WO1998010116A1 - Alimentation par buse a ultrasons pour reseaux de couches minces a depot en phase vapeur activees par plasma - Google Patents

Alimentation par buse a ultrasons pour reseaux de couches minces a depot en phase vapeur activees par plasma Download PDF

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Publication number
WO1998010116A1
WO1998010116A1 PCT/US1997/015806 US9715806W WO9810116A1 WO 1998010116 A1 WO1998010116 A1 WO 1998010116A1 US 9715806 W US9715806 W US 9715806W WO 9810116 A1 WO9810116 A1 WO 9810116A1
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WO
WIPO (PCT)
Prior art keywords
monomer
atomizing nozzle
reactor
liquid monomer
delivery system
Prior art date
Application number
PCT/US1997/015806
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English (en)
Inventor
Omprakash S. Kolluri
Original Assignee
Talison Research
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Talison Research filed Critical Talison Research
Publication of WO1998010116A1 publication Critical patent/WO1998010116A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/62—Plasma-deposition of organic layers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C23C16/4486—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by producing an aerosol and subsequent evaporation of the droplets or particles

Definitions

  • the present invention generally relates to plasma deposited functional film networks. More particularly, the invention relates to an ultrasonic nozzle system for plasma polymerization.
  • the partial pressure of the monomer vapor in the carrier gas is high enough to deliver sufficient concentrations of monomer to the plasma reactor.
  • high boiling and/or low vapor pressure monomer it is difficult to entrain enough monomer vapor in the carrier gas without heating the monomer to high temperatures. This is often not possible since some of the noted monomers are thermally sensitive and either degrade upon heating or are susceptible to "runaway polymerization".
  • U.S. Patent No. 5,451,260 discloses a system for delivering liquid materials to a reactor using ultrasonic nozzles wherein the liquid monomer is fed by gravity from a storage container to the ultrasonic nozzle via a series of valves. The nozzle then feeds the monomer to the reactor as a mist.
  • the amount of liquid monomer delivered to the nozzles is determined by a complex and sequential operation of solenoid valves.
  • the system provides for a delivery tube to be filled with a liquid monomer which is subsequently delivered to the nozzle. Excess liquid monomer is then drained into a storage container.
  • the noted system further requires precise operation of complex control systems. This is often quite difficult to achieve. It is also well known in the art that, when employing gravity feed, the amount of liquid delivered to the reactor is proportional to the liquid level in the container. As the liquid level decreases, the static head and the rate at which the liquid drains into the discharge tube are reduced. By relying on timing sequences of valves with a gravity drain, the amount of liquid delivered can, and in many instances will, vary with the level in the reservoir.
  • the solenoid valves on the noted system are operated by electrical means. During normal operation, the heat generated by the electrical devices increases the temperature of the valve body. Under these circumstances, it has been found that thermally sensitive materials, such as those that polymerize upon exposure to heat, clog the valves. Moreover, solutions wherein the solute crystallizes, present similar problems.
  • a monomer delivery system for a chemical vapor deposition apparatus comprising at least one ultrasonic atomizing nozzle disposed in the reactor chamber of the chemical vapor deposition apparatus for supplying a vaporized liquid monomer to the reactor chamber for depositing a film on at least one substrate contained therein, a supply vessel for storing liquid monomer, metering means disposed between the supply vessel and the atomizing nozzle for controlling the amount of liquid monomer delivered to the atomizing nozzle and pulse damping means in communication with said metering means for providing a substantially even flow of liquid monomer to said atomizing nozzle.
  • Figure 1 is a schematic diagram of a CVD system constructed in accordance with a preferred embodiment of the present invention.
  • FIGS 2-5 are schematic diagrams of additional embodiments of the CVD system according to the invention.
  • the present invention substantially reduces or eliminates all of the problems associated with the prior art.
  • the invention comprises a system and method for delivering complex monomers to RF plasma polymerization reactors using an ultrasonic nozzle and precision fluid metering pumps equipped with a pulse damping devices.
  • the system provides a steady stream of monomer, in the form of a uniform atomized fine mist, to the RF plasma polymerization reactor at a very precise and controlled rate.
  • the precise controls of the invention are particularly important when depositing plasma polymerized films on substrates which commonly move through the plasma region of the RF plasma polymerization reactor, such as a moving film, fabric, or web.
  • the ultrasonic nozzle delivery system 10 of the invention which includes a monomer supply vessel 14, monomer metering means to control the amount of liquid monomer delivered to the ultrasonic nozzle(s) and CVD reactor 40 having a chamber 41 therein.
  • the monomer metering means comprises one or more metering pumps.
  • the reactor chamber 41 can be any type of conventional hot wall or cold wall
  • the CVD reactor chamber and is preferably made of stainless steel or a quartz tube. Contained within the reactor is at least one susceptor 43 which supports the substrates 68 to be coated.
  • the reactor chamber 41 further includes heating means. According to the invention, the heating means comprises one or more electrodes 70.
  • the electrodes 70 are connected to an external power source 71 and are capable of heating the substrates 68 to any desired temperature. A typical range of operating temperatures is from room temperature up to 1200°C.
  • the monomer supply vessel 14 of the system 10 is adapted to sealably store the liquid monomer.
  • the supply vessel 14 is preferably constructed of stainless steel or other like material.
  • the monomer supply vessel 14 includes means for maintaining the vessel 14 at a constant temperature. This is preferably achieved by enclosing the sides of the vessel 14 in a electrical heating jacket 16 or a heating jacket through which a heat transfer fluid 18 is circulated.
  • the monomer supply vessel 14 is also equipped with a transfer tube 20 for introducing an inert gas.
  • the transfer tube 20 includes a conventional check and needle valves 25, 27.
  • a relief valve 22 is also provided to prevent excessive pressure build up. This feature is provided so that "inert blanketing" of the monomer can be achieved to prevent degradation of monomers that are sensitive to exposure to air or oxygen.
  • a discharge tube 24 and associated discharge valve 23 are also provided to drain the monomer prior cleaning the vessel 14.
  • the feed tubes 30a, 30b submerged below the liquid level proximate the bottom of the supply vessel 14, facilitate the transfer of the liquid monomer to metering pumps 32a, 32b.
  • the metering pumps 32a, 32b are preferably positive displacement pumps such as those manufactured by Fluid Metering Incorporated of Oyster Bay, New York.
  • the pumps can comprise conventional gear pumps wherein in the pumping action is created by a pair of gears rotating counter to one another and pumping the fluid entrained in the space between the enmeshed gears.
  • various positive displacement pumps capable of self priming and pulling liquid up from a reservoir can be employed within the scope of this invention.
  • the metering pumps 32a, 32b are connected to ultrasonic nozzles 36a, 36b proximate the discharge ends 35a, 35b of the delivery tubes 30a, 30b.
  • the nozzles 36a, 36b are of conventional construction, and by way of example can be of a type manufactured by Sono-Tek. Milton, New York.
  • the ultrasonic nozzles 36a, 36b are connected to the reactor chamber 40 and preferably deliver the monomer mist directly to the reactor chamber 41.
  • the monomer mist is delivered to a distant location inside the reactor via a delivery tube.
  • direct discharge of the atomized mist is employed.
  • the liquid monomer from positive displacement pump 32a is directly fed to a respective ultrasonic nozzle 36a.
  • a separate pump 32b and nozzle 36b combination is employed to deliver the atomized mist to a different position in the reactor chamber 41.
  • a key feature of the present invention is the pulse damping means which provides a substantially even flow of liquid monomer at a substantially constant pressure to each nozzle 36a, 36b.
  • the pulse damping means can be an integral feature of metering pumps 32a, 32b or separate components (not shown).
  • the pulse damping means of the invention are designed and adapted to smooth out the pressure variations inherent in the discharge of positive displacement pumps.
  • the pulse damping means comprises a conventional pulse damper such as that manufactured by Fluid Metering Incorporated. Oyster Bay, New York. Applicant has specifically found that a unique synergism is achieved between the metering means (i.e., pumps 32a, 32b) and pulse damping means of the invention. This unique synergism provides for a precisely controlled, substantially uniform flow of liquid monomer to and through the ultrasonic nozzles. As a result, substantially uniform CVD films can be achieved on a variety of stationary and moving substrates.
  • the ultrasonic nozzles are affixed to a side of the reactor 40 such that the ultrasonic nozzle tips 37, 38 direct vaporized liquid monomer in a substantially horizontal direction toward the substrates 68 to be coated.
  • any number e.g., from 1 to 6) of the ultrasonic nozzles 36a, 36b can be employed within the scope of the invention.
  • the use of multiple nozzles permits the formation of complex films on a multitude of substrate shapes and orientations.
  • a conventional microprocessor 60 can be employed to control the delivery system, including the supply vessel valves 22, 25, 27, metering pumps 32a, 32b and nozzles 36a, 36b.
  • the microprocessor 60 can also be adapted to control operation of the reactor chamber electrodes 70, vacuum pump 45 and associated exhaust valve 44.
  • a single pump 38 is employed to feed a set of ultrasonic nozzles 39a, 39b via line supply line 33.
  • the manifold 50 is provided with supply valves 5 la, 51b, to assure that an equal amount of liquid monomer is being delivered to each nozzle 39a, 39b.
  • various pump/nozzle combinations can be employed to deliver different fluids to the reactor at the same time or in a programmed sequence.
  • a series of ultrasonic nozzles may be employed (or a single unit) which are placed in such a manner that when depositing plasma polymerized films on to films, fabrics or webs, there is a uniform distribution of monomer mist being transported through the plasma deposition zone.
  • the monomer mist or aerosol be fed into the zone 69 that is encompassed by the electrodes 70 of the RF plasma polymerization reactor 40 such that the monomer mist or aerosol is fed directly into the RF field and the zone 69 where the substrate 68 to be coated is located.
  • the electrodes 70 in the reactor and the substrates 68 can be arranged in any orientation in 360° space since the mist will be delivered to the substrate regardless of its orientation.
  • electrode 75 is curved to follow the contour of a drum 72 which transports a continuous web type substrate 73 on its surface.
  • a uniform coating of the substrate is assured.
  • This example illustrates a completely different and novel orientation of the electrode 75 and substrate 73.
  • a continuous fabric or web type substrate 74 is transported through a festoon type arrangement of rollers 80.
  • the continuous web type substrate 74 is transported between electrodes 78 and baffles 79.
  • the ultrasonic delivery nozzles 81 are disposed proximate the rear wall of the reactor 40 such that the monomer mist is directed into the space between the electrodes 78 and, thus, into the ionization zone 90.
  • the system described herein is designed to assure a uniform distribution of the monomer into the ionization zone and thus the zone of film deposition. It will be apparent to those skilled in the art that there are several possible approaches that can be used to orient the substrate, electrodes and the delivery of the monomer mist depending on the specific requirements of the plasma deposition system.
  • the vapor pressure of this monomer is so low at temperatures much below its boiling point that even when inert gas is bubbled through a container of this material, insufficient monomer is delivered to a process vessel such a plasma polymerization reactor.
  • This materials is also thermally sensitive and autopolymerizes into a high molecular weight gel when heated to temperatures above 60°C. Thus, heating the monomer to increase its vapor pressure is not possible. It is also impossible to deliver any significant quantity of this monomer to a plasma polymerization reactor using conventional methods.
  • 2-Hydroxyethylmethacrylate was delivered to a 4.0 liter plasma reactor with internal electrodes spaced 2.0 inches apart and driven by a 200 watt RF generator operating at 13.56 Mhz.
  • the reaction chamber was connected to an Alcatel 2020 CP vacuum pump with a pumping capacity of 16 cfm.
  • a manual throttle valve was employed to control the reaction chamber pressure independent of the monomer flow.
  • the monomer which is a iiquid at room temperature, was placed in an 150 ml round bottom flask equipped with a stopper through which a VX tubing had been inserted.
  • the flask was filled to the 50% level with the monomer.
  • the other end of the tubing was connected to the suction side of the displacement pump.
  • the output of the pump was fed directly to the feed port of the ultrasonic nozzle.
  • the nozzle was mounted directly on the reaction chamber such that the mist is directed between the electrodes, as illustrated in Figure 3.
  • a single nozzle was adequate for directing the mist towards the vertically oriented substrate in sufficient quantity and in a uniform manner.
  • a silicone tubing was placed equidistant from the two electrodes and secured on a plastic fixture located at the base of the reactor.
  • the stroke setting on the pump was set for 300 strokes per minute which delivers the monomer at a rate of 30 cc/min.
  • the liquid was atomized by the ultrasonic nozzle and at this flow rate the reactor is maintained at a pressure of 300 mTorr.
  • RF power is set at 120 watts for a period of five (5) minutes.
  • the tubing was removed and examined for evidence of a plasma deposited film.
  • the presence of the plasma polymerized film was detected by the change in the color of the tubing from its natural clear state to one having a coating with a very visible amber color.
  • the presence of a substantial thickness of coating was determined by staining the coated tubing with Congo Red. A very intense red color was developed on the surface of the coating and this color did not wash away indicating the coating was firmly adhered on the surface.
  • the monomer 1 ,6-hexanediamine is a difunctional amine monomer, with a six carbon spacer, and offers an opportunity to deposit amine functional films where the amine group is spaced a sufficient distance from the surface of the substrate to enhance their reactivity.
  • This monomer is, however, a solid at room temperature having a melting point of 42°C, is very corrosive, and has a high boiling point of 204°C. Feeding this monomer into a plasma reactor poses several problems. For example, if an inert gas is used to bubble though the heated liquid, the amount of monomer delivered to the reactor is insufficient to allow deposition of a thick enough film with the requisite functional density.
  • the density of functional groups is less than 0.1 nmoles/cm . This is because much of the reactor pressure is derived from the presence of high concentration of the inert carrier gas rather than the monomer itself.
  • An additional problem that is encountered is the cooling of the vapor in the delivery tube and subsequent blockage due to solidification of this cooled and liquefied vapor in the delivery tube.
  • the noted monomer was mixed with less than 10% of another amine monomer, such as cthylene diamine which serves to maintain the mixture in a liquid state.
  • This mixture was then delivered to a plasma polymerization reactor using the ultrasonic nozzle system illustrated in Figure 3.
  • the plasma reactor was a 4.0 liter cylindrical vessel with internal electrodes spaced 2.0 inches apart and driven by a 200 watt RF generator operating at 13.56 Mhz.
  • the reaction chamber was connected to an Alcatel 2020 CP vacuum pump with a pumping capacity of 16 cfm.
  • a manual throttle valve was employed to control the reaction chamber pressure independent of the monomer flow.
  • the monomer mixture which is a liquid at room temperature was placed in an 150 ml round bottom flask equipped with a stopper through which a " tubing has been inserted.
  • the flask was filled to the 50% level with the monomer.
  • the other end of the tubing was connected to the suction side of the pump.
  • the output of the pump was fed directly to the feed port of the ultrasonic nozzle.
  • the nozzle was mounted directly on the reaction chamber such that the mist is directed between the electrodes (as shown in Figure 3) except that the mist was directed in a plane parallel to the plane in which the substrate to be coated is located.
  • the reactor used in this example had a small volume, a single nozzle was adequate for directing the mist towards petri dishes containing 120 ⁇ m polystyrene beads.
  • the petri dishes containing the beads were placed on top of a plastic bar placed horizontally at the bottom of the reactor chamber. Instead of the flow being vertically directed as shown on Figure 3, the mist was directed horizontally into the chamber above the petri dishes containing the polystyrene beads.
  • the stroke setting on the pump was set for 600 strokes per minute which delivers the monomer at a rate of 60 cc/min.
  • the liquid was atomized by the ultrasonic nozzle and at this flow rate the reactor is maintained at a pressure of 450 mTorr.
  • RF power is set at 90 watts for a period of three (3) beads were removed from the reactor.
  • the beads were washed in methanol and tested for the presence of amine functional groups on the surface.
  • Chemical analysis using a ninhydrin assay for primary amines showed a concentration of 1.15 ⁇ moles/gm. Since the beads have a surface area of 309 cm /gm, this equates to a surface functional density of 3.7 nmoles/cm . From these examples, it will be apparent to those skilled in the art that many possible electrode orientations, substrates and nozzle locations (such as that illustrated in Figures 1 through Figure 5), can be employed to deposit plasma enhanced CVD films on a variety of stationary and moving substrates. Further, both single monomers and mixtures of monomers can be delivered to plasma polymerization reactors for the purpose of depositing plasma enhanced CVD films on a variety of substrates using the methods described in this invention.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

Un système de distribution de monomères destiné à un appareil de dépôt en phase vapeur par procédé chimique, comprend au moins une buse d'atomisation à ultrasons disposée dans la chambre du réacteur de l'appareil de dépôt en phase vapeur par procédé chimique, destinée à l'alimentation en momomère liquide vaporisé de la chambre du réacteur afin de procéder au dépôt d'une couche mince sur au moins un substrat contenu dans celle-ci, une cuve d'alimentation destinée à contenir ledit monomère liquide, un moyen de dosage disposé entre la cuve d'alimentation et la buse d'atomisation afin de réguler la quantité de monomère liquide distribué à la buse d'atomisation, ainsi qu'un moyen d'amortissement d'impulsions en communication avec ledit moyen de dosage afin de fournir un écoulement régulier de monomère liquide à la buse d'atomisation, à une pression sensiblement constante.
PCT/US1997/015806 1996-09-05 1997-09-04 Alimentation par buse a ultrasons pour reseaux de couches minces a depot en phase vapeur activees par plasma WO1998010116A1 (fr)

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US2551296P 1996-09-05 1996-09-05
US60/025,512 1996-09-05

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WO1999064085A1 (fr) * 1998-06-09 1999-12-16 Franz Herbst Procede pour produire des surfaces biocompatibles
WO2000035601A1 (fr) * 1998-12-16 2000-06-22 Battelle Memorial Institute Procede de fabrication d'une matiere composite de polymere electroluminescent
US6207238B1 (en) 1998-12-16 2001-03-27 Battelle Memorial Institute Plasma enhanced chemical deposition for high and/or low index of refraction polymers
US6207239B1 (en) 1998-12-16 2001-03-27 Battelle Memorial Institute Plasma enhanced chemical deposition of conjugated polymer
US6217947B1 (en) 1998-12-16 2001-04-17 Battelle Memorial Institute Plasma enhanced polymer deposition onto fixtures
US6224948B1 (en) 1997-09-29 2001-05-01 Battelle Memorial Institute Plasma enhanced chemical deposition with low vapor pressure compounds
US6228434B1 (en) 1998-12-16 2001-05-08 Battelle Memorial Institute Method of making a conformal coating of a microtextured surface
US6268695B1 (en) 1998-12-16 2001-07-31 Battelle Memorial Institute Environmental barrier material for organic light emitting device and method of making
US6274204B1 (en) 1998-12-16 2001-08-14 Battelle Memorial Institute Method of making non-linear optical polymer
US6358570B1 (en) 1999-03-31 2002-03-19 Battelle Memorial Institute Vacuum deposition and curing of oligomers and resins
US6413645B1 (en) 2000-04-20 2002-07-02 Battelle Memorial Institute Ultrabarrier substrates
US6492026B1 (en) 2000-04-20 2002-12-10 Battelle Memorial Institute Smoothing and barrier layers on high Tg substrates
US6506461B2 (en) 1999-03-31 2003-01-14 Battelle Memorial Institute Methods for making polyurethanes as thin films
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US6632470B2 (en) 2001-01-31 2003-10-14 Percardia Methods for surface modification
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WO2006092614A3 (fr) * 2005-03-03 2006-11-30 Univ Durham Procede et appareil pour former un revetement sur un substrat
CN1314301C (zh) * 2002-04-10 2007-05-02 陶氏康宁爱尔兰有限公司 大气压等离子体组件
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4529427A (en) * 1977-05-19 1985-07-16 At&T Bell Laboratories Method for making low-loss optical waveguides on an industrial scale
US4640221A (en) * 1985-10-30 1987-02-03 International Business Machines Corporation Vacuum deposition system with improved mass flow control
US5322710A (en) * 1990-10-05 1994-06-21 U.S. Philips Corporation Method of providing a substrate with a surface layer from a vapor
US5451260A (en) * 1994-04-15 1995-09-19 Cornell Research Foundation, Inc. Method and apparatus for CVD using liquid delivery system with an ultrasonic nozzle
US5462014A (en) * 1990-03-09 1995-10-31 Nippon Telegraph And Telephone Corporation Apparatus for growing a thin metallic film
US5609897A (en) * 1995-04-07 1997-03-11 Abbott Laboratories Powdered beverage concentrate or additive fortified with calcium and vitamin D
US5620524A (en) * 1995-02-27 1997-04-15 Fan; Chiko Apparatus for fluid delivery in chemical vapor deposition systems

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4529427A (en) * 1977-05-19 1985-07-16 At&T Bell Laboratories Method for making low-loss optical waveguides on an industrial scale
US4640221A (en) * 1985-10-30 1987-02-03 International Business Machines Corporation Vacuum deposition system with improved mass flow control
US5462014A (en) * 1990-03-09 1995-10-31 Nippon Telegraph And Telephone Corporation Apparatus for growing a thin metallic film
US5322710A (en) * 1990-10-05 1994-06-21 U.S. Philips Corporation Method of providing a substrate with a surface layer from a vapor
US5451260A (en) * 1994-04-15 1995-09-19 Cornell Research Foundation, Inc. Method and apparatus for CVD using liquid delivery system with an ultrasonic nozzle
US5620524A (en) * 1995-02-27 1997-04-15 Fan; Chiko Apparatus for fluid delivery in chemical vapor deposition systems
US5609897A (en) * 1995-04-07 1997-03-11 Abbott Laboratories Powdered beverage concentrate or additive fortified with calcium and vitamin D

Cited By (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6224948B1 (en) 1997-09-29 2001-05-01 Battelle Memorial Institute Plasma enhanced chemical deposition with low vapor pressure compounds
US6656537B2 (en) 1997-09-29 2003-12-02 Battelle Memorial Institute Plasma enhanced chemical deposition with low vapor pressure compounds
US6627267B2 (en) 1997-09-29 2003-09-30 Battelle Memorial Institute Plasma enhanced chemical deposition with low vapor pressure compounds
WO1999064085A1 (fr) * 1998-06-09 1999-12-16 Franz Herbst Procede pour produire des surfaces biocompatibles
US6497598B2 (en) 1998-12-16 2002-12-24 Battelle Memorial Institute Environmental barrier material for organic light emitting device and method of making
US6497924B2 (en) 1998-12-16 2002-12-24 Battelle Memorial Institute Method of making non-linear optical polymer
US6228434B1 (en) 1998-12-16 2001-05-08 Battelle Memorial Institute Method of making a conformal coating of a microtextured surface
US6228436B1 (en) 1998-12-16 2001-05-08 Battelle Memorial Institute Method of making light emitting polymer composite material
US6268695B1 (en) 1998-12-16 2001-07-31 Battelle Memorial Institute Environmental barrier material for organic light emitting device and method of making
US6274204B1 (en) 1998-12-16 2001-08-14 Battelle Memorial Institute Method of making non-linear optical polymer
US6613395B2 (en) 1998-12-16 2003-09-02 Battelle Memorial Institute Method of making molecularly doped composite polymer material
US6811829B2 (en) 1998-12-16 2004-11-02 Battelle Memorial Institute Method of making a coating of a microtextured surface
WO2000035601A1 (fr) * 1998-12-16 2000-06-22 Battelle Memorial Institute Procede de fabrication d'une matiere composite de polymere electroluminescent
US6217947B1 (en) 1998-12-16 2001-04-17 Battelle Memorial Institute Plasma enhanced polymer deposition onto fixtures
US6909230B2 (en) 1998-12-16 2005-06-21 Battelle Memorial Institute Method of making molecularly doped composite polymer material
US6207239B1 (en) 1998-12-16 2001-03-27 Battelle Memorial Institute Plasma enhanced chemical deposition of conjugated polymer
US6509065B2 (en) 1998-12-16 2003-01-21 Battelle Memorial Institute Plasma enhanced chemical deposition of conjugated polymer
US6522067B1 (en) 1998-12-16 2003-02-18 Battelle Memorial Institute Environmental barrier material for organic light emitting device and method of making
US6544600B2 (en) 1998-12-16 2003-04-08 Battelle Memorial Institute Plasma enhanced chemical deposition of conjugated polymer
US6207238B1 (en) 1998-12-16 2001-03-27 Battelle Memorial Institute Plasma enhanced chemical deposition for high and/or low index of refraction polymers
US6570325B2 (en) 1998-12-16 2003-05-27 Battelle Memorial Institute Environmental barrier material for organic light emitting device and method of making
US6506461B2 (en) 1999-03-31 2003-01-14 Battelle Memorial Institute Methods for making polyurethanes as thin films
US6358570B1 (en) 1999-03-31 2002-03-19 Battelle Memorial Institute Vacuum deposition and curing of oligomers and resins
US8955217B2 (en) 1999-10-25 2015-02-17 Samsung Display Co., Ltd. Method for edge sealing barrier films
US6573652B1 (en) 1999-10-25 2003-06-03 Battelle Memorial Institute Encapsulated display devices
US6548912B1 (en) 1999-10-25 2003-04-15 Battelle Memorial Institute Semicoductor passivation using barrier coatings
US6923702B2 (en) 1999-10-25 2005-08-02 Battelle Memorial Institute Method of making encapsulated display devices
US6492026B1 (en) 2000-04-20 2002-12-10 Battelle Memorial Institute Smoothing and barrier layers on high Tg substrates
US6413645B1 (en) 2000-04-20 2002-07-02 Battelle Memorial Institute Ultrabarrier substrates
US7455892B2 (en) 2000-10-04 2008-11-25 Dow Corning Ireland Limited Method and apparatus for forming a coating
US6632470B2 (en) 2001-01-31 2003-10-14 Percardia Methods for surface modification
US6623861B2 (en) 2001-04-16 2003-09-23 Battelle Memorial Institute Multilayer plastic substrates
WO2003085693A1 (fr) * 2002-04-10 2003-10-16 Dow Corning Ireland Limited Ensemble de production de plasma a pression atmospherique
US7678429B2 (en) * 2002-04-10 2010-03-16 Dow Corning Corporation Protective coating composition
CN100437884C (zh) * 2002-04-10 2008-11-26 陶氏康宁爱尔兰有限公司 大气压等离子体组件
CN1314301C (zh) * 2002-04-10 2007-05-02 陶氏康宁爱尔兰有限公司 大气压等离子体组件
US8900366B2 (en) 2002-04-15 2014-12-02 Samsung Display Co., Ltd. Apparatus for depositing a multilayer coating on discrete sheets
US9839940B2 (en) 2002-04-15 2017-12-12 Samsung Display Co., Ltd. Apparatus for depositing a multilayer coating on discrete sheets
WO2003101621A2 (fr) 2002-06-01 2003-12-11 Surface Innovations Limited Application d'un materiau de formation de revetement sur au moins un substrat
WO2006021670A3 (fr) * 2004-08-06 2006-05-04 Synergies Pour Equipements En Dispositif d'introduction dans une enceinte de precurseurs liquides en mode pulse avec mesure et controle du debit
FR2874028A1 (fr) * 2004-08-06 2006-02-10 Qualiflow Sa Sa Dispositif d'introduction dans une enceinte de precurseurs liquides en mode pulse avec mesure et controle du debit
GB2437235A (en) * 2005-03-03 2007-10-17 Univ Durham Method and apparatus for producing a coating of substrate
WO2006092614A3 (fr) * 2005-03-03 2006-11-30 Univ Durham Procede et appareil pour former un revetement sur un substrat
US20090318609A1 (en) * 2005-04-18 2009-12-24 Jas Pal Singh Badyal Method for producing a nitrogen functionalised surface
US8859056B2 (en) 2005-05-12 2014-10-14 Dow Corning Ireland, Ltd. Bonding an adherent to a substrate via a primer
US9822454B2 (en) 2006-12-28 2017-11-21 3M Innovative Properties Company Nucleation layer for thin film metal layer formation
US10950821B2 (en) 2007-01-26 2021-03-16 Samsung Display Co., Ltd. Method of encapsulating an environmentally sensitive device
US9184410B2 (en) 2008-12-22 2015-11-10 Samsung Display Co., Ltd. Encapsulated white OLEDs having enhanced optical output
US9362530B2 (en) 2008-12-22 2016-06-07 Samsung Display Co., Ltd. Encapsulated white OLEDs having enhanced optical output
US9337446B2 (en) 2008-12-22 2016-05-10 Samsung Display Co., Ltd. Encapsulated RGB OLEDs having enhanced optical output
US8904819B2 (en) 2009-12-31 2014-12-09 Samsung Display Co., Ltd. Evaporator with internal restriction
CN102744024A (zh) * 2011-04-22 2012-10-24 苏州市奥普斯等离子体科技有限公司 一种低温等离子体接枝汽化方法及装置
CN111111799A (zh) * 2019-12-26 2020-05-08 重庆创芯生物科技有限公司 一种微流控芯片表面亲水改性的方法

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