejected from the nozzless. Ejector actuator and nozzle hole alignment also has an effect on the mass and velocity )f the fluid droplets ejected through the nozzles.
Conventional photoresist layers used for the thick film layer are derived from components that affect the properties and characteristics of the thick film layer once ;he layer is imaged and developed. For example, conventional photoresist layers are subject to developing stress cracks, imperfections, and distortions that reduce idhesion between the thick film layer and the nozzle plate attached to the thick film iayer. Accordingly, there is a need for, for example, improved photoresist or photoimageable materials that provide enhanced characteristics and dimensional stability for use in micro-fluid ejection head structures.
Amongst other embodiments of the present invention, there is provided a thick BIm layer for a micro-fluid ejection head, a micro-fluid ejection head, and a method for making a micro-fluid ejection head. One such thick film layer includes a negative photoresist layer derived from a composition containing a multi-functional epoxy compound, a difunctional epoxy compound, a photoacid generator devoid of aryl sulfonium salts, an adhesion enhancer, and an aryl ketone solvent. The negative photoresist layer has increased planarity subsequent to photoimaging and developing the photoresist layer.
In another embodiment, there is provided a method for increasing the planarity of a surface of a thick film layer after photoimaging and developing flow features therein for a micro-fluid ejection head. The method includes applying a negative photoresist layer adjacent (e.g., to) a device surface of a substrate. The negative photoresist layer is derived from a multi-functional epoxy compound, a difunctional epoxy compound, a photoacid generator devoid of aryl sulfonium salts, an adhesion enhancer, and an aryl ketone solvent. The photoresist layer is imaged and developed to provide the flow features therein, wherein the thick film layer has a substantially planar thick film layer surface.
In yet another embodiment, there is provided a micro-fluid ejection head including a substrate having a device surface. The ejection head has a photoimaged and developed thick film layer applied adjacent the device surface of the substrate. The thick film layer is a negative photoresist layer derived from a multi-functional epoxy compound, a difunctional epoxy compound, a photoacid generator devoid of
aryl sulfonium salts, an adhesion enhancer, and an aryl ketone solvent. Upon imaging and developing, the negative photoresist layer has increased planarity for use in the micro-fluid ejection head. A nozzle member is adjacent the imaged and developed thick film layer.
A further embodiment of the disclosure provides a dimensionally stable thick film layer for a micro-fluid ejection head. The dimensionally stable thick film layer is derived from a difunctional epoxy component having a weight average molecular weight ranging from about 2500 to about 4000 Daltons, a photoacid generator, an aryl ketone solvent, and an adhesion enhancing component. The dimensionally stable thick film layer has a cross-link density upon curing that increases the dimensional stability of the thick film layer sufficient to provide flow features therein having substantially vertical walls.
An advantage of the compositions and methods according to at least some of the exemplary embodiments of the disclosure is that the thick film layer may be made and processed with fewer imperfections. For example, stress cracking of the thick film layer may be reduced. Also, planarity of the thick film layer and resistance to various fluids may also significantly improved over conventional thick film layers. The improved planarity of the thick film layer is effective to provide improved adhesion between the nozzle member and the thick film layer thereby reducing the incidence of delamination that may occur.
Additionally, thick film layers made according to at least some of the exemplary embodiments of the disclosure may exhibit significantly increased dimensional stability during subsequent micro-fluid ejection head manufacturing steps. An increase in dimensional stability of the thick film layer may be achieved by increasing the cross-link density of the thick film layer to a predetermined level. The dimensional stability of the thick film layer may be determined, for example, by observing the amount of deformation of flow features formed in the thick film layer during a step of bonding a nozzle member to the thick film layer. Excessive shrinkage of the thick film layer, which may reduce adhesion of the thick film layer to a substrate, may result if the cross-link density is too high. Accordingly, the compositions described herein may provide suitable thick film layers that provide the desirable stability and adhesion characteristics required for micro-fluid ejection heads.
For purposes of the disclosure, "difunctional epoxy" means epoxy compounds and materials having only two epoxy functional groups in the molecule.
"Multifunctional epoxy" means epoxy compounds and materials having more than two epoxy functional groups in the molecule.
BRIEF DESCRIPTION OF THE DRAWINGS
Further advantages of the exemplary embodiments will become apparent by reference to the detailed description when considered in conjunction with the figures, which are not to scale, wherein like reference numbers indicate like elements through the several views, and wherein:
FIG. 1 is a cross-sectional view, not to scale, of a portion of a prior art micro- fluid ejection head;
FIG. 2 is a cross-sectional view, not to scale, of a portion of another micro- fluid ejection head containing a prior art thick film layer;
FIG. 3 is a perspective view, not to scale, of a fluid cartridge containing a micro-fluid ejection head;
FIG. 4 is a perspective view, not to scale, of a micro-fluid ejection device;
FIG. 5 is a photomicrograph of a thick film layer made with a formulation according to one embodiment after imaging and developing;
FIG. 6 is a photomicrograph of a thick film layer made with a formulation according to another embodiment after imaging and developing;
FIGS. 7-8 are schematic views of a process for imaging a thick film layer according to an embodiment of the disclosure;
FIG. 9 is a partial plan view of a thick film layer after imaging on a substrate; and
FIG. 10 cross-sectional view, not to scale, of a portion of a micro-fluid ejection head according to the disclosure containing a nozzle member laminated to a thick film layer.
DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
With reference to FIG. 1, there is shown, in partial cross-sectional view, a portion of a prior art micro-fluid ejection head 10. The micro-fluid ejection head 10 includes a substrate 12 having various insulative, conductive, resistive, and passivating layers providing a fluid ejector actuator 16.
In a prior art micro-fluid ejection head 10, a nozzle plate 18 is attached as by an adhesive 20 to a device surface 22 of the substrate 12. In such a micro-fluid ejection head 10, the nozzle plate 18 is made out of a laser ablated material, such as polyimide. The polymiide material is laser ablated to provide a fluid chamber 24 in fluid flow communication with a fluid supply channel 26. Upon activation of the ejector actuator, fluid is expelled through a nozzle hole 28 that is also laser ablated in the polyimide material of the nozzle plate 18. The fluid chamber 24 and fluid supply channel 26 are collectively referred to as "flow features." A fluid feed slot 30 is etched in the substrate 12 to provide fluid via the fluid supply channel 26 to the fluid chamber 24.
In order to provide the laser ablated nozzle plate 18, the polyimide material is laser ablated from a flow feature side 32 thereof before the nozzle plate 18 is attached to the substrate 12. Accordingly, misalignment between the flow features in the nozzle plate 18 and the fluid ejector actuator 16 may be detrimental to the functioning of the micro-fluid ejection head 10.
Another prior art micro-fluid ejection head 34 is illustrated in FIG. 2. In this prior art micro-fluid ejection head 34, a thick film layer 36 provides the flow features, i.e., a fluid supply channel 38 and a fluid chamber 40 for providing fluid to the fluid ejector actuator 16. In such an ejection head 34, the thick film layer 36 is a photoresist material that is spin coated onto the device surface 22 of the substrate 12. The photoresist material is then imaged and developed using conventional photoimaging techniques to provide the flow features. A separate nozzle plate 42 containing only nozzles, such as nozzle 44 is then attached to the thick film layer 36 as by thermal compression bonding or by use of an adhesive. As in FIG. 1 , the nozzle plate 42 may be made of a laser ablated polyimide material.
The microfluid ejection head 10 or 34 may be attached to a fluid supply reservoir 50 as illustrated in FIG. 3. The fluid reservoir 50 includes a flexible circuit 52 containing electrical contacts 54 thereon for providing control and actuation of the fluid ejector actuators 16 on the substrate 12 via conductive traces 56. One or more reservoirs 50 containing the ejection heads 10 or 34 may be used in a micro-fluid ejection device 60, such as an ink jet printer as shown in FIG. 4 to provide control and ejection of fluid from the ejection heads 10 or 34.
Referring again to FIG.2, while the thick film layer 36 enables more accurate alignment of the flow features with the ejector actuator 16, conventional photoresist
materials for providing the thick film layer 36 may develop cracks and/or imperfections such as non-planar areas 62 (FIG. 2) which may create gaps 64 or otherwise reduce adhesion between the nozzle plate 42 and the thick film layer 36. Such reduced adhesion may lead to delamination of the nozzle plate 42 from the thick film layer. Additionally, the gaps 64 caused by the raised areas 62 may cause misalignment or distortion of the nozzle holes 44 thereby resulting in poor performance of the ejection head 34.
FIG. 5 is a photomicrograph of a portion of a thick film layer 66 made with a photoresist formulation according to one embodiment of the invention. Upon imaging and developing the thick film layer 66 to provide the flow features 68, imperfections 70 develop in the thick film layer 66. By comparison, a thick film layer 72 made according to another embodiment of the disclosure is much improved in planarity and has much more well-defined flow features 74 without the imperfections 70 of the previous photoresist material.
A photoresist formulation that provides the thick film layer 66 according to one embodiment of the disclosure includes a difunctional epoxy component, a photoacid generator, a non-reactive solvent, and, optionally, an adhesion enhancing agent. In another embodiment of the disclosure, a photoresist formulation that provides the improved thick film layer 72 further includes a multi-functional epoxy compound.
In the photoresist formulations according to the first and second embodiments of the disclosure, the difunctional epoxy component may be selected from difunctional epoxy compounds which include diglycidyl ethers of bisphenol-A (e.g. those available under the trade designations "EPON 1007F", "EPON 1007" and "EPON 1009F", available from Shell Chemical Company of Houston, Tex., "DER- 331", "DER-332", and "DER-334", available from Dow Chemical Company of Midland, Mich., 3,4-epoxycyclohexylmethyl-3,4-epoxycyclo-hexene carboxylate (e.g. "ERL-4221" available from Union Carbide Corporation of Danbury, Connecticut, 3,4- epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcy-clohexene carboxylate (e.g. "ERL-4201" available from Union Carbide Corporation), bis(3,4-epoxy-6- methylcyclohexylmethyl) adipate (e.g. "ERL-4289" available from Union Carbide Corporation), and bis(2,3-epoxycyclopentyl) ether (e.g. "ERL-0400" available from Union Carbide Corporation.
An exemplary difunctional epoxy component is a bisphenol- A/epichlorohydrin epoxy resin available from Shell Chemical Company of Houston, Tex. under the trade name EPON resin 1007F having an epoxide equivalent of greater than about 1000. An "epoxide equivalent" is the number of grams of resin containing 1 gram-equivalent of epoxide. The weight average molecular weight of the difunctional epoxy component is typically above 2500, e.g., from about 2800 to about 3500 weight average molecular weight in Daltons. The amount of difunctional epoxy component in the photoresist formulation may range from about 30 to about 95 percent by weight based on the weight of the cured resin.
The photoresist formulation according to embodiments of the disclosure also includes a photoacid generator. The photoacid generator may be selected from a compound or mixture of compounds capable of generating a cation such as an aromatic complex salt which may be selected from onium salts of a Group VA element, onium salts of a Group VIA element, and aromatic halonium salts. Aromatic complex salts, upon being exposed to ultraviolet radiation or electron beam irradiation, are capable of generating acid moieties which initiate reactions with epoxides. The photoacid generator may be present in the photoresist formulation in an amount ranging from about 0.5 to about 15 weight percent based on the weight of the cured resin.
Examples of triaryl-substituted sulfonium complex salt photoinitiators which may be used in the formulations according to the first embodiment include, but are not limited to: triphenylsulfonium tetrafluoroborate triphenylsulfoniumhexafluorophosphate triphenylsulfonium hexafluoroantimonate tritolysulfonium hexafluorophosphate anisyldiphenylsulfonium hexafluoroantimonate
4-butoxyphenyidiphenylsulfonium tetrafluoroborate
4-chlorophenyidiphenylsulfonium hexafluoroantimonate
4-acetoxy-phenyldiphenylsulfonium tetrafluoroborate
4-acetamidophenyldiphenylsulfonium tetrafluoroborate
Of the triaryl-substituted sulfonium complex salts which are suitable for use in lie formulations of the first embodiment, an exemplary salt may be a mixture of
triarylsulfonium hexafluoroantimonate salt, commercially available from Union Carbide Corporation under the trade name CYRACURE UVI-6974.
Of the aromatic complex salts which may be suitable for use in an exemplary photoresist formulation according to the second embodiment of the disclosure, suitable salts may include di- and triaryl-substituted iodonium salts which are substantially devoid of aryl sulfonium salts. Examples of aryl-substituted iodonium complex salt photoacid generates include, but are not limited to: diphenyliodonium trifluoromethanesulfonate,
(p-tert-butoxyphenyl)phenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate,
(p-tert-butoxyphenyl)-phenyliodonium p-toluenesulfonate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, and diphenyliodonium hexafluoroantimonate.
An exemplary iodonium salt for use as a photoacid generator for the formulations of the second embodiment described herein is a mixture of diaryliodonium hexafluoroantimonate salts, commercially available from the Polyset, Company of Mechanicsville, New York under the trade name PC-2506.
As previously noted, in the second embodiment of the disclosure, the photoresist formulation also contains a multifunctional epoxy component. A suitable multifunctional epoxy component may be selected from aromatic epoxides such as glycidyl ethers of polyphenols. An exemplary multifunctional epoxy resin is a polyglycidyl ether of a phenolformaldehyde novolac resin such as a novolac epoxy resin having an epoxide gram equivalent weight ranging from about 190 to about 250 and a viscosity at 130° C. ranging from about 10 to about 60 poise, which is available from Resolution Performance Products of Houston, Texas under the trade name EPON RESIN SU-8.
The multi-functional epoxy component of the photoresist formulation according to such an embodiment may have a weight average molecular weight of about 3,000 to about 5,000 as determined by gel permeation chromatography, and an average epoxide group functionality of greater than 3, such as from about 6 to about 10. In an exemplary embodiment, the amount of multifunctional epoxy resin in the photoresist formulation according to the second embodiment ranges from about 30 to about 50 percent by weight based on the weight of the cured thick film layer 80.
The photoresist formulations may optionally include an effective amount of an adhesion enhancing agent such as a silane compound. Silane compounds that are compatible with the components of the photoresist formulation typically have a functional group capable of reacting with at least one member selected from the group consisting of the multifunctional epoxy compound (in embodiments wherein the same is included in the photoresist formulation), the difunctional epoxy compound and the photoinitiator. Such an adhesion enhancing agent may be a silane with an epoxide functional group such as a glycidoxyalkyltrialkoxysilane, e.g., gamma- glycidoxypropyltrimethoxysilane. When used, in an exemplary embodiment, the adhesion enhancing agent is present in an amount ranging from about 0.5 to about 5 weight percent, such as from about 0.9 to about 4.5 weight percent based on total weight of the cured resin, including all ranges subsumed therein (including, e.g., an exemplary range of from about 1.0 to about 1.5). Adhesion enhancing agents, as used herein, are defined to include organic materials soluble in the photoresist composition which assist the film forming and adhesion characteristics of the thick film layer 80 adjacent the device surface 22 of the substrate 12.
In order to provide the thick film layer 80 adjacent the device surface 22 of the substrate 12 (FIG. 7), a suitable solvent is used. An exemplary solvent is a solvent which is non-photoreactive. Non-photoreactive solvents include, but are not limited to, gamma-butyrolactone, C1-6 acetates, tetrahydrofuran, low molecular weight ketones, mixtures thereof and the like. An exemplary non-photoreactive solvent is acetophenone. The non-photoreactive solvent is present in the formulation mixtures used to provide the thick film layer 80 in an amount ranging of from about 20 to about 90 weight percent, such as from about 40 to about 60 weight percent, based on the total weight of the photoresist formulation. In an exemplary embodiment, the non- photoreactive solvent does not remain in the cured thick film layer 80 and is thus is removed prior to or during the thick film layer 80 curing steps.
According to an exemplary procedure, a non-photoreactive solvent and a difunctional epoxy compound are mixed together in a suitable container, such as an amber bottle or flask and the mixture is put in a roller mill overnight at about 60° C. to assure suitable mixing of the components. After mixing the solvent and difunctional epoxy compound, the multifunctional epoxy compound, if used, is added to the container and the resulting mixture is rolled for two hours on a roller mill at about 60° C. The other components, such as the photoacid generator and/or the adhesion
enhancing agent, are also added one at a time to the container and the container is rolled for about two hours at about 60° C. after adding all of the components to the container to provide a wafer coating mixture.
The photoresist formulations and resulting thick film layer 80 described herein are substantially devoid of acrylate or methacylate polymers and nitrile groups. Without desiring to be bound by theory, it is believed that the higher molecular weight difunctional epoxy material contributes sufficient thermoplastic properties to the thick film layer 36 to enable use of a photocurrable formulation that is substantially devoid of acrylate or methacrylate polymers and nitrile rubber components. Additionally, a photoresist formulation, substantially devoid of acrylate or methacrylate polymers, may have an increased shelf life as compared to the same photoresist formulation containing acrylate or methacrylate polymers.
A method for making the improved photoimaged thick film layer 80 will now be described with reference to FIGS. 7-9. In order to apply the photoresist formulation described above adjacent (e.g., to) the device surface 22 of the substrate (FIG. 7), such as a slicon substrate, a silicon substrate wafer is centered on an appropriate sized chuck of either a resist spinner or conventional wafer resist deposition track. The photoresist formulation mixture is either dispensed by hand or mechanically into the center of the wafer. The chuck holding the wafer is then rotated at a. predetermined number of revolutions per minute to evenly spread the mixture from the center of the wafer to the edge of the wafer. The rotational speed of the wafer may be adjusted or the viscosity of the coating mixture may be altered to vary the resulting resin film thickness. Rotational speeds of 2500 rpm or more may be used. The amount of photoresist formulation applied to device surface 22 should be sufficient to provide the thick film layer 80 having the desired thickness for flow features imaged therein. Accordingly, the thickness of layer 80 after curing may range from about 10 to about 25 microns or more.
The resulting substrate wafer containing the thick film layer 80 is then removed from the chuck either manually or mechanically and placed on either a temperature controlled hotplate or in a temperature controlled oven at a temperature of about 90° C. for about 30 seconds to about 1 minute until the material is "soft" baked. This step removes at least a portion of the solvent from the thick film layer 80 resulting in a partially dried film adjacent the device surface 22 of the substrate 12. The wafer is removed from the heat source and allowed to cool to room temperature.
Pπor to imaging and developing the thick film layer 80, the fluid feed slot 30 is formed in the substrate, such as by an etching process. An exemplary etching process is a dry etch process such as deep reactive ion etching or inductively coupled plasma etching. During the etching process, the photoresist layer 80 acts as an etch stop layer.
In order to define flow features in the thick film layer 80 such as a fluid chamber 82 and fluid supply channel 84, the layer 80 is masked with a mask 86 containing substantially transparent areas 88 and substantially opaque areas 90 thereon. Areas of the thick film layer 80 masked by the opaque areas 90 of the mask 86 will be removed upon developing to provide the flow features described above.
In FIG. 7, a radiation source provides actinic radiation indicated by arrows 92 to image the thick film layer 80. A suitable source of radiation emits actinic radiation at a wavelength within the ultraviolet and visible spectral regions. Exposure of the thick film layer 80 may be from less than about 1 second to 10 minutes or more, such as from about 5 seconds to about one minute, depending upon the amounts of particular epoxy materials and aromatic complex salts being used in the formulation and depending upon the radiation source, distance from the radiation source, and the thickness of the thick film layer 80. The thick film layer 80 may optionally be exposed to electron beam irradiation instead of ultraviolet radiation.
The foregoing procedure is similar to a standard semiconductor lithographic process. The mask 86 is a clear, flat substrate usually glass or quartz with opaque areas 90 defining the areas to be removed from the layer 80 (i.e. a negative acting photoresist layer 80). The opaque areas 90 prevent the ultraviolet light from cross- linking the layer 80 masked beneath it. The exposed areas of the layer 80 provided by the substantially transparent areas 88 of the mask 86 are subsequently baked at a temperature of about 90° C. for about 30 seconds to about 10 minutes, such as from about 1 to about 5 minutes to complete the curing of the thick film layer 80.
The non-imaged areas of the thick film layer 80 are then solubilized by a developer and the solubilized material is removed leaving the imaged and developed thick film layer 80 adjacent the device surface 22 of the substrate 12 as shown in FIG. 8 and in plan view in FIG. 9. The developer comes in contact with the substrate 12 and thick film layer 80 through either immersion and agitation in a tank-like setup or by spraying the developer on the substrate 12 and thick film layer 80. Either spray or immersion will adequately remove the non-imaged material. Illustrative developers
include, for example, butyl cellosolve acetate, a xylene and butyl cellosolve acetate mixture, and C1-6 acetates like butyl acetate. After developing the layer 80, the substrate 12 having the layer 80 is optionally baked at a temperature ranging from about 150° C. to about 200° C, such as from about from about 170° C. to about 190° C. for about 1 minute to about 60 minutes, such as from about 15 to about 30 minutes. Referring again to FIGS. 5 and 6, a formulation, generally in accordance with the first embodiment, was used to make thick film layer 66. The formulation used was as follows:
Table 1
For comparison purposes, a formulation, generally in accordance with the second embodiment, was used to make the thick film layer 72 (FIG. 6) and includes:
Table 2
While the formulation of Table 1 may provide thick film layers 66 with suitable dimensional stability, the planarity of the thick film layer 66 may be significantly improved by use of the formulation in Table 2 as illustrated by the thick film layer 72 in FIG. 6. In addition, the thick film layer 72 made with the formulation of Table 2 provided substantially improved image resolution. For example, such a thick film layer 72 had a resolution of greater than about 10 microns (e.g., 6 microns at 13 to 20 microns thickness), with an aspect ratio of less than about 2:1 (e.g., about 5:1). The increased resolution of the thick film layer 72 as compared to thick film layer 66 is believed to be the result of incorporating the multifunctional epoxy component (EPON SU-8) into the formulation. Compared to the EPON 1007F component, the EPON SU-8 component allows an increase in functionality by 2 per
repeat units, which enables an increase in cross link density and a reduction in swelling during development.
Another aid in improving image resolution of the thick film layer 72 is believed to be the use of the Polyset photoacid generator instead of the CYRACURE component. The Polyset photoacid generator has shown improvements in the rates of reaction and a larger energy window. The increase in the rate of reaction allows the progression of the cationic cure to propagate through the thickness of the thick film layer 72 at a faster rate insuring uniform distribution of cure as a function of depth.
Though epoxy materials provide outstanding strength, chemical resistance, and high temperature durability, epoxies undergo shrinkage during the curing and cooling process which may result in internal stresses within the thick film layer 66 that may provide the imperfections 70 shown in FIG. 5. The stresses may manifest themselves in the form of interfacial delamination or stress cracks through the thick film layer 66. Such stress cracks may cause the surface of the thick film layer 66 to be non-planar which may lead to non uniform etching (pitting and over etching) of the substrate 12 when forming the fluid supply slot 30 by a deep reactive ion etching process.
A technique to remove such stresses in the thick film layer 66 is the incorporation of a rubbery, flexible second phase within the epoxy. This rubbery phase forms soft, stress-relieving domains within the epoxy that will relieve some of the internal stresses and prevent the propagation of cracks. Most rubber phase materials are provided by nitrile groups. The nitrile groups on the rubber backbone enhance the interaction with the epoxy. However, the nitrile groups reduce the chemical resistance and decrease the cure rate of the thick film layer 66.
Another problem that may be evident with formulations for thick film layers is the "edge crispness" after development. After standard imaging and developing of the thick film layer, the flow features may show distortions and surface planarity irregularities 62, as illustrated in FIG. 2. Such surface irregularities may lead to significant problems during lamination of a dry film nozzle plate to a thick film layer. In order for the dry film lamination process to work effectively, a thick film layer should be substantially planar after imaging and development. The formulation of Table 2 more readily satisfies the planar requirements of the thick film layer.
Another formulation which may be used to provide improved thick film layers s illustrated in Table 3 and generally corresponds to the formulation of the first xnbodiment of the disclosure.
Table 3
Thick film layers made with formulations according to Table 3 are expected to exhibit increased dimensional stability over prior art formulations with respect to thermal bonding of components to the thick film layer. Such formulations may be used where higher image resolutions requirements are absent.
With reference now to FIG. 10, subsequent to imaging and developing the thick film layer 80, a nozzle member, such as plate 94, is laminated adjacent (e.g., to) the thick film layer 80. The nozzle plate 94 is substantially rectangular and is aligned with the substrate 12 and thick film layer 80 so that the nozzles 96 are in axial alignment with corresponding fluid ejector actuators 16 on the device surface 22 of the substrate 12 and with the fluid chambers 82 in the thick film layer 80. In the case of a polyimide nozzle plate 94, the nozzle plate 94 may be adhesively attached to the thick film layer 80. hi the case of a photoresist nozzle plate 94, the nozzle plate 94 may be laminated to the thick film layer 80 using pressure and heat.
Having described various aspects and exemplary embodiments and several advantages thereof, it will be recognized by those of ordinary skills that the disclosed embodiments is susceptible to various modifications, substitutions and revisions within the spirit and scope of the appended claims.
Claims
1. A dimensionally stable thick film layer for a micro-fluid ejection head, the dimensionally stable thick film layer being derived from a composition comprising a difunctional epoxy component having a weight average molecular weight ranging from about 2500 to about 4000 Daltons, a photoacid generator, an aryl ketone solvent, and an adhesion enhancing component, wherein, upon curing, the dimensionally stable thick film layer has a cross-link density that increases the dimensional stability of the thick film layer sufficient to provide flow features therein having substantially vertical walls.
2. The thick film layer of claim 1, wherein the aryl ketone solvent comprises acetophenone.
3. The thick film layer of claim 1, wherein the adhesion enhancer comprises an alkoxysilane compound.
4. The thick film layer of claim 3, wherein the methoxysilane compound comprises gamma-glycidoxypropyltrimethoxysilane.
5. The thick film layer of claim 1, wherein the thick film layer is derived from a composition comprising from about 35 to about 55 percent by weight difunctional epoxy compound, from about 0.5 to about 15 percent by weight photoacid generator and from about 0.5 to about 5.0 percent by weight adhesion enhancer, and the balance solvent.
6. A thick film layer for a micro-fluid ejection head, comprising a negative photoresist layer derived from a composition comprising a multi-functional epoxy compound, a difunctional epoxy compound, a photoacid generator devoid of aryl sulfonium salts, an adhesion enhancer, and an aryl ketone solvent, wherein the negative photoresist layer has increased planarity subsequent to photoimaging and developing the photoresist layer.
7. The thick film layer of claim 6, wherein the photoacid generator comprises a diaryliodonium hexafluoroantimonate.
8. The thick film layer of claim 6, wherein the composition includes substantially equal parts of the multi-functional epoxy compound and the difunctional epoxy compound.
9. The thick film layer of claim 6, wherein the aryl ketone solvent comprises acetophenone.
10. The thick film layer of claim 6, wherein the adhesion enhancer comprises an alkoxysilane compound.
11. The thick film layer of claim 10, wherein the methoxysilane compound comprises gamma-glycidoxypropyltrimethoxysilane.
12. The thick film layer of claim 6, wherein the thick film layer comprises from about 30 to about 50 percent by weight multifunctional epoxy compound, from about 30 to about 50 percent by weight difunctional epoxy compound, from about 10 to about 25 percent by weight photoacid generator and from about 0.05 to about 2.0 percent by weight adhesion enhancer.
13. A method for increasing the planarity of a surface of a thick film layer after photoimaging and developing flow features therein for a micro-fluid ejection head, the method comprising: applying a negative photoresist layer adjacent a device surface of a substrate, wherein the negative photoresist layer is derived from a multi-functional epoxy compound, a difunctional epoxy compound, a photoacid generator devoid of aryl sulfonium salts, an adhesion enhancer, and an aryl ketone solvent; imaging flow features in the photoresist layer; and developing the imaged photoresist layer to provide the plurality of flow features therein and the substantially planar thick film layer surface.
14. The method of claim 13, wherein the photoacid generator comprises a diaryliodonium hexafluoroantimonate.
15. The method of claim 13, wherein the negative photoresist layer includes substantially equal parts of the multi-functional epoxy compound and the difunctional epoxy compound.
16. The method of claim 13, wherein photoresist layer is applied to the substrate by spin coating the photoresist layer onto the substrate.
17. The method of claim 13, wherein the adhesion enhancer comprises gamma- glycidoxypropyltrimethoxysilane.
18. A micro-fluid ejection head comprising a substrate having a device surface, the ejection head comprising: a photoimaged and developed thick film layer applied adjacent the device surface of the substrate, the thick film layer comprising a negative photoresist layer derived from a composition comprising a multi-functional epoxy compound, a difunctional epoxy compound, a photoacid generator devoid of aryl sulfonium salts, an adhesion enhancer, and an aryl ketone solvent, wherein the negative photoresist layer has increased planarity subsequent to photoimaging and developing flow features in the photoresist layer; and a nozzle member adjacent the imaged and developed thick film layer.
19. A micro-fluid ejection head comprising a thick film layer having an image resolution of greater than about 10 microns with an aspect ratio of less than about 2:1.
20. The micro-fluid ejection head of claim 19, wherein the image resolution is about 6 microns for thicknesses of about 13 to about 20 microns), with an aspect ratio of about 5:1.
Priority Applications (1)
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EP06815601A EP1986856A2 (en) | 2005-09-30 | 2006-09-28 | Thick film layers and methods relating thereto |
Applications Claiming Priority (4)
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US72276705P | 2005-09-30 | 2005-09-30 | |
US60/722,767 | 2005-09-30 | ||
US11/361,731 US7571979B2 (en) | 2005-09-30 | 2006-02-24 | Thick film layers and methods relating thereto |
US11/361,731 | 2006-02-24 |
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WO2007041173A2 true WO2007041173A2 (en) | 2007-04-12 |
WO2007041173A3 WO2007041173A3 (en) | 2009-04-30 |
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PCT/US2006/037727 WO2007041173A2 (en) | 2005-09-30 | 2006-09-28 | Thick film layers and methods relating thereto |
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EP (1) | EP1986856A2 (en) |
TW (1) | TW200716377A (en) |
WO (1) | WO2007041173A2 (en) |
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KR101388519B1 (en) | 2007-07-23 | 2014-04-24 | 주식회사 동진쎄미켐 | Method Of Fabricating Thin Film Transistor Substrate And Photosensitive Resin Composition Used To The Same |
AU2009356743B2 (en) * | 2009-12-17 | 2014-11-06 | Essilor International | Heat-curable epoxy functional composition and transparent heat-cured caustic-resistant hard-coatings prepared therefrom |
US20110318882A1 (en) | 2010-06-24 | 2011-12-29 | Xiaoming Wu | Method of restricting chip movement upon bonding to rigid substrate using spray coatable adhesive |
US8394575B2 (en) * | 2010-09-30 | 2013-03-12 | Lexmark International, Inc. | Formulations for environmentally friendly photoresist film layers |
US8678555B1 (en) * | 2012-11-01 | 2014-03-25 | Funai Electric Co., Ltd. | Encapsulation of inkjet heater chip for ion beam cross-section polishing and method of preparing chip cross-section sample |
US9599893B2 (en) * | 2014-09-25 | 2017-03-21 | Canon Kabushiki Kaisha | Production process for optically shaped product and production process for liquid discharge head |
US11577513B2 (en) | 2020-10-06 | 2023-02-14 | Funai Electric Co., Ltd. | Photoimageable nozzle member for reduced fluid cross-contamination and method therefor |
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Also Published As
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US20090098488A1 (en) | 2009-04-16 |
US20090269707A1 (en) | 2009-10-29 |
TW200716377A (en) | 2007-05-01 |
US7571979B2 (en) | 2009-08-11 |
EP1986856A2 (en) | 2008-11-05 |
WO2007041173A3 (en) | 2009-04-30 |
US20070076059A1 (en) | 2007-04-05 |
US8007990B2 (en) | 2011-08-30 |
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