US20150103504A1 - Surface properties of polymeric materials with nanoscale functional coating - Google Patents
Surface properties of polymeric materials with nanoscale functional coating Download PDFInfo
- Publication number
- US20150103504A1 US20150103504A1 US14/579,464 US201414579464A US2015103504A1 US 20150103504 A1 US20150103504 A1 US 20150103504A1 US 201414579464 A US201414579464 A US 201414579464A US 2015103504 A1 US2015103504 A1 US 2015103504A1
- Authority
- US
- United States
- Prior art keywords
- plasma
- layer
- precursor molecules
- reacted
- graphed
- Prior art date
- Legal status (The legal status 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 status listed.)
- Abandoned
Links
Images
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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/18—Printed circuits structurally associated with non-printed electric components
- H05K1/182—Printed circuits structurally associated with non-printed electric components associated with components mounted in the printed circuit board, e.g. insert mounted components [IMC]
- H05K1/185—Components encapsulated in the insulating substrate of the printed circuit or incorporated in internal layers of a multilayer circuit
-
- 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
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
- B05D3/141—Plasma treatment
- B05D3/142—Pretreatment
- B05D3/144—Pretreatment of polymeric substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/14—Surface shaping of articles, e.g. embossing; Apparatus therefor by plasma treatment
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0005—Other surface treatment of glass not in the form of fibres or filaments by irradiation
- C03C23/006—Other surface treatment of glass not in the form of fibres or filaments by irradiation by plasma or corona discharge
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/284—Applying non-metallic protective coatings for encapsulating mounted components
-
- 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
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
- B05D3/141—Plasma treatment
- B05D3/142—Pretreatment
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/31—Pre-treatment
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0183—Dielectric layers
- H05K2201/0195—Dielectric or adhesive layers comprising a plurality of layers, e.g. in a multilayer structure
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/09—Shape and layout
- H05K2201/09818—Shape or layout details not covered by a single group of H05K2201/09009 - H05K2201/09809
- H05K2201/09872—Insulating conformal coating
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/09—Treatments involving charged particles
- H05K2203/095—Plasma, e.g. for treating a substrate to improve adhesion with a conductor or for cleaning holes
Definitions
- This application is directed, in general, to a process for depositing films, the films formed by the process and, more specifically, to a process for forming conformal surface film coatings for protecting electronic and other devices.
- the device comprises a substrate having a component-side surface.
- the device comprises a moisture protection film covering the component-side surface.
- the moisture protection film includes a first water layer bonded to component-side surface that is an activated surface, wherein the activated surface has a lower water contact angle than the substrate surface before the surface activation.
- the film includes a first graphed layer of a plasma-reacted first set of precursor molecules graphed to the first water layer, wherein the first water layer forms a first bonding link between the substrate surface and the reacted first set precursor molecules.
- the film includes a second water layer bonded to the first graphed layer.
- the film includes a second graphed layer of a plasma-reacted second set of precursor molecules graphed to the second water layer, wherein the second water layer forms a second bonding link between the second water layer and the reacted second set of precursor molecules.
- FIG. 1 shows a flow diagram showing steps in an example process of the present invention
- FIG. 2 shows a cross-sectional view of an example film formed on a substrate is accordance with a process of the disclosure such as any of the embodiment discussed in the context of FIG. 1 ;
- FIG. 3 shows a simulated time-of-flight secondary ion mass spectrometry (TOF-SIMS) trace of an example film formed on a substrate is accordance with a process of the disclosure such as an embodiment (e.g., a one-pass embodiment) of the film deposition process presented in FIG. 1 ;
- TOF-SIMS time-of-flight secondary ion mass spectrometry
- FIG. 4 shows an optical interferometry of an example masked step edge plasma-assisted silicon oxide (SiOx) deposited film on a glass substrate, produced in an example embodiment of the process flow in FIG. 1 , where tetraethoxysilane (TEOS) was used as the precursor in the step following the exposure of the cleaned and activated surface to water vapor;
- SiOx silicon oxide
- TEOS tetraethoxysilane
- FIG. 5 presents a summary of example air flow rate deviations measured after an example autoclave cycling tests such as described in Example 2 of the application.
- FIG. 6 presents an example optical interferometry image of an example 60 nm styrene film edge on a de-masked glass sample substrate in accordance to with a process of the disclosure such as an embodiment of the process presented in FIG. 1 .
- forming a water layer after a plasma cleaning and activating step enhances the formation of films, such as conformal films for the purpose of providing a moisture and environmental barrier to protect electronic or other devices.
- This discovery was made by accident when, between a first plasma treatment to atomically clean and activate a substrate's surface, and a second plasma treatment to expose the activated surface to pre-cursors molecules, the activated surface was inadvertently exposed to air having a high moisture content.
- the term atomically cleaned and activated refers to the treatment of a substrate surface with low molecular weight molecules or atoms (e.g., Helium, Argon, Nitrogen, Neon, Silane, Hydrogen and Oxygen) in the presence of a radiofrequency plasma, to clean the substrate's surface by making the surface free of contaminants such as organic contaminants and water.
- a plasma treatment referred to a first plasma treatment herein, also actives the substrate's surface by breaking up covalent and/or other chemical bonds of the substrate molecules at the surface, thereby making the substrate surface easier to react with plasma treated pre-cursors molecule.
- a quantitative indicator of the presences of such an activated surface is that the surfaces has a lower water contact angle (e.g., at least about 10 percent and in some cases at least about 20 percent lower) than the substrate surface before the surface activation.
- water layer refers to one or more self-assembled monolayers of water molecules.
- the water layer can range from a monolayer (e.g., a thickness of about 0.3 nanometers) to several monolayers (e.g., a thickness of about 2 nanometers).
- a monolayer e.g., a thickness of about 0.3 nanometers
- monolayers e.g., a thickness of about 2 nanometers.
- One skilled in the art would appreciate how the extent of adsorption and thickness of the resultant water layer would be controlled by the thermodynamic conditions present in the plasma chamber containing the substrate and water vapor.
- FIG. 1 shows a flow diagram showing selected steps in an example film deposition process 100 of the disclosure.
- FIG. 2 shows a cross-sectional view of an example device 200 (e.g., a circuit board) have film 202 formed on a substrate 205 , in accordance with a process of the disclosure such as any of the embodiment discussed in the context of FIG. 1 .
- an example device 200 e.g., a circuit board
- the example process 100 comprises a first step 110 of exposing a surface 210 of a substrate 205 to a first plasma treatment having plasma reactants in a plasma chamber 215 to form an activated substrate surface 210 .
- the substrate 205 can be a circuit board and the surface 210 is a component-side surface of the circuit board.
- the film layer 202 can be a conformal coating designed to protect an electronic device, such as a circuit board, from moisture under autoclave sterilization conditions.
- step 110 can serve to atomically clean and activate the substrate's surface 210 .
- the process 100 also comprises a step 120 of introducing water vapor into the plasma chamber to form a water layer 220 on the activated surface 210 .
- the process 100 also comprises a step 130 of introducing pre-cursors molecules into the plasma chamber 215 in the presence of a second plasma treatment to graft a layer 225 of reacted pre-cursor molecules on the water layer 220 .
- the first plasma reactants in step 110 are formed from one or more of Helium, Argon, Nitrogen, Neon, Silane, Hydrogen and Oxygen.
- reactants are in the presence of the first plasma treatment that includes: a radiofrequency power in the range of about 30 to 500 Watts, a temperature in range of about 0° C. to about 100° C. for a time period in a range of about 0.5 to 10 minutes.
- the first plasma reactants are formed from Argon at pressures between about 50 and 500 mTorr in the presence of the first plasma treatment that includes a radiofrequency power in the range of about 50 to 200 Watts, a temperature in range of about 0° C. to about 100° C. for a time period in a range of about 0.5 to about 10 minutes.
- the substrate surface 210 having the water layer 220 thereon is exposed a flux of plasma-cracked, reactive organic or ceramic precursor intermediates.
- such intermediates can be formed from monomers introduced into a modified plasma environment, under conditions that preserve the integrity of the reactive intermediate species formed.
- the plasma generation conditions should not result in the total fragmentation or decomposition of the precursor molecules, nor should the intermediates have very short residence time in the reactor.
- the intermediates should be able to adsorb and react on the water layer on the cleaned and activated substrate surface 210 .
- the water layer 220 formed in step 120 is desirably not greater in thickness 230 than about 2 nanometers.
- the outermost water molecules of the layer 220 are not tenaciously bound, either chemically or physically, to the substrate surface 210 .
- These outermost water molecules can desorb and react with the incoming precursor species in step 130 to form new species which may be undesirable or not beneficial to the film deposition process 100 .
- the desorbed excess water molecules can adsorb on the plasma chamber walls 240 , and later on leach off of the wall 240 to thereby contaminate and impede the film deposition process 100 .
- a water layer thickness 230 of 0.1 to 2 nanometers produces a balanced situation where the benefits of the water layer 220 are realized while avoiding the undesirable effects of excess water.
- step 130 it is thought that, in some cases, under the reduced pressure of the process conditions used in step 130 , all or some of the adsorbed water layer 220 can be lost through desorption.
- step 130 it is also thought that water molecules of the layer 220 can deprotonate to afford reactive oxygen-radical rich surfaces with chemically unsatisfied dangling bonds exposed to the flux of cracked monomer intermediates.
- the reactive surface is thought to rapidly react with the reactive species in the process chamber 215 to form strong chemical bonds (e.g., covalent bonds), which result in the grafted layer 225 being bonded to the substrate surface 210 .
- the deposited film 202 having the grafted layer 225 of reacted pre-cursor molecules after step 130 , retains at least part of the water layer 220 in-between the surface 210 of the substrate 205 and the grafted layer 225 .
- the retained water layer 220 has a thickness 230 in a range from about 0.1 to 2 nanometers.
- the retained water layer has a thickness 230 in a range from about 0.3 to 1.8 nanometers (e.g., a stack of about 1 to 6 self-assembled monolayers of water).
- the molecules of the water layer 220 form a bonding link between the grafted layer 225 of reacted pre-cursor molecules and the substrate surface 210 .
- organic e.g., simple olefins to fluoro-olefins
- pre-ceramic monomers pre-cursor molecules are applied in step 130 to form graphed layers 225 having a thickness 235 in a range of about 50 to 500 nanometers.
- the grafted layer 130 (and in some cases retained water layer 220 ) provide complete coverage, conformal to an irregular substrate surface 210 and are tightly bounded with high durability.
- the precursor molecules in step 130 include hexafluoropropylene and Argon at pressures between about 100 and 500 mTorr and the second plasma treatment includes: a radiofrequency power in the range of about 50 to 250 Watts, a temperature in range of about 10° C. to about 80° C. for a time period in a range of about 15 to about 60 minutes.
- the process 100 can further include a step 140 of evacuating the plasma chamber 215 of the first plasma reactants (e.g., in step 110 ) after forming the activated substrate surface 210 and before introducing the water vapor into the plasma chamber 215 (e.g., in step 120 ).
- evacuating the plasma chamber 215 includes reducing the atmospheric pressure in the chamber 215 to less than about 100 Torr for at least about 5 minutes.
- Step 140 can advantageously mitigate the formation of undesirable or not beneficial species from the reaction between the water vapor introduced in step 120 and plasma reactants formed in the chamber 215 in step 110 .
- the water vapor is in the chamber 215 when the second plasma treatment (e.g., step 130 ) is commenced. That is, as part of step 120 the water vapor is introduced into the plasma chamber to expose the activated surface to the water vapor before introducing the pre-cursors molecules into the plasma chamber 215 (e.g., step 130 ). It is also desirable to introduce the water vapor for a sufficient period to form the desired thickness 230 of water layer 220 but as discussed above, not to form an overly thick layer 220 .
- the water vapor is in the chamber 215 for at least about 5 minutes before the second plasma treatment in (e.g., step 130 ) is commenced.
- the water vapor is in the chamber 215 for at least about 5 minutes and not longer than 10 minutes before the second plasma treatment is (e.g., step 130 ) is commenced.
- introducing the water vapor into the plasma chamber 215 includes introducing air into the chamber, wherein the air has a humidity of least about 45 percent at about 20° C. for at least about 5 minutes, and in some cases, not longer than about 10 minutes, before introducing the pre-cursors molecules into the plasma chamber 215 (e.g., step 130 ).
- a single-pass through steps 110 , 120 , 130 is sufficient to product the desired film layer 202 and therefore in decision step 150 , it is decided the target film has been achieved and the process 100 is ceased at stop step 160 .
- the process 100 can include repeating in step 170 , at least one time, each of the sequence of steps of exposing the surface (step 110 ), introducing the water vapor (step 120 ) and introducing the pre-cursors molecules (step 130 ) and sometimes optional step 140 .
- step 140 There can be repeated passes, e.g., a three or more passes, through steps 110 , 120 , 130 and sometimes optional step 140 .
- steps 110 , 120 , 130 and sometimes optional step 140 there can be multiple pairs of retained water and grafted layers 220 , 220 ′, 225 , 225 ′ that comprise the film 202 formed by such repeated passes in accordance with step 170 .
- the process 100 is compatible with a wide range of substrate material composition and shapes, as well as monomer chemistry types that can be deposited in step 130 .
- the surface characteristics of the final film 202 can be adjusted according to the second plasma treatment conditions and pre-cursor molecules in each pass through steps 110 - 140 .
- first and second plasma treatments as part of steps 110 and 130 , as also presented in U.S. application Ser. No. 12/206,013 and U.S. Provisional Application Ser. No. 60/970,582 which are incorporated by reference if reproduced in their entirety herein.
- Still other examples of first and second plasma treatments as part of steps 110 and 130 are presented in U.S. Pat. Nos. 6,579,604 and 6,846,225 which are incorporated by reference herein in their entirety.
- a film layer 202 modification of a substrate surface 210 can be characterized by time-of-flight secondary ion mass spectrometry (TOF-SIMS).
- FIG. 3 shows a generalized simulated expected TOF-SIMS trace of such a surface.
- “Oxide Yield” is defined as the detected relative concentration of oxygen containing species emanating from the sputtered surface reaching the detector of the TOF-SIMS tool.
- the time from T 0 to T 1 represents the time it takes to sputter through the outermost graphed layer 225 in FIG. 2 .
- the time T 1 to T 2 represents the time it takes to sputter through the residual water-derived interfacial water layer 220 .
- atomically clean surfaces can be characterized by time-of-flight secondary ion mass spectrometry (TOF-SIMS) traces devoid of any elemental yields other than that of the substrate.
- TOF-SIMS time-of-flight secondary ion mass spectrometry
- the suitable materials for deposition by some embodiments of the disclosure offer a very wide range of physical, chemical and optical properties and some are well known polymers from bulk polymerization processes.
- self-cleaning barrier films or coatings that provide catalytic self-cleaning and barrier properties e.g., layers of TiO 2 ZnO 2 and SnO 2
- TiO x structures on a variety of substrates have been demonstrated using embodiments of the process.
- FIG. 4 shows an optical interferometry of a masked step edge silicon oxide (SiO x ) plasma assisted film on a glass substrate produced by a two-stage process where tetraethoxysilane (TEOS) was used as the precursor molecule in the final stage (step 130 ).
- TEOS tetraethoxysilane
- the applied film 202 is dense, smooth and of about 200 nm in thickness.
- the specific properties of the deposited film 202 are sensitive to the precise process conditions used in the deposition. It is well known in the art that in the case of deposition on thermoplastic substrates, it is important to conduct the deposition at low temperatures to avoid dimensional distortion of the substrate. Likewise, the process of the current invention is designed to circumvent the typical 1-2 day surface reversion to low energy observed for many thermoplastic substrates treated with plasma. This invention takes advantage of the surprising beneficial effect of humid air on the atomically cleaned substrate surface to provide compact conformal films with excellent conformal barrier films with excellent adhesion properties.
- the customized versions of the multi-stage platform for nanoscale plasma enhanced coatings can afford a rapid low cost method for applying application specific coating combinations to industrial parts to improve impact strength, abrasion resistance and corrosion resistance. Examples of the demonstrated coatings include, but not limited to titanium oxide coatings for glass objects, silicon oxide coatings for corrosion resistant rotor blades and aircraft parts.
- a film 202 can be formed of polymeric materials by a process 100 that includes exposing a polymeric substrate to at least two plasma treatments (e.g., in steps 110 and 130 ).
- a first plasma treatment creates a modified reactive surface on the substrate.
- the subsequent second plasma treatment produces a grafted layer 225 thereon.
- the initial plasma treatment is done while controlling the temperature of a radiofrequency electrodes to about 10 to 100° C.
- the specific conditions used during the first plasma treatment can strongly influence characteristics of the polymeric substrate's surface. For instance, different initial plasma treatments followed by the same subsequent plasma treatment can result in grafted layer surfaces that are either hydrophilic or hydrophobic.
- the first plasma treatment can include a plasma reactant such as Helium, Argon, Nitrogen, Neon, Silane, Hydrogen and Oxygen and mixtures thereof. In some cases, the initial plasma treatment reaction is conducted at a radiofrequency power of 30 to 500 Watts.
- the second subsequent plasma treatment can have subsequent plasma reactants that include vinyl or acrylic monomers.
- Example monomers include monomers 1-Vinyl-2-pyrrolidinone, 2-Hydroxyethylmethacrylate, Allyl Alcohol, Allyl Amine, Substituted Allyl Amines of 4-10 Carbon Atoms, Acrylic Acid, Acrylic Esters of 2-10 Carbon Atoms, Acrylamides of 3-10 Carbon Atoms.
- the resulting surface can be used as a tie layer under a conventional solvent, spray, dip or powder coating. The conventional coating can then be used to bind a drug or other therapeutic material.
- the subsequent plasma treatment can have subsequent plasma reactants that include metal alkoxide esters of Silicon, Titanium, Tantalum, Aluminum, Zirconium, or Zinc.
- the process 100 can adapt the multi-pass plasma grafting technique described above into a multiple step process specifically designed for modifying and functionalizing the surfaces of medical devices.
- An advantage of the method described in this application is the ability to apply coatings on a dry-in dry-out basis, and/or in a sterile anaerobic environments. Using this method, parts can be placed into a treatment chamber dry and emerge after treatment both dry and sterile.
- the thin film coatings produced by the disclosed techniques are chemically bonded to the surface and are thus highly resistant to adhesion failures, delamination, flaking or debonding.
- the films are also coherent and uniform and are resistant to decohesion and tearing. Areas of the coated devices that need to remain non lubricious can be easily masked during the plasma coating process.
- the lubricity of the coating is activated by treatment of the surface with water or body fluids.
- the so-deposited film stack 202 could be comprised of organic and or inorganic polymers.
- the organic polymers are made from monomers can be selected of a group comprising, but not limited to, common lubricious monomers such as N-vinylpyrrolidinone and hydroxyethylmethacrylate and their copolymers ethylene and propylene oxide and their derivatives.
- the polymers are created in-situ at the substrate surface from treatment of the substrate in the plasma/monomer environment.
- These plasma created polymer coatings provide lubricity when contacted with water or saline solution.
- the coated device is dry to the touch prior to water treatment for facile handling by medical or surgical personnel.
- the mechanical properties of the coatings can be modified by incorporation during the plasma polymerization of volatile crosslinking agents such as diallylethers, polyallylamines, gylcoldiacrylates or glycoldimethacrylates into the monomer stream.
- volatile crosslinking agents such as diallylethers, polyallylamines, gylcoldiacrylates or glycoldimethacrylates into the monomer stream.
- Monomers with reactive functional groups containing amine, hydroxyl, and carboxylic acid functional groups can provide sites for the further coupling of surface binding or other materials and polymers, including designer drugs for targeted delivery.
- known lubricious urethane polymers can be attached to preceding layers containing these reactive surfaces.
- direct attachment or binding of gel mixtures of antibiotic or other drugs can be accomplished using standard solution coating or gas phase under non-plasma vacuum/reduced pressure techniques.
- the coatings of this invention including common lubricious monomers such as N-vinylpyrrolidinone, which provides lubricity when contacted with water or saline solution, have been applied on a dry-in/dry-out basis.
- the coated device is dry to the touch prior to water treatment for facile handling by medical or surgical personnel.
- coating of monomers with reactive handles containing amine, hydroxyl, and carboxylic acid functional groups can provide sites for the surface binding of antibiotic or other drugs have been demonstrated.
- Table 1 is a compendium of the conditions in a coating processes on miscellaneous substrates using the process 100 which includes two steps: a first plasma treatment in accordance with step 110 (step P 1 ) and a second plasma treatment in accordance with step 130 (step P 2 ), and the characterization data of the resultant articles.
- the substrates used in these experiments were made from polymers commonly associated with biomedical devices. In all cases, the modified surfaces showed permanent improvements in their hydrophilic (reduced water contact angles relative to the untreated substrates)
- the first plasma treatment (P1 stage) and second plasma treatment (P2 stage) are interspersed with humid air exposure in accordance with step 120.
- P1 P2 Sample P1 RF P1 P1 Pres- P2 P2 RF P2 RF P2 Pres- ID Substrates Power Time Gas sure Monomer Power Time Gas sure 1-10A Tygon Tubing NA NA NA NA NA NA NA NA NA NA NA NA 1-10B Tygon Tubing 50 4 20% O2, 350 TYZOR TPT 50 20 Ar 350 80% Ar 1-3B Tygon Tubing 100 15 Ar 250 TEOS 50 20 Ar 250 1-5A Tygon Tubing 100 15 Ar 250 2-Hydroxyethyl 50 20 Ar 250 Methracrylate 1-2B Tygon Tubing 100 15 250 N-Vinylpyrrolidinone 50 20 Ar 250 1-11A Red Rubber 50 3 20% O2, 350 Hexamethyldisilazane 50 20 Ar 350 Bard Urethral 80% Ar Catheter 1-5E Lex
- Table 1 shows that the process conditions used in the atomic cleaning and activation step P 1 (step 110 of FIG. 1 ) strongly influence the eventual surface characteristics.
- sample 1 - 3 F is hydrophilic while sample 1 - 5 D is hydrophobic.
- the principal difference is in the plasma step P 1 process condition; the process gas composition, plasma power and time were different.
- substrates 205 comprising feeding tube connectors and balloon catheters are surface modified by of the process 100 resulting in a graphed layer 225 of an elastomeric conformal coating.
- the precursor molecule of step 130 can include polymerize 2-methyl-1,3-butadiene (isoprene) onto a variety of substrates using a single pass through of the process 100 (steps 110 - 130 , and in in some cases step 140 ). This is a special case of the general olefin polymerization process, since a coating is produced which can be further cross-linked by plasma post treatment or by other means
- device substrates 205 benefit from a dry low friction, biologically inert grafted layer 225 surface with low adhesion to the biological tissues.
- dry lubricious Such surfaces are useful in particular for invasive medical devices such as catheters, arthroscopic tubes and implements. Implements of this type are advantageous during surgical insertion since no additional surface treatment water or external fluids are required during insertion.
- Some such embodiments of the disclosure use commercially available fluoro-monomers in producing low energy, hydrophobic, low coefficient of friction coatings via our two stage plasma coating process.
- the process 100 comprises a first grafted layer 225 of a conformal organic coating and subsequent grafted layers 225 ′ (one or more repeated passes in accordance with step 170 ) of a plasma-assisted deposited, ceramic metal oxide coating.
- the forming of a plurality of subsequent grafted layers 225 ′ (and in some cases water subsequent layers 220 ′) where there exists one or more subsequent grafted layer 225 and (in some cases subsequent water layer 220 ) can in some cases include in step 110 exposing the upper-most preceding grafted layer 225 to a short burst of inert gas plasma designed to clean at the atomic level and to activate the surface of the preceding grafted layer 225 , and then exposure to humid air in step 120 , followed by plasma assisted deposition of a thin film comprised of ceramic metal oxide of ceramic-polymer hybrid conformal surface in step 130 .
- the ceramic metal oxide is in step 130 chosen from the group of Si, Al, Ti, Ta, Zr, Zn, Sn, Zr.
- the ceramic metal sub-oxide is chosen from the group of Si, Al, Ti, Zr, Zn, Sn, Zr.
- the subsequent graphed layer 225 ′ can be another conformal organic coating such as an olefinic deposited conformal surface.
- one or both the preceding graphed layer 225 and subsequent graphed layer 225 ′ includes an olefinic precursor molecules chosen from the group of tyrene, 1-Hexene, or isoprene.
- one or both the preceding graphed layer 225 and subsequent graphed layer 225 ′ includes an olefinic precursor molecules that are paracyclophanes, such as parylene.
- the organic coating is an olefinic hydrocarbon of 4-15 carbon atoms.
- the organic coating is styrene.
- one or both the preceding graphed layer 225 and subsequent graphed layer 225 ′ includes an olefinic precursor molecules that are olefinic hydrocarbon of 4-15 carbon atoms.
- the precursor molecule used in step 130 is a monomer selected for subsequent direct chemical reaction binding of the grafted layer 225 to the substrate surface 110 are taken from the group of: acrylic acid, primary and acrylamides of up to 10 carbon atoms, allyl alcohol, primary and secondary allylamines up to 15 carbon atoms, allylglycidylether, hydroxyethylacrylate and methacrylate, hydroxypropylacrylate and methacrylate.
- the precursor molecules used in step 130 is 4-diallylaminopyridine.
- the subsequent grafted layer 225 ′ can be fromed from precursor molecules of acrylic and methacrylic acids, tertiary allylamines in some cases 4-diallylaminopyridine.
- the film layer 202 produced is active in destroying chemical warfare agents. In some cases, the film produced is active in destroying toxic industrial fluids. In some cases, the film produced by the current invention is active in destroying organic molecules under electromagnetic wave irradiation. In some cases, the film 202 produced is active in destroying metal-organic complex molecules under electromagnetic wave irradiation.
- the precursor molecule used in step 130 provides a conformal inert hydrogenated amorphous carbon film coating 202 , in some cases containing sp3 and sp2 hybridized carbon, as well as C—H bonds, e.g., formed from precursor molecules that include volatile carbon-rich fluids such as one or more of carbon tetrachloride, chloroform, benzene, and xylene
- the subsequent or second grafted layer 225 is a conformal inert hydrogenated amorphous carbon film coatings, formed in a repeated pass in accordance with step 170 .
- the precursor molecule used in step 130 provides a conformal electrically and or thermally conducting film 202 , e.g., formed from precursor molecules that include pyrrole, thiophene and aniline.
- the process produced a yellow conformal coating.
- the thickness of the coating increased monotonically with increasing stage-two treatment time, reaching a thickness of about 100 nm in 60 minutes on all of the test surfaces. This suggests that the film deposition rate depended on the reactive precursor species reaching the activated surface, where it is readily incorporated into the growing film.
- the films produced on all the test surfaces were smooth and hydrophobic, with static water contact angles of between 120°-125° C. and no contact hysteresis.
- the films were also highly adherent to the substrates, based on the results from a modified qualitative “Scotch tape peel” tests. In these tests, a piece of ScotchTM brand tape was firmly pressed onto the coated substrate for 5 minutes and then quickly removed at 90-degrees. If little or none of the yellowish coating was peeled substrate surface, then the adhesion of the film to the substrate is considered good. All the tested samples, produced in this example passed this test.
- an electronic board previously coated with Parylene-C was subjected to a two stage plasma activation and deposition process.
- the first stage was carried out in argon plasma at 250 mTorr at 100 W power for up to 5 minutes.
- humid air or water saturated air was allowed to bleed into the deposition chamber, which was partially pre-filled with an inert gas, until the chamber pressure reached 1 atmosphere, and then the system was evacuated to base pressure, backfilled with the inert gas and pumped down to base pressure twice before the plasma assisted deposition stage was then initiated.
- subsequent, tetraethyloxyorthosilane [TEOS] was introduced and plasma conditions of 250 mTorr and 100 W maintained for 25 minutes to yield a conformal SiO x overcoating.
- a circuit board controller was first subjected to a two stage plasma activation and deposition process.
- the first stage was carried out in argon plasma at 250 mTorr at 100 W power for up to 5 minutes.
- Tetraethyloxyorthosilane [TEOS] was introduced and plasma conditions of 250 mTorr and 100 W maintained for 25 minutes to yield a conformal SiO x coating. This was followed by thermal vapor coating with Parylene-C, and then finally coated again with the two stage plasma process, interspersed with humid-air breaks of Example 1 to create a three layer conformal barrier coating.
- the electronic control boards were evaluated using a modified unbiased autoclave test (JEDEC Standard JESD22-A102, http:www.jedec.org, incorporated by reference herein in its entirety).
- JEDEC Standard JESD22-A102 test is a highly accelerated test which employs conditions of pressure, humidity and temperature under condensing conditions to accelerate moisture penetration through the external coating materials and along the interface between the external protective film material and the underlying metallic components.
- the autoclave test used to simulate device survivability in harsh conditions and/or long-term reliability testing.
- the circuit boards were subjected to multiple heat and cool cycles.
- the failure criterion is a flow deviation at 20%; any device showing flow deviation of greater than 20% at any gas flow set point is considered to have failed.
- FIG. 5 and Table 4 summarize the results from these tests. The results clearly show that the under- and over-coat of parlyene with SiO x from the current invention significantly improved the performance and the long-term reliability of the control electronics evaluated.
- Polyethylene blow-molded fuel tanks for small engines were sealed to mitigate permeation of hydrocarbon fluids.
- the untreated tanks have inherent permeability of hydrocarbon fluids and the current state of the art mitigation treatments, such as gaseous fluorination of the tank surfaces in large chambers and multilayer polymer co-extrusion are environmentally less preferred and capital intensive respectively.
- a commercial polyethylene blow molded small engine fuel tank (e.g., obtained from Mergon Corporation, Anderson, SC) was coated with SiO x using the process of this invention.
- the blow molded fuel tanks were coated in the two stage plasma process consisting of a plasma activation stage from 2-10 minutes at 50-100 W Argon plasma at 100-500 MTorr, preferably at 250 mTorr, followed by a plasma grafting stage, where Tetraethyloxyorthosilane [TEOS] was introduced.
- the plasma conditions of the grafing stage were 100-250 MTorr and 100 W maintained for 25 minutes.
- the resultant thickness of the conformal SiO x over-coating was about 150 nm.
- the coated tanks were filled with commercial 87 octane gasoline, closed with a commercial small engine fuel tank cap, placed in a covered, 10 gallon polyethylene buckets, and stored at room temperature for 26 months. Identical, but uncoated control tanks were likewise filled and similarly stored. After 26 months, the mean net weight of the fuel remaining in the coated tanks was 397 g, as compared to 372 g remaining in the uncoated tanks. This demonstrates that the conformal coatings from this invention deposited on the fuel tanks were effective in mitigating hydrocarbon fuel loss due to permeation polyethylene blow molded fuel tank.
- multi stage plasma based coatings were produced with a variety of olefinic monomers (Styrene, 1-Hexene, Isoprene) in the subsequent grafting stage to produce nanoscale conformal barrier coatings.
- the substrates were coated in the two stage plasma process consisting of a plasma activation stage from 1-10 minutes at 50-100 W argon plasma at 100-500 mTorr, preferably at 250 mTorr, followed by a plasma grafting stage, where olefinic monomers were introduced.
- the plasma conditions of the grafting stage were 100-250 mTorr, and preferably 100 W maintained for up to 30 minutes.
- FIG. 6 shows an optical interferometry example image of an example 60 nm styrene coating edge on a de-masked borosilicate glass sample.
- the reactive surfaces demonstrated in example 4 can be employed as tie and/or priming coats and sub-coats to bind other materials to the surface or to catalyze chemical reactions at the surface.
- the grafting of allyl alcohol and allylamine to a variety of substrates were demonstrated.
- other suitable monomers such as allylglycidylether, were used to graft a reactive epoxy coating onto the substrate, and then used to couple 4-diallylaminopyridine, to produce a grafted dialkylaminopyridine catalytic surface.
- Polymeric dialkylaminopyridines have been shown to be useful in catalyzing the destruction of chemical warfare agents and toxic industrial materials. (See e.g., Yokley and Nielsen, US Patent Application, US20110028774, Hypernucleophilic Catalysts for Detoxification of Chemical Threat Agents, incorporated by reference herein in its entirety).
- Electrically conducting coatings were applied to polypropylene and polyethylene tubes, polycarbonate and acrylic sheets, aluminum sheets, borosilicate glass slides and on inter-digitated conductive test structures; the substrates were treated in a two phase plasma coating process.
- the activation phase was conducted at 75 W power at 300 mTorr pressure using a 67% argon and 33% air plasma for 2 minutes.
- the subsequent phase admitted pyrrole into the plasma chamber at a pressure ranging from 300-400 mTorr for 75 W for 30 minutes.
- the chamber temperature rose from 12° C. to 18° C.
- a thin colorless conformal coating of about 12 nm in thickness was deposited as characterized with an optical interferometry.
- the coatings were uniform, smooth and adherent.
- the electrical conductivity of the prepared conducting polymer films (comprised of mostly polypyrrole) was measured at room temperature by four-point probe technique, taking the average value of several readings at various points of the films. The electrical data varied significantly from site to site over the samples, and from sample to sample. The best conductivity of the as-deposited undoped films measured was about 1 ⁇ 10 ⁇ 2 S/cm.
- Inert hydrogenated amorphous carbon film coatings (possibly containing sp3 and sp2 hybridized carbon, as well as C—H bonds) were applied to polypropylene and polyethylene tubes, polycarbonate and acrylic sheets, aluminum sheets, and glass slides; the substrates were treated in a two phase plasma coating process.
- the activation phase was conducted for 2 minutes at 175-300 mTorr and 75 W power, with argon as the background gas.
- Carbon Tetrachloride (CCl 4 ) was introduced into the plasma chamber with argon as the carrier and background gas in the subsequent phase, at 75 W power and 175-300 mTorr for 30 minutes.
- xylene (C 7 H 8 ) was introduced into the plasma chamber with argon as the carrier and background gas in the subsequent phase, also at 75 W power and 175-300 mTorr for 30 minutes.
- the process produced a colorless conformal and hydrophobic coating.
- the thickness of the coating increased monotonically with increasing stage-two treatment time, reaching a thickness of about 150 nm in 30 minutes on all of the test surfaces. This suggests that the film deposition rate was independent of the carbon source, but depended only on the reactive precursor species reaching the activated surface, where it is readily incorporated into the growing film.
- the coatings of this invention are uniquely able to perform these operations since the activation is driven by the plasma which accesses all surfaces within the plasma reaction chamber, and the volatile monomers are delivered to the activated surface sites in the gas phase.
- the advantages of a rapid, general, and chemically flexible system that can be used on finished configurations on a dry-in/dry-out basis are clearly evident to those skilled in the art.
- an embodiment of the process 100 of the disclosure was used to modify a variety of filter membranes materials, to create surfaces capable of binding metal ions through dative bonding.
- soft ligands e.g., aliphatic-, thiols, amines, etc.
- coinage metal ions Au, etc. . . .
- the allyamine surfaces created in example 1 bind copper ions, and were used to reduce the concentration of Cu 2+ in aqueous solutions placed in contact with such surfaces.
- PVA objects e.g. PVA brushes
- PVA brushes polyvinylalcohol objects
- the performance of PVA objects are constrained by, but not limited to, the difficulties in hydration (requiring brushes to shipped in wet envelopes), bio-fouling (bacteria growth in the brushes leading to high particle count) and lack of application specificity (′one-size fits all′ approach, use the same brush for all substrate)
- the inventors successfully modified commercial PVA brushes with secondary coatings that bind detrimental metallic species, such as Cu- and other metallic ions, to proactively address yield and reliability limiting dielectric contamination in semiconductor manufacturing.
- detrimental metallic species such as Cu- and other metallic ions
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
An electronic device comprising a substrate having a component-side surface and a moisture protection film covering the component-side surface. The moisture protection film includes a first water layer bonded to component-side surface that is an activated surface, wherein the activated surface has a lower water contact angle than the substrate surface before the surface activation. The film includes a first graphed layer of a plasma-reacted first set of precursor molecules graphed to the first water layer, wherein the first water layer forms a first bonding link between the substrate surface and the reacted first set precursor molecules. The film includes a second water layer bonded to the first graphed layer. The film includes a second graphed layer of a plasma-reacted second set of precursor molecules graphed to the second water layer, wherein the second water layer forms a second bonding link between the second water layer and the reacted second set of precursor molecules.
Description
- This is a continuation application of U.S. application Ser. No. 13/665,314 filed on Oct. 31, 2012, which in turn is a continuation in part application of U.S. application Ser. No. 12/206,013 filed on Sep. 8, 2008, entitled Surface Properties of Polymeric Materials with Nanoscale Functional Coating to Yokley and Obeng, which in turn claims the benefit of U.S. Provisional Application Ser. No. 60/970,582 filed on Sep. 7, 2007, entitled, Improving Surface Properties of Polymeric Materials by the Creation of Nanoscale Functional Coatings, to Yokley and Obeng, and also claims the benefit of U.S. Provisional Application Ser. No. 61/564,415 filed on Nov. 29, 2011 entitled, Surface Properties of Polymeric Materials with Conformal Dry Nanoscale Functional Coatings to Yokley and Obeng, all being incorporated herein by reference.
- This application is directed, in general, to a process for depositing films, the films formed by the process and, more specifically, to a process for forming conformal surface film coatings for protecting electronic and other devices.
- There is a growing requirement for conformal barrier coatings or films having high adhesion for corrosion protection, water proofing, surface decoration, for medical device passivation, circuit board moisture protection, consumer electronic devices and a wide variety of industrial, consumer devices and similar objects. There is a need to better engineer the air-substrate interface of such films for specific applications. For example, it is often desirable for films to modify the substrate surface without altering the bulk properties of the substrate. It is sometimes desirable to engineer films to have the potential to enhance the structural and functional performance of fabricated polymeric devices. Enhancement of the surface can occur with designed organic, inorganic or hybrid polymeric coatings. However, many existing films suffer from poor adhesive bonding to the underlying surface, since the device materials construction are inherently non-reactive to reduce the incidence of reactions with the surrounding tissues.
- One embodiment of the disclosure provides an electronic device. The device comprises a substrate having a component-side surface. The device comprises a moisture protection film covering the component-side surface. The moisture protection film includes a first water layer bonded to component-side surface that is an activated surface, wherein the activated surface has a lower water contact angle than the substrate surface before the surface activation. The film includes a first graphed layer of a plasma-reacted first set of precursor molecules graphed to the first water layer, wherein the first water layer forms a first bonding link between the substrate surface and the reacted first set precursor molecules. The film includes a second water layer bonded to the first graphed layer. The film includes a second graphed layer of a plasma-reacted second set of precursor molecules graphed to the second water layer, wherein the second water layer forms a second bonding link between the second water layer and the reacted second set of precursor molecules.
- Reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which:
-
FIG. 1 shows a flow diagram showing steps in an example process of the present invention; -
FIG. 2 shows a cross-sectional view of an example film formed on a substrate is accordance with a process of the disclosure such as any of the embodiment discussed in the context ofFIG. 1 ; -
FIG. 3 shows a simulated time-of-flight secondary ion mass spectrometry (TOF-SIMS) trace of an example film formed on a substrate is accordance with a process of the disclosure such as an embodiment (e.g., a one-pass embodiment) of the film deposition process presented inFIG. 1 ; -
FIG. 4 shows an optical interferometry of an example masked step edge plasma-assisted silicon oxide (SiOx) deposited film on a glass substrate, produced in an example embodiment of the process flow inFIG. 1 , where tetraethoxysilane (TEOS) was used as the precursor in the step following the exposure of the cleaned and activated surface to water vapor; -
FIG. 5 presents a summary of example air flow rate deviations measured after an example autoclave cycling tests such as described in Example 2 of the application; and -
FIG. 6 presents an example optical interferometry image of an example 60 nm styrene film edge on a de-masked glass sample substrate in accordance to with a process of the disclosure such as an embodiment of the process presented inFIG. 1 . - As part of the present disclosure, it was discovered that forming a water layer after a plasma cleaning and activating step enhances the formation of films, such as conformal films for the purpose of providing a moisture and environmental barrier to protect electronic or other devices. This discovery was made by accident when, between a first plasma treatment to atomically clean and activate a substrate's surface, and a second plasma treatment to expose the activated surface to pre-cursors molecules, the activated surface was inadvertently exposed to air having a high moisture content.
- For the purposes of the present disclosure, the term atomically cleaned and activated, or, plasma cleaned and activated, refers to the treatment of a substrate surface with low molecular weight molecules or atoms (e.g., Helium, Argon, Nitrogen, Neon, Silane, Hydrogen and Oxygen) in the presence of a radiofrequency plasma, to clean the substrate's surface by making the surface free of contaminants such as organic contaminants and water. Such a plasma treatment, referred to a first plasma treatment herein, also actives the substrate's surface by breaking up covalent and/or other chemical bonds of the substrate molecules at the surface, thereby making the substrate surface easier to react with plasma treated pre-cursors molecule.
- It is counter-intuitive to think that it would be beneficial to first expose such a cleaned and activated surface to water vapor before exposing the surface to plasma treated pre-cursors molecules. It is counter-intuitive because one of the goals of such a plasma treatment is to remove contaminates from a surface, which typically includes removing water from the surface. While not limiting the scope of the invention by theoretical considerations, it is thought that exposure of the cleaned and activated substrate surface to water vapor results in the adsorption or chemisorption of a water layer, e.g., one or more monolayers of water, onto the surface. It is thought that a water layer at the interface between the substrate and grafted layered of various plasma treated pre-cursors molecules promotes the formation of strong bonds between the grafted material and the substrate. A quantitative indicator of the presences of such an activated surface is that the surfaces has a lower water contact angle (e.g., at least about 10 percent and in some cases at least about 20 percent lower) than the substrate surface before the surface activation.
- The term water layer as used herein refers to one or more self-assembled monolayers of water molecules. For instance, the water layer can range from a monolayer (e.g., a thickness of about 0.3 nanometers) to several monolayers (e.g., a thickness of about 2 nanometers). One skilled in the art would appreciate how the extent of adsorption and thickness of the resultant water layer would be controlled by the thermodynamic conditions present in the plasma chamber containing the substrate and water vapor.
-
FIG. 1 shows a flow diagram showing selected steps in an examplefilm deposition process 100 of the disclosure.FIG. 2 shows a cross-sectional view of an example device 200 (e.g., a circuit board) havefilm 202 formed on asubstrate 205, in accordance with a process of the disclosure such as any of the embodiment discussed in the context ofFIG. 1 . - With continuing reference to
FIGS. 1 and 2 throughout, theexample process 100 comprises afirst step 110 of exposing asurface 210 of asubstrate 205 to a first plasma treatment having plasma reactants in aplasma chamber 215 to form an activatedsubstrate surface 210. For instance, in any of the embodiments of theprocess 100, thesubstrate 205 can be a circuit board and thesurface 210 is a component-side surface of the circuit board. In some embodiments thefilm layer 202 can be a conformal coating designed to protect an electronic device, such as a circuit board, from moisture under autoclave sterilization conditions. - As discussed above,
step 110 can serve to atomically clean and activate the substrate'ssurface 210. Theprocess 100 also comprises astep 120 of introducing water vapor into the plasma chamber to form awater layer 220 on the activatedsurface 210. Theprocess 100 also comprises astep 130 of introducing pre-cursors molecules into theplasma chamber 215 in the presence of a second plasma treatment to graft alayer 225 of reacted pre-cursor molecules on thewater layer 220. - In some embodiments of the
process 100, the first plasma reactants instep 110 are formed from one or more of Helium, Argon, Nitrogen, Neon, Silane, Hydrogen and Oxygen. In some cases reactants are in the presence of the first plasma treatment that includes: a radiofrequency power in the range of about 30 to 500 Watts, a temperature in range of about 0° C. to about 100° C. for a time period in a range of about 0.5 to 10 minutes. In some such embodiments, the first plasma reactants are formed from Argon at pressures between about 50 and 500 mTorr in the presence of the first plasma treatment that includes a radiofrequency power in the range of about 50 to 200 Watts, a temperature in range of about 0° C. to about 100° C. for a time period in a range of about 0.5 to about 10 minutes. - In some embodiments of the
process 100, following exposure to water vapor as humid air (in step 120), instep 130, thesubstrate surface 210 having thewater layer 220 thereon is exposed a flux of plasma-cracked, reactive organic or ceramic precursor intermediates. Illustratively, such intermediates can be formed from monomers introduced into a modified plasma environment, under conditions that preserve the integrity of the reactive intermediate species formed. Specifically, the plasma generation conditions should not result in the total fragmentation or decomposition of the precursor molecules, nor should the intermediates have very short residence time in the reactor. Also, the intermediates should be able to adsorb and react on the water layer on the cleaned and activatedsubstrate surface 210. - In some embodiments the
water layer 220 formed instep 120, is desirably not greater inthickness 230 than about 2 nanometers. When thewater layer thickness 230 is greater than 2 nanometers, the outermost water molecules of thelayer 220 are not tenaciously bound, either chemically or physically, to thesubstrate surface 210. These outermost water molecules can desorb and react with the incoming precursor species instep 130 to form new species which may be undesirable or not beneficial to thefilm deposition process 100. Furthermore, the desorbed excess water molecules can adsorb on theplasma chamber walls 240, and later on leach off of thewall 240 to thereby contaminate and impede thefilm deposition process 100. Experiments performed as part of the present disclosure, suggest awater layer thickness 230 of 0.1 to 2 nanometers produces a balanced situation where the benefits of thewater layer 220 are realized while avoiding the undesirable effects of excess water. - While not limiting the scope of the invention by theoretical considerations, it is thought that, in some cases, under the reduced pressure of the process conditions used in
step 130, all or some of theadsorbed water layer 220 can be lost through desorption. Duringstep 130, it is also thought that water molecules of thelayer 220 can deprotonate to afford reactive oxygen-radical rich surfaces with chemically unsatisfied dangling bonds exposed to the flux of cracked monomer intermediates. The reactive surface is thought to rapidly react with the reactive species in theprocess chamber 215 to form strong chemical bonds (e.g., covalent bonds), which result in the graftedlayer 225 being bonded to thesubstrate surface 210. - In some cases, the deposited
film 202 having the graftedlayer 225 of reacted pre-cursor molecules, afterstep 130, retains at least part of thewater layer 220 in-between thesurface 210 of thesubstrate 205 and the graftedlayer 225. For example, in some cases, the retainedwater layer 220 has athickness 230 in a range from about 0.1 to 2 nanometers. For example, in some cases, the retained water layer has athickness 230 in a range from about 0.3 to 1.8 nanometers (e.g., a stack of about 1 to 6 self-assembled monolayers of water). In such embodiments, it is thought that the molecules of thewater layer 220 form a bonding link between the graftedlayer 225 of reacted pre-cursor molecules and thesubstrate surface 210. - In some embodiments of the
process 100, organic (e.g., simple olefins to fluoro-olefins) or pre-ceramic monomers pre-cursor molecules are applied instep 130 to form graphedlayers 225 having a thickness 235 in a range of about 50 to 500 nanometers. In some embodiments the grafted layer 130 (and in some cases retained water layer 220) provide complete coverage, conformal to anirregular substrate surface 210 and are tightly bounded with high durability. - In some embodiments of the
process 100, the precursor molecules instep 130 include hexafluoropropylene and Argon at pressures between about 100 and 500 mTorr and the second plasma treatment includes: a radiofrequency power in the range of about 50 to 250 Watts, a temperature in range of about 10° C. to about 80° C. for a time period in a range of about 15 to about 60 minutes. - As further illustrated in
FIG. 2 , theprocess 100 can further include astep 140 of evacuating theplasma chamber 215 of the first plasma reactants (e.g., in step 110) after forming the activatedsubstrate surface 210 and before introducing the water vapor into the plasma chamber 215 (e.g., in step 120). For instance, some embodiments ofstep 140 evacuating theplasma chamber 215 includes reducing the atmospheric pressure in thechamber 215 to less than about 100 Torr for at least about 5 minutes. Step 140 can advantageously mitigate the formation of undesirable or not beneficial species from the reaction between the water vapor introduced instep 120 and plasma reactants formed in thechamber 215 instep 110. - In some embodiments of the
process 100, it is desirable to introduce the water vapor into thechamber 215 instep 120 to form thewater layer 220. For instance, in some cases, the water vapor is in thechamber 215 when the second plasma treatment (e.g., step 130) is commenced. That is, as part ofstep 120 the water vapor is introduced into the plasma chamber to expose the activated surface to the water vapor before introducing the pre-cursors molecules into the plasma chamber 215 (e.g., step 130). It is also desirable to introduce the water vapor for a sufficient period to form the desiredthickness 230 ofwater layer 220 but as discussed above, not to form an overlythick layer 220. For instance, in some cases, the water vapor is in thechamber 215 for at least about 5 minutes before the second plasma treatment in (e.g., step 130) is commenced. For instance, in some cases, the water vapor is in thechamber 215 for at least about 5 minutes and not longer than 10 minutes before the second plasma treatment is (e.g., step 130) is commenced. It is also desirable to introduce the water vapor in a sufficient concentration to form the desiredthickness 230 ofwater layer 220 and not to form an overly-thick layer 220. For instance, in some cases, as part ofstep 120, introducing the water vapor into theplasma chamber 215 includes introducing air into the chamber, wherein the air has a humidity of least about 45 percent at about 20° C. for at least about 5 minutes, and in some cases, not longer than about 10 minutes, before introducing the pre-cursors molecules into the plasma chamber 215 (e.g., step 130). - In some embodiments of the
process 100, a single-pass throughsteps film layer 202 and therefore indecision step 150, it is decided the target film has been achieved and theprocess 100 is ceased atstop step 160. However in other cases, if it is decided instep 150 that the film layer should comprise multiple graftedlayers 225, theprocess 100 can include repeating instep 170, at least one time, each of the sequence of steps of exposing the surface (step 110), introducing the water vapor (step 120) and introducing the pre-cursors molecules (step 130) and sometimesoptional step 140. There can be repeated passes, e.g., a three or more passes, throughsteps optional step 140. For instance, as further illustrated inFIG. 2 , there can be multiple pairs of retained water and graftedlayers film 202 formed by such repeated passes in accordance withstep 170. - For instance, there is no upper limit to the number post surface activation steps and hence the number of layers of different materials that can be deposited on the
substrate surface 210. As illustrated in the examples to follow, theprocess 100 is compatible with a wide range of substrate material composition and shapes, as well as monomer chemistry types that can be deposited instep 130. The surface characteristics of thefinal film 202 can be adjusted according to the second plasma treatment conditions and pre-cursor molecules in each pass through steps 110-140. - Presented below are examples of how the above-described steps in the
process 100 could be monitored and implemented for particular embodiments of films 202 (sometimes referred to as a coating herein) on various types of substrate surfaces. Additional examples of first and second plasma treatments as part ofsteps steps - A
film layer 202 modification of asubstrate surface 210, such as formed in accordance with theprocess 100 inFIG. 1 and as depicted inFIG. 2 , can be characterized by time-of-flight secondary ion mass spectrometry (TOF-SIMS).FIG. 3 shows a generalized simulated expected TOF-SIMS trace of such a surface. In this example application, “Oxide Yield” is defined as the detected relative concentration of oxygen containing species emanating from the sputtered surface reaching the detector of the TOF-SIMS tool. In the trace depicted inFIG. 3 , the time from T0 to T1 represents the time it takes to sputter through the outermost graphedlayer 225 inFIG. 2 . The time T1 to T2 represents the time it takes to sputter through the residual water-derivedinterfacial water layer 220. - In this disclosure, atomically clean surfaces can be characterized by time-of-flight secondary ion mass spectrometry (TOF-SIMS) traces devoid of any elemental yields other than that of the substrate. The suitable materials for deposition by some embodiments of the disclosure offer a very wide range of physical, chemical and optical properties and some are well known polymers from bulk polymerization processes. For example, self-cleaning barrier films or coatings that provide catalytic self-cleaning and barrier properties (e.g., layers of TiO2 ZnO2 and SnO2) can be formed. TiOx structures on a variety of substrates have been demonstrated using embodiments of the process. In this disclosure metal oxides of uncertain stoichiometry are denoted as MOx where M=Si, Al, Ti, Ta, Zr, Zn, Sn, or Zr, and, —Ox represents oxide or sub-oxides (e.g., x=1 to 4 in some cases).
- Using the multi-stage platform for nanoscale plasma enhanced single and multi-layered organic and ceramic
nanoscale films 202 can be established on anysubstrate 205 of arbitrary composition and geometry. This flexibility permits the capability to tailor the surface modification chemistry to many applications. As an illustrative example,FIG. 4 shows an optical interferometry of a masked step edge silicon oxide (SiOx) plasma assisted film on a glass substrate produced by a two-stage process where tetraethoxysilane (TEOS) was used as the precursor molecule in the final stage (step 130). The appliedfilm 202 is dense, smooth and of about 200 nm in thickness. - The specific properties of the deposited
film 202 are sensitive to the precise process conditions used in the deposition. It is well known in the art that in the case of deposition on thermoplastic substrates, it is important to conduct the deposition at low temperatures to avoid dimensional distortion of the substrate. Likewise, the process of the current invention is designed to circumvent the typical 1-2 day surface reversion to low energy observed for many thermoplastic substrates treated with plasma. This invention takes advantage of the surprising beneficial effect of humid air on the atomically cleaned substrate surface to provide compact conformal films with excellent conformal barrier films with excellent adhesion properties. The customized versions of the multi-stage platform for nanoscale plasma enhanced coatings can afford a rapid low cost method for applying application specific coating combinations to industrial parts to improve impact strength, abrasion resistance and corrosion resistance. Examples of the demonstrated coatings include, but not limited to titanium oxide coatings for glass objects, silicon oxide coatings for corrosion resistant rotor blades and aircraft parts. - A
film 202 can be formed of polymeric materials by aprocess 100 that includes exposing a polymeric substrate to at least two plasma treatments (e.g., insteps 110 and 130). A first plasma treatment creates a modified reactive surface on the substrate. The subsequent second plasma treatment produces a graftedlayer 225 thereon. The initial plasma treatment is done while controlling the temperature of a radiofrequency electrodes to about 10 to 100° C. - The specific conditions used during the first plasma treatment can strongly influence characteristics of the polymeric substrate's surface. For instance, different initial plasma treatments followed by the same subsequent plasma treatment can result in grafted layer surfaces that are either hydrophilic or hydrophobic. The first plasma treatment can include a plasma reactant such as Helium, Argon, Nitrogen, Neon, Silane, Hydrogen and Oxygen and mixtures thereof. In some cases, the initial plasma treatment reaction is conducted at a radiofrequency power of 30 to 500 Watts.
- The second subsequent plasma treatment can have subsequent plasma reactants that include vinyl or acrylic monomers. Example monomers include monomers 1-Vinyl-2-pyrrolidinone, 2-Hydroxyethylmethacrylate, Allyl Alcohol, Allyl Amine, Substituted Allyl Amines of 4-10 Carbon Atoms, Acrylic Acid, Acrylic Esters of 2-10 Carbon Atoms, Acrylamides of 3-10 Carbon Atoms. In some cases the resulting surface can be used as a tie layer under a conventional solvent, spray, dip or powder coating. The conventional coating can then be used to bind a drug or other therapeutic material. In other cases, the subsequent plasma treatment can have subsequent plasma reactants that include metal alkoxide esters of Silicon, Titanium, Tantalum, Aluminum, Zirconium, or Zinc.
- The
process 100 can adapt the multi-pass plasma grafting technique described above into a multiple step process specifically designed for modifying and functionalizing the surfaces of medical devices. An advantage of the method described in this application is the ability to apply coatings on a dry-in dry-out basis, and/or in a sterile anaerobic environments. Using this method, parts can be placed into a treatment chamber dry and emerge after treatment both dry and sterile. The thin film coatings produced by the disclosed techniques are chemically bonded to the surface and are thus highly resistant to adhesion failures, delamination, flaking or debonding. The films are also coherent and uniform and are resistant to decohesion and tearing. Areas of the coated devices that need to remain non lubricious can be easily masked during the plasma coating process. The lubricity of the coating is activated by treatment of the surface with water or body fluids. - The so-deposited
film stack 202 could be comprised of organic and or inorganic polymers. The organic polymers are made from monomers can be selected of a group comprising, but not limited to, common lubricious monomers such as N-vinylpyrrolidinone and hydroxyethylmethacrylate and their copolymers ethylene and propylene oxide and their derivatives. The polymers are created in-situ at the substrate surface from treatment of the substrate in the plasma/monomer environment. - These plasma created polymer coatings provide lubricity when contacted with water or saline solution. The coated device is dry to the touch prior to water treatment for facile handling by medical or surgical personnel. The mechanical properties of the coatings, such as the flexibility of the deposited coating, can be modified by incorporation during the plasma polymerization of volatile crosslinking agents such as diallylethers, polyallylamines, gylcoldiacrylates or glycoldimethacrylates into the monomer stream. Monomers with reactive functional groups containing amine, hydroxyl, and carboxylic acid functional groups can provide sites for the further coupling of surface binding or other materials and polymers, including designer drugs for targeted delivery. For example, known lubricious urethane polymers can be attached to preceding layers containing these reactive surfaces. Further, direct attachment or binding of gel mixtures of antibiotic or other drugs can be accomplished using standard solution coating or gas phase under non-plasma vacuum/reduced pressure techniques. The coatings of this invention, including common lubricious monomers such as N-vinylpyrrolidinone, which provides lubricity when contacted with water or saline solution, have been applied on a dry-in/dry-out basis. The coated device is dry to the touch prior to water treatment for facile handling by medical or surgical personnel. Further, coating of monomers with reactive handles containing amine, hydroxyl, and carboxylic acid functional groups can provide sites for the surface binding of antibiotic or other drugs have been demonstrated.
- Table 1 is a compendium of the conditions in a coating processes on miscellaneous substrates using the
process 100 which includes two steps: a first plasma treatment in accordance with step 110 (step P1) and a second plasma treatment in accordance with step 130 (step P2), and the characterization data of the resultant articles. The substrates used in these experiments were made from polymers commonly associated with biomedical devices. In all cases, the modified surfaces showed permanent improvements in their hydrophilic (reduced water contact angles relative to the untreated substrates) -
TABLE 1 A compendium of the processing conditions, and the characterization data of the resultant articles. The first plasma treatment (P1 stage) and second plasma treatment (P2 stage) are interspersed with humid air exposure in accordance with step 120.P1 P2 Sample P1 RF P1 P1 Pres- P2 P2 RF P2 RF P2 Pres- ID Substrates Power Time Gas sure Monomer Power Time Gas sure 1-10A Tygon Tubing NA NA NA NA NA NA NA NA NA 1-10B Tygon Tubing 50 4 20% O2, 350 TYZOR TPT 50 20 Ar 350 80% Ar 1-3B Tygon Tubing 100 15 Ar 250 TEOS 50 20 Ar 250 1-5A Tygon Tubing 100 15 Ar 250 2-Hydroxyethyl 50 20 Ar 250 Methracrylate 1-2B Tygon Tubing 100 15 250 N-Vinylpyrrolidinone 50 20 Ar 250 1-11A Red Rubber 50 3 20% O2, 350 Hexamethyldisilazane 50 20 Ar 350 Bard Urethral 80% Ar Catheter 1-5E Lexan Panel 50 5.5 20% O2, 350 2-Hydroxyethyl 50 20 Ar 350 80% Ar Methracrylate 1-10C Polycarbonate 50 4 20% O2, 350 TYZOR TPT 50 20 Ar 350 Panels 80% Ar 1-5A Silicone Medical 100 15 Ar 250 2-Hydroxyethyl 50 20 Ar 250 Tubing Methracrylate 1-3C Silicone Medical 100 15 Ar 250 TEOS 50 20 Ar 250 Tubing 1-3C Silicone Medical 100 15 Ar 250 TEOS 50 20 Ar 250 Tubing 1-3D Epoxy/Graphite 100 15 Ar 250 TEOS 50 20 Ar 250 Cylinder 1-3B Latex Gloves 100 15 Ar 250 TEOS 50 20 Ar 250 1-10D Latex Gloves 50 4 20% O2, 350 TYZOR TPT 50 20 Ar 350 80% Ar 1-5A Latex Gloves 100 15 Ar 250 2-Hydroxyethyl 50 20 Ar 250 Methracrylate - The data in Table 1 shows that the process conditions used in the atomic cleaning and activation step P1 (step 110 of
FIG. 1 ) strongly influence the eventual surface characteristics. For example, starting with same substrate and finishing with identical monomer and plasma step P2 conditions, sample 1-3F is hydrophilic while sample 1-5D is hydrophobic. The principal difference is in the plasma step P1 process condition; the process gas composition, plasma power and time were different. -
TABLE 2 A compendium of the 2-Step processing conditions of Miscellaneous Substrates, and the characterization data of the resultant articles. The P1 and P2 stages are interspersed with humid air exposure in accordance with step 120.P1 RF P1 P1 P2 RF P2 P2 Contact Substrates Power Time P1 Gas Pressure P2 Monomer Power Time P2 Gas Pressure Angle Tygon Tubing NA NA NA NA NA NA NA NA NA 102 Tygon Tubing 50 4 20% O2, 350 TYZOR TPT 50 20 Ar 350 82 80% Ar Tygon Tubing 100 15 Ar 250 TEOS 50 20 Ar 250 TygonTubing 100 15 Ar 250 2-Hydroxyethyl 50 20 Ar 250 Methracrylate Tygon Tubing 100 15 250 N-Vinylpyrrolidinone 50 20 Ar 250 69 Red Rubber Bard 50 3 20% O2, 350 Hexamethyldisilazane 50 20 Ar 350 70 Urethral Catheter 80% Ar Lexan Panel 50 5.5 20% O2, 350 2-Hydroxyethyl 50 20 Ar 350 80% Ar Methracrylate Polycarbonate Panels 50 4 20% O2, 350 TYZOR TPT 50 20 Ar 350 80% Ar Silicone Medical 100 15 Ar 250 2-Hydroxyethyl 50 20 Ar 250 Tubing Methracrylate Silicone Medical 100 15 Ar 250 TEOS 50 20 Ar 250 Tubing Silicone Medical 100 15 Ar 250 TEOS 50 20 Ar 250 Tubing Epoxy/ Graphite 100 15 Ar 250 TEOS 50 20 Ar 250 Cylinder Latex Gloves 100 15 Ar 250 TEOS 50 20 Ar 250 Latex Gloves 50 4 20% O2, 350 TYZOR TPT 50 20 Ar 350 80% Ar - In some embodiments,
substrates 205 comprising feeding tube connectors and balloon catheters are surface modified by of theprocess 100 resulting in a graphedlayer 225 of an elastomeric conformal coating. In such an embodiments of the precursor molecule ofstep 130 can include polymerize 2-methyl-1,3-butadiene (isoprene) onto a variety of substrates using a single pass through of the process 100 (steps 110-130, and in in some cases step 140). This is a special case of the general olefin polymerization process, since a coating is produced which can be further cross-linked by plasma post treatment or by other means - In some embodiments,
device substrates 205 benefit from a dry low friction, biologically inert graftedlayer 225 surface with low adhesion to the biological tissues. These surfaces can be described as “dry lubricious”. Such surfaces are useful in particular for invasive medical devices such as catheters, arthroscopic tubes and implements. Implements of this type are advantageous during surgical insertion since no additional surface treatment water or external fluids are required during insertion. Some such embodiments of the disclosure use commercially available fluoro-monomers in producing low energy, hydrophobic, low coefficient of friction coatings via our two stage plasma coating process. - In some cases, the
process 100 comprises a first graftedlayer 225 of a conformal organic coating and subsequent graftedlayers 225′ (one or more repeated passes in accordance with step 170) of a plasma-assisted deposited, ceramic metal oxide coating. The forming of a plurality of subsequent graftedlayers 225′ (and in some cases watersubsequent layers 220′) where there exists one or more subsequent graftedlayer 225 and (in some cases subsequent water layer 220) can in some cases include instep 110 exposing the upper-most preceding graftedlayer 225 to a short burst of inert gas plasma designed to clean at the atomic level and to activate the surface of the preceding graftedlayer 225, and then exposure to humid air instep 120, followed by plasma assisted deposition of a thin film comprised of ceramic metal oxide of ceramic-polymer hybrid conformal surface instep 130. In some cases, the ceramic metal oxide is instep 130 chosen from the group of Si, Al, Ti, Ta, Zr, Zn, Sn, Zr. The ceramic metal sub-oxide is chosen from the group of Si, Al, Ti, Zr, Zn, Sn, Zr. - In other cases, the subsequent graphed
layer 225′ can be another conformal organic coating such as an olefinic deposited conformal surface. In some cases, one or both the preceding graphedlayer 225 and subsequent graphedlayer 225′ includes an olefinic precursor molecules chosen from the group of tyrene, 1-Hexene, or isoprene. In some cases, one or both the preceding graphedlayer 225 and subsequent graphedlayer 225′ includes an olefinic precursor molecules that are paracyclophanes, such as parylene. In some cases, the organic coating is an olefinic hydrocarbon of 4-15 carbon atoms. In some cases, the organic coating is styrene. In some cases, one or both the preceding graphedlayer 225 and subsequent graphedlayer 225′ includes an olefinic precursor molecules that are olefinic hydrocarbon of 4-15 carbon atoms. - In some embodiments, the precursor molecule used in
step 130 is a monomer selected for subsequent direct chemical reaction binding of the graftedlayer 225 to thesubstrate surface 110 are taken from the group of: acrylic acid, primary and acrylamides of up to 10 carbon atoms, allyl alcohol, primary and secondary allylamines up to 15 carbon atoms, allylglycidylether, hydroxyethylacrylate and methacrylate, hydroxypropylacrylate and methacrylate. In some embodiments the precursor molecules used instep 130 is 4-diallylaminopyridine. In some cases the subsequent graftedlayer 225′ can be fromed from precursor molecules of acrylic and methacrylic acids, tertiary allylamines in some cases 4-diallylaminopyridine. - In some embodiments, the
film layer 202 produced is active in destroying chemical warfare agents. In some cases, the film produced is active in destroying toxic industrial fluids. In some cases, the film produced by the current invention is active in destroying organic molecules under electromagnetic wave irradiation. In some cases, thefilm 202 produced is active in destroying metal-organic complex molecules under electromagnetic wave irradiation. - In some embodiments the precursor molecule used in
step 130 provides a conformal inert hydrogenated amorphouscarbon film coating 202, in some cases containing sp3 and sp2 hybridized carbon, as well as C—H bonds, e.g., formed from precursor molecules that include volatile carbon-rich fluids such as one or more of carbon tetrachloride, chloroform, benzene, and xylene In some cases, the subsequent or second graftedlayer 225 is a conformal inert hydrogenated amorphous carbon film coatings, formed in a repeated pass in accordance withstep 170. - In some embodiments, the precursor molecule used in
step 130 provides a conformal electrically and or thermally conductingfilm 202, e.g., formed from precursor molecules that include pyrrole, thiophene and aniline. - Some further illustrative examples of
films 202 formed in accordance with theprocess 100 as presented below: - Polypropylene tubes, polyethylene test tubes, aluminum sheet, and masked glass microscope slides, were placed in a plasma deposition chamber held between 0° C. and 100° C. and activated with Argon plasma at pressures between 50 and 500 mTorr at power between 50 and 200 Watts. Following activation, humid air or water saturated air was allowed to bleed into the deposition chamber until the chamber pressure reached 1 atmosphere, and then the system was evacuated to base pressure. The plasma assisted deposition stage was then initiated. Hexafluoropropylene was introduced into the plasma chamber under Argon plasma at pressures from 100 to 500 mTorr and power between 50 and 250 Watts and treatment was continued for between 15 to 60 minutes.
- The process produced a yellow conformal coating. The thickness of the coating increased monotonically with increasing stage-two treatment time, reaching a thickness of about 100 nm in 60 minutes on all of the test surfaces. This suggests that the film deposition rate depended on the reactive precursor species reaching the activated surface, where it is readily incorporated into the growing film.
- The films produced on all the test surfaces were smooth and hydrophobic, with static water contact angles of between 120°-125° C. and no contact hysteresis. The films were also highly adherent to the substrates, based on the results from a modified qualitative “Scotch tape peel” tests. In these tests, a piece of Scotch™ brand tape was firmly pressed onto the coated substrate for 5 minutes and then quickly removed at 90-degrees. If little or none of the yellowish coating was peeled substrate surface, then the adhesion of the film to the substrate is considered good. All the tested samples, produced in this example passed this test.
- Experiments were conducted to evaluate the efficacy of various barrier coatings in protecting electronic circuitry. In this example, the ability to reduce the shifts caused by autoclaving in the air flow characteristic of arthroscopic flow-meters was evaluated. The device was built as normal, calibrated for air flow and verified in normal ambient tests. The devices were then disassembled, and the control electronics coated by the methods of this invention, as described below. The devices were then reassembled with coated electronics boards then retested for air flow at pre-determined set points.
- In one embodiment, an electronic board previously coated with Parylene-C was subjected to a two stage plasma activation and deposition process. The first stage was carried out in argon plasma at 250 mTorr at 100 W power for up to 5 minutes. Following activation, humid air or water saturated air was allowed to bleed into the deposition chamber, which was partially pre-filled with an inert gas, until the chamber pressure reached 1 atmosphere, and then the system was evacuated to base pressure, backfilled with the inert gas and pumped down to base pressure twice before the plasma assisted deposition stage was then initiated. In the plasma assisted deposition stage, subsequent, tetraethyloxyorthosilane [TEOS] was introduced and plasma conditions of 250 mTorr and 100 W maintained for 25 minutes to yield a conformal SiOx overcoating.
- In another embodiment, a circuit board controller was first subjected to a two stage plasma activation and deposition process. The first stage was carried out in argon plasma at 250 mTorr at 100 W power for up to 5 minutes. In the plasma assisted deposition stage, Tetraethyloxyorthosilane [TEOS] was introduced and plasma conditions of 250 mTorr and 100 W maintained for 25 minutes to yield a conformal SiOx coating. This was followed by thermal vapor coating with Parylene-C, and then finally coated again with the two stage plasma process, interspersed with humid-air breaks of Example 1 to create a three layer conformal barrier coating.
- The electronic control boards were evaluated using a modified unbiased autoclave test (JEDEC Standard JESD22-A102, http:www.jedec.org, incorporated by reference herein in its entirety). The JEDEC Standard JESD22-A102 test is a highly accelerated test which employs conditions of pressure, humidity and temperature under condensing conditions to accelerate moisture penetration through the external coating materials and along the interface between the external protective film material and the underlying metallic components. The autoclave test used to simulate device survivability in harsh conditions and/or long-term reliability testing. The circuit boards were subjected to multiple heat and cool cycles.
- Large air flow deviations at low flow set points are characteristics of the flow meters tested in this example, and such deviations were used as index of flow meter performance. In these tests. The failure criterion is a flow deviation at 20%; any device showing flow deviation of greater than 20% at any gas flow set point is considered to have failed.
-
FIG. 5 and Table 4 summarize the results from these tests. The results clearly show that the under- and over-coat of parlyene with SiOx from the current invention significantly improved the performance and the long-term reliability of the control electronics evaluated. -
TABLE 3 Summary of the results from Autoclave Cycling tests in Example 2 Max Number of Coating Type Cycles Before Fail None 0 40 nm Parylene Only 10 40 nm Parlyene + 100 nm SiO2 Overcoat >20 100 nm SiO2 undercoat/40 nm Parlyene/100 nm >20 SiO2 overcoat - Polyethylene blow-molded fuel tanks for small engines were sealed to mitigate permeation of hydrocarbon fluids. The untreated tanks have inherent permeability of hydrocarbon fluids and the current state of the art mitigation treatments, such as gaseous fluorination of the tank surfaces in large chambers and multilayer polymer co-extrusion are environmentally less preferred and capital intensive respectively.
- A commercial polyethylene blow molded small engine fuel tank (e.g., obtained from Mergon Corporation, Anderson, SC) was coated with SiOx using the process of this invention. The blow molded fuel tanks were coated in the two stage plasma process consisting of a plasma activation stage from 2-10 minutes at 50-100 W Argon plasma at 100-500 MTorr, preferably at 250 mTorr, followed by a plasma grafting stage, where Tetraethyloxyorthosilane [TEOS] was introduced. The plasma conditions of the grafing stage were 100-250 MTorr and 100 W maintained for 25 minutes. The resultant thickness of the conformal SiOx over-coating was about 150 nm.
- To evaluate the effectiveness of the coatings in suppressing fuel loss, the coated tanks were filled with commercial 87 octane gasoline, closed with a commercial small engine fuel tank cap, placed in a covered, 10 gallon polyethylene buckets, and stored at room temperature for 26 months. Identical, but uncoated control tanks were likewise filled and similarly stored. After 26 months, the mean net weight of the fuel remaining in the coated tanks was 397 g, as compared to 372 g remaining in the uncoated tanks. This demonstrates that the conformal coatings from this invention deposited on the fuel tanks were effective in mitigating hydrocarbon fuel loss due to permeation polyethylene blow molded fuel tank.
- In a series of demonstration experiments, multi stage plasma based coatings were produced with a variety of olefinic monomers (Styrene, 1-Hexene, Isoprene) in the subsequent grafting stage to produce nanoscale conformal barrier coatings. The substrates were coated in the two stage plasma process consisting of a plasma activation stage from 1-10 minutes at 50-100 W argon plasma at 100-500 mTorr, preferably at 250 mTorr, followed by a plasma grafting stage, where olefinic monomers were introduced. The plasma conditions of the grafting stage were 100-250 mTorr, and preferably 100 W maintained for up to 30 minutes. Coatings were applied to polypropylene and polyethylene tubes, polycarbonate and acrylic sheets, aluminum sheets, and borosilicate glass slide substrates. The coatings were uniform, smooth and adherent between 60 and 200 nm in thickness deepening on specific process conditions.
FIG. 6 shows an optical interferometry example image of an example 60 nm styrene coating edge on a de-masked borosilicate glass sample. - Other functional olefinic monomers can likewise be employed by the methods of this invention to produce reactive grafted surface polymers.
- The reactive surfaces demonstrated in example 4 can be employed as tie and/or priming coats and sub-coats to bind other materials to the surface or to catalyze chemical reactions at the surface. In example 1, the grafting of allyl alcohol and allylamine to a variety of substrates were demonstrated. In this example, other suitable monomers such as allylglycidylether, were used to graft a reactive epoxy coating onto the substrate, and then used to couple 4-diallylaminopyridine, to produce a grafted dialkylaminopyridine catalytic surface. Polymeric dialkylaminopyridines have been shown to be useful in catalyzing the destruction of chemical warfare agents and toxic industrial materials. (See e.g., Yokley and Nielsen, US Patent Application, US20110028774, Hypernucleophilic Catalysts for Detoxification of Chemical Threat Agents, incorporated by reference herein in its entirety).
- Electrically conducting coatings were applied to polypropylene and polyethylene tubes, polycarbonate and acrylic sheets, aluminum sheets, borosilicate glass slides and on inter-digitated conductive test structures; the substrates were treated in a two phase plasma coating process. The activation phase was conducted at 75 W power at 300 mTorr pressure using a 67% argon and 33% air plasma for 2 minutes. The subsequent phase admitted pyrrole into the plasma chamber at a pressure ranging from 300-400 mTorr for 75 W for 30 minutes. The chamber temperature rose from 12° C. to 18° C.
- A thin colorless conformal coating of about 12 nm in thickness was deposited as characterized with an optical interferometry. The coatings were uniform, smooth and adherent. The electrical conductivity of the prepared conducting polymer films (comprised of mostly polypyrrole) was measured at room temperature by four-point probe technique, taking the average value of several readings at various points of the films. The electrical data varied significantly from site to site over the samples, and from sample to sample. The best conductivity of the as-deposited undoped films measured was about 1×10−2 S/cm.
- Inert hydrogenated amorphous carbon film coatings (possibly containing sp3 and sp2 hybridized carbon, as well as C—H bonds) were applied to polypropylene and polyethylene tubes, polycarbonate and acrylic sheets, aluminum sheets, and glass slides; the substrates were treated in a two phase plasma coating process. The activation phase was conducted for 2 minutes at 175-300 mTorr and 75 W power, with argon as the background gas. In one embodiment, Carbon Tetrachloride (CCl4) was introduced into the plasma chamber with argon as the carrier and background gas in the subsequent phase, at 75 W power and 175-300 mTorr for 30 minutes. In another embodiment, xylene (C7H8) was introduced into the plasma chamber with argon as the carrier and background gas in the subsequent phase, also at 75 W power and 175-300 mTorr for 30 minutes.
- In both embodiments, the process produced a colorless conformal and hydrophobic coating. The thickness of the coating increased monotonically with increasing stage-two treatment time, reaching a thickness of about 150 nm in 30 minutes on all of the test surfaces. This suggests that the film deposition rate was independent of the carbon source, but depended only on the reactive precursor species reaching the activated surface, where it is readily incorporated into the growing film.
- Specialty filtration membranes and related devices are becoming an integral part of bioprocessing, semiconductor and other high value industrial processes. Likewise, micro-reactor technology where the configurations take advantage of high reactor surface to volume ratios to achieve specific surface binding of catalysts or other reaction modifiers are becoming items of intense study. In most cases the filter media are made from chemically inert and low surface energy materials such as polyethylene, polypropylene, other polyolefins or polysulfone. The coatings of this invention have the ability to directly and selectively modify the chemical properties of channels, micro-pinholes and tortuous paths of specific filters. The coatings of this invention are uniquely able to perform these operations since the activation is driven by the plasma which accesses all surfaces within the plasma reaction chamber, and the volatile monomers are delivered to the activated surface sites in the gas phase. The advantages of a rapid, general, and chemically flexible system that can be used on finished configurations on a dry-in/dry-out basis are clearly evident to those skilled in the art.
- In this example, an embodiment of the
process 100 of the disclosure was used to modify a variety of filter membranes materials, to create surfaces capable of binding metal ions through dative bonding. For example, by functionalizing the membrane with soft ligands (e.g., aliphatic-, thiols, amines, etc.) one can selectively bind coinage metal ions (Ag, Au, etc. . . . ). Specifically, the allyamine surfaces created in example 1, bind copper ions, and were used to reduce the concentration of Cu2+ in aqueous solutions placed in contact with such surfaces. - The performance of polyvinylalcohol (PVA) objects (e.g. PVA brushes) in aqueous environments are constrained by, but not limited to, the difficulties in hydration (requiring brushes to shipped in wet envelopes), bio-fouling (bacteria growth in the brushes leading to high particle count) and lack of application specificity (′one-size fits all′ approach, use the same brush for all substrate)
- Current efforts to address these concerns utilize modifications to the composition of the aqueous environments (e.g., cleaning solutions, etc.). Such modifications are not always successful. We propose to mitigate these limitations, without negatively impacting performance, with appropriate choice of secondary coatings on the brush bristles.
- Specifically, using the inventions in this disclosure the inventors successfully modified commercial PVA brushes with secondary coatings that bind detrimental metallic species, such as Cu- and other metallic ions, to proactively address yield and reliability limiting dielectric contamination in semiconductor manufacturing. By appropriate choice of such coatings, it is possible to also prevent bio-fouling (bacteria growth in the brushes leading to high particle count) and lack of application specificity.
- The effects of sand erosion and/or ablation on helicopter rotors blades is a perennial problem in sandy environments and rotor blade replacement represents a significant cost over a helicopter's operational life. Most helicopter rotor blades include erosion protection in the form of leading edge strips made from metals such as nickel, titanium and stainless steel. Polyurethane-based coatings, tapes and boots have also been used for erosion protection. However, neither strategy gives optimal erosion resistance from both rain and sand. Metal leading edges have excellent rain resistance but poor sand erosion performance. Conversely, polyurethane-based coatings have good sand erosion protection, but poor rain resistance.
- Increased durability of ceramic modified thermoplastics in corrosive aqueous abrasive environments have been demonstrated. In particular, two stage plasma based coatings of this invention of SiOx and TiOx to both thermoplastic and thermoset materials are used to improve durability. The coatings of this invention, in particular the inorganic oxides as applied to the previously described polyurethane rotor protection boots can provide effective aqueous surface protection in a high abrasive environment.
- Those skilled in the art to which the invention relates will appreciate that other and further additions, deletions, substitutions and modifications may be made to the described embodiments without departing from the scope of the invention.
Claims (19)
1. A electronic device, comprising:
a substrate having a component-side surface; and
a moisture protection film covering the component-side surface, the moisture protection film including:
a first water layer bonded to component-side surface that is an activated surface, wherein the activated surface has a lower water contact angle than the substrate surface before the surface activation;
a first graphed layer of a plasma-reacted first set of precursor molecules graphed to the first water layer, wherein the first water layer forms a first bonding link between the substrate surface and the reacted first set precursor molecules;
a second water layer bonded to the first graphed layer; and
a second graphed layer of a plasma-reacted second set of precursor molecules graphed to the second water layer, wherein the second water layer forms a second bonding link between the second water layer and the reacted second set of precursor molecules.
2. The device of claim 1 , wherein:
the component-side surface was exposed a first plasma treatment having plasma reactants in a plasma chamber to form the activated substrate surface;
the first water layer was formed after removing the plasma reactants from the plasma chamber and then introducing water vapor into the plasma chamber to form the first water layer bonded to the activated surface; and then
the plasma-reacted first set of precursor molecules was formed in a second plasma treatment that includes introducing the precursor molecules of the first set into the plasma chamber at a plasma chamber pressure that is in a range from 100 mTorr to 500 mTorr.
3. The device of claim 2 , wherein the precursor molecules of the first set include olefinic hydrocarbon of 4-15 carbon atoms.
4. The device of claim 2 , wherein the olefinic precursor molecules includes paracyclophanes.
5. The device of claim 2 , wherein the olefinic precursor molecules includes parylene.
6. The device of claim 2 , wherein the precursor molecules of the first set include tetraethyloxyorthosilane.
7. The device of claim 2 , wherein:
the second water layer was formed after removing the precursor molecules of the first set from the plasma chamber and then introducing water vapor into the plasma chamber to form the second water layer bonded to the the plasma-reacted first set of precursor molecules; and then
the plasma-reacted second set of precursor molecules was formed in a third plasma treatment that includes introducing the precursor molecules of the second set into the plasma chamber at a plasma chamber pressure that is in a range from 100 mTorr to 500 mTorr.
8. The device of claim 7 , wherein the precursor molecules of the first set include olefinic hydrocarbon of 4-15 carbon atoms.
9. The device of claim 7 , wherein the olefinic precursor molecules includes paracyclophanes.
10. The device of claim 7 , wherein the olefinic precursor molecules includes parylene.
11. The device of claim 7 , wherein the precursor molecules of the first set include tetraethyloxyorthosilane.
12. The device of claim 1 , wherein the component-side surface includes a borosilicate glass surface.
13. The device of claim 1 , wherein the component-side surface includes a surface of a thermal vapor coating of parylene.
14. The device of claim 1 , wherein the component-side surface includes a surface of electrically conductive polymer.
15. The device of claim 1 , wherein the first graphed layer of the plasma-reacted first set of precursor molecules is a parylene layer and the second graphed layer of the plasma-reacted second set of precursor molecules is a parylene layer.
16. The device of claim 1 , wherein the first graphed layer of the plasma-reacted first set of precursor molecules is a silicon oxide layer and the second graphed layer of the plasma-reacted second set of precursor molecules is a silicon oxide layer.
17. The device of claim 1 , wherein the first graphed layer of the plasma-reacted first set of precursor molecules is a silicon oxide layer and the second graphed layer of the plasma-reacted second set of precursor molecules is a parylene layer.
18. The device of claim 1 , wherein the first graphed layer of the plasma-reacted first set of precursor molecules is a parylene layer and the second graphed layer of the plasma-reacted second set of precursor molecules is a silicon oxide layer.
19. The device of claim 1 , wherein the moisture protection film covering the component-side surface is a conformal coating.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/579,464 US20150103504A1 (en) | 2007-09-07 | 2014-12-22 | Surface properties of polymeric materials with nanoscale functional coating |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US97058207P | 2007-09-07 | 2007-09-07 | |
US12/206,013 US20090069790A1 (en) | 2007-09-07 | 2008-09-08 | Surface properties of polymeric materials with nanoscale functional coating |
US201161564415P | 2011-11-29 | 2011-11-29 | |
US13/665,314 US8962097B1 (en) | 2007-09-07 | 2012-10-31 | Surface properties of polymeric materials with nanoscale functional coating |
US14/579,464 US20150103504A1 (en) | 2007-09-07 | 2014-12-22 | Surface properties of polymeric materials with nanoscale functional coating |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/665,314 Continuation US8962097B1 (en) | 2007-09-07 | 2012-10-31 | Surface properties of polymeric materials with nanoscale functional coating |
Publications (1)
Publication Number | Publication Date |
---|---|
US20150103504A1 true US20150103504A1 (en) | 2015-04-16 |
Family
ID=50627989
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/665,314 Active US8962097B1 (en) | 2007-09-07 | 2012-10-31 | Surface properties of polymeric materials with nanoscale functional coating |
US14/579,464 Abandoned US20150103504A1 (en) | 2007-09-07 | 2014-12-22 | Surface properties of polymeric materials with nanoscale functional coating |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/665,314 Active US8962097B1 (en) | 2007-09-07 | 2012-10-31 | Surface properties of polymeric materials with nanoscale functional coating |
Country Status (2)
Country | Link |
---|---|
US (2) | US8962097B1 (en) |
WO (1) | WO2014070750A1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016198870A1 (en) * | 2015-06-10 | 2016-12-15 | Semblant Limited | Coated electrical assembly |
WO2017216544A1 (en) * | 2016-06-14 | 2017-12-21 | Surface Innovations Limited | Coating |
CN108141963A (en) * | 2015-09-24 | 2018-06-08 | 欧洲等离子公司 | Polymer coating and the method for deposited polymeric coatings |
WO2019108730A1 (en) * | 2017-11-30 | 2019-06-06 | The Trustees Of Princeton University | Adhesion layer bonded to an activated surface |
US10872478B2 (en) | 2015-09-14 | 2020-12-22 | Neology, Inc. | Embedded on-board diagnostic (OBD) device for a vehicle |
US11786930B2 (en) | 2016-12-13 | 2023-10-17 | Hzo, Inc. | Protective coating |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9250178B2 (en) * | 2011-10-07 | 2016-02-02 | Kla-Tencor Corporation | Passivation of nonlinear optical crystals |
US20220259394A1 (en) * | 2014-12-17 | 2022-08-18 | Sio2 Medical Products, Inc. | Polymeric surface having reduced biomolecule adhesion to thermoplastic articles and methods of plasma treatment |
US20190092916A1 (en) * | 2014-12-17 | 2019-03-28 | Sio2 Medical Products, Inc. | Plasma treatment with non-polymerizing compounds that leads to reduced biomolecule adhesion to thermoplastic articles |
EP3377565B1 (en) * | 2015-11-16 | 2020-12-23 | SiO2 Medical Products, Inc. | Polymeric substrate with a surface having reduced biomolecule adhesion, and thermoplastic articles of such substrate |
KR101989468B1 (en) * | 2017-06-22 | 2019-06-14 | 성균관대학교 산학협력단 | Preparing method of substrate for culturing stem cell |
CN111197176B (en) * | 2019-12-30 | 2022-03-08 | 中国科学院青海盐湖研究所 | Electrochemical treatment method of copper foil and composite copper foil material |
CN115262211B (en) * | 2022-07-15 | 2023-08-29 | 南方科技大学 | Super-hydrophobic fabric and preparation method thereof |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4573768A (en) * | 1983-12-05 | 1986-03-04 | The Signal Companies, Inc. | Electrochromic devices |
US4729062A (en) * | 1986-06-16 | 1988-03-01 | Hughes Aircraft Company | Reworkable encapsulated electronic assembly |
US4921723A (en) * | 1987-10-16 | 1990-05-01 | The Curators Of The University Of Missouri | Process for applying a composite insulative coating to a substrate |
US5153986A (en) * | 1991-07-17 | 1992-10-13 | International Business Machines | Method for fabricating metal core layers for a multi-layer circuit board |
US5376400A (en) * | 1990-10-24 | 1994-12-27 | University Of Florida Research Foundation, Inc. | Combined plasma and gamma radiation polymerization method for modifying surfaces |
US5711987A (en) * | 1996-10-04 | 1998-01-27 | Dow Corning Corporation | Electronic coatings |
US5880518A (en) * | 1996-09-10 | 1999-03-09 | Mitsubishi Denki Kabushiki Kaisha | Semiconductor device including a two-layer protective insulating layer |
US20040195960A1 (en) * | 2001-08-20 | 2004-10-07 | Grzegorz Czeremuszkin | Coatings with low permeation of gases and vapors |
Family Cites Families (60)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3941730A (en) | 1972-06-05 | 1976-03-02 | E. I. Du Pont De Nemours And Company | Polyvinyl alcohol microgel precursor blends |
US3941728A (en) | 1972-06-05 | 1976-03-02 | E. I. Du Pont De Nemours And Company | Polyvinyl alcohol-polysaccharide microgels |
US3839307A (en) | 1972-06-05 | 1974-10-01 | Du Pont | Process of producing polyvinyl alcohol microgels |
JPS5814453B2 (en) * | 1979-07-16 | 1983-03-19 | 信越化学工業株式会社 | Surface treatment method for plastic molded products |
US4269896A (en) * | 1979-08-31 | 1981-05-26 | Hughes Aircraft Company | Surface passivated alkali halide infrared windows |
US4569850A (en) * | 1983-11-23 | 1986-02-11 | Auburn Research Foundation | Method for thermally blasting outer coverings from food products |
EP0280673B1 (en) * | 1987-02-25 | 1991-07-31 | Nippon Shokubai Kagaku Kogyo Co., Ltd | Method for production of inorganic minute globular particles |
US4927676A (en) | 1988-07-01 | 1990-05-22 | Becton, Dickinson And Company | Method for rapid adherence of endothelial cells onto a surface and surfaces prepared thereby |
US5019210A (en) * | 1989-04-03 | 1991-05-28 | International Business Machines Corporation | Method for enhancing the adhesion of polymer surfaces by water vapor plasma treatment |
US5013338A (en) | 1989-09-01 | 1991-05-07 | Air Products And Chemicals, Inc. | Plasma-assisted polymerization of monomers onto polymers and gas separation membranes produced thereby |
JP2990608B2 (en) * | 1989-12-13 | 1999-12-13 | 株式会社ブリヂストン | Surface treatment method |
US5314724A (en) * | 1991-01-08 | 1994-05-24 | Fujitsu Limited | Process for forming silicon oxide film |
US5227023A (en) * | 1991-08-26 | 1993-07-13 | James River Corporation Of Virginia | Multi-layer papers and tissues |
US5344462A (en) * | 1992-04-06 | 1994-09-06 | Plasma Plus | Gas plasma treatment for modification of surface wetting properties |
NO931809L (en) | 1993-05-19 | 1994-11-21 | Norsk Hydro As | hemophilia |
US5622626A (en) | 1994-04-15 | 1997-04-22 | Pall Corporation | Multiple compartment filter and method for processing parenteral fluid |
US5576072A (en) * | 1995-02-01 | 1996-11-19 | Schneider (Usa), Inc. | Process for producing slippery, tenaciously adhering hydrogel coatings containing a polyurethane-urea polymer hydrogel commingled with at least one other, dissimilar polymer hydrogel |
US5993972A (en) | 1996-08-26 | 1999-11-30 | Tyndale Plains-Hunter, Ltd. | Hydrophilic and hydrophobic polyether polyurethanes and uses therefor |
IT1291710B1 (en) * | 1997-05-30 | 1999-01-21 | Gilles Picard | METHOD AND EQUIPMENT FOR THE PREPARATION OF MONOLAYER FILM OF PARTICLES OR MOLECULES. |
US6316055B1 (en) * | 1998-05-01 | 2001-11-13 | Virginia Tech Intellectual Properties, Inc. | Near-room temperature thermal chemical vapor deposition of oxide films |
US6550915B1 (en) * | 1998-12-21 | 2003-04-22 | Bausch & Lomb Incorporated | Surface treatment of fluorinated contact lens materials |
WO2001029118A1 (en) * | 1999-10-19 | 2001-04-26 | Commonwealth Scientific And Industrial Research Organisation | Preparation of functional polymeric surface |
JP3915365B2 (en) * | 2000-03-10 | 2007-05-16 | コニカミノルタホールディングス株式会社 | Silver halide photographic material for heat development and method for producing the same |
US6428861B2 (en) * | 2000-06-13 | 2002-08-06 | Procter & Gamble Company | Apparatus and process for plasma treatment of particulate matter |
US6596388B1 (en) | 2000-11-29 | 2003-07-22 | Psiloquest | Method of introducing organic and inorganic grafted compounds throughout a thermoplastic polishing pad using a supercritical fluid and applications therefor |
US7059946B1 (en) | 2000-11-29 | 2006-06-13 | Psiloquest Inc. | Compacted polishing pads for improved chemical mechanical polishing longevity |
US6688956B1 (en) | 2000-11-29 | 2004-02-10 | Psiloquest Inc. | Substrate polishing device and method |
US20050266226A1 (en) | 2000-11-29 | 2005-12-01 | Psiloquest | Chemical mechanical polishing pad and method for selective metal and barrier polishing |
US6579604B2 (en) | 2000-11-29 | 2003-06-17 | Psiloquest Inc. | Method of altering and preserving the surface properties of a polishing pad and specific applications therefor |
US6846225B2 (en) | 2000-11-29 | 2005-01-25 | Psiloquest, Inc. | Selective chemical-mechanical polishing properties of a cross-linked polymer and specific applications therefor |
US6684704B1 (en) | 2002-09-12 | 2004-02-03 | Psiloquest, Inc. | Measuring the surface properties of polishing pads using ultrasonic reflectance |
US6706383B1 (en) | 2001-11-27 | 2004-03-16 | Psiloquest, Inc. | Polishing pad support that improves polishing performance and longevity |
US6764574B1 (en) | 2001-03-06 | 2004-07-20 | Psiloquest | Polishing pad composition and method of use |
US6575823B1 (en) | 2001-03-06 | 2003-06-10 | Psiloquest Inc. | Polishing pad and method for in situ delivery of chemical mechanical polishing slurry modifiers and applications thereof |
US6818301B2 (en) | 2001-06-01 | 2004-11-16 | Psiloquest Inc. | Thermal management with filled polymeric polishing pads and applications therefor |
US20040132308A1 (en) | 2001-10-24 | 2004-07-08 | Psiloquest, Inc. | Corrosion retarding polishing slurry for the chemical mechanical polishing of copper surfaces |
US20060093771A1 (en) | 2002-02-15 | 2006-05-04 | Frantisek Rypacek | Polymer coating for medical devices |
US6716733B2 (en) | 2002-06-11 | 2004-04-06 | Applied Materials, Inc. | CVD-PVD deposition process |
US7303575B2 (en) | 2002-08-01 | 2007-12-04 | Lumen Biomedical, Inc. | Embolism protection devices |
US6838169B2 (en) | 2002-09-11 | 2005-01-04 | Psiloquest, Inc. | Polishing pad resistant to delamination |
US7579077B2 (en) | 2003-05-05 | 2009-08-25 | Nanosys, Inc. | Nanofiber surfaces for use in enhanced surface area applications |
CN1863644A (en) | 2003-09-15 | 2006-11-15 | 皮斯洛奎斯特公司 | Polishing pad for chemical mechanical polishing |
US20050153631A1 (en) | 2004-01-13 | 2005-07-14 | Psiloquest | System and method for monitoring quality control of chemical mechanical polishing pads |
EP1735811B1 (en) * | 2004-04-02 | 2015-09-09 | California Institute Of Technology | Method and system for ultrafast photoelectron microscope |
US8323754B2 (en) | 2004-05-21 | 2012-12-04 | Applied Materials, Inc. | Stabilization of high-k dielectric materials |
US20060251795A1 (en) * | 2005-05-05 | 2006-11-09 | Boris Kobrin | Controlled vapor deposition of biocompatible coatings for medical devices |
US20060154579A1 (en) | 2005-01-12 | 2006-07-13 | Psiloquest | Thermoplastic chemical mechanical polishing pad and method of manufacture |
WO2006132308A1 (en) * | 2005-06-10 | 2006-12-14 | Bridgestone Corporation | Process for producing ultrafine particle or ultrafine particle aggregate |
US8216663B2 (en) | 2005-06-28 | 2012-07-10 | Canaan Precision Co., Ltd. | Surface-modified member, surface-treating process and apparatus therefor |
KR100712525B1 (en) * | 2005-08-16 | 2007-04-30 | 삼성전자주식회사 | Capacitor of semiconductor device and method for fabricating the same |
JP4855758B2 (en) * | 2005-10-19 | 2012-01-18 | 東海旅客鉄道株式会社 | Method for producing diamond having acicular protrusion arrangement structure on surface |
WO2007064594A2 (en) * | 2005-11-29 | 2007-06-07 | Bausch & Lomb Incorporated | New coatings on ophthalmic lenses |
US20070172666A1 (en) * | 2006-01-24 | 2007-07-26 | Denes Ferencz S | RF plasma-enhanced deposition of fluorinated films |
WO2007127989A2 (en) * | 2006-04-28 | 2007-11-08 | Medtronic, Inc. | Wettable eptfe medical devices |
US20080044588A1 (en) * | 2006-08-15 | 2008-02-21 | Sakhrani Vinay G | Method for Treating a Hydrophilic Surface |
WO2008045433A1 (en) | 2006-10-10 | 2008-04-17 | Massachusetts Institute Of Technology | Absorbant superhydrophobic materials, and methods of preparation and use thereof |
WO2008060522A2 (en) * | 2006-11-10 | 2008-05-22 | The Regents Of The University Of California | Atmospheric pressure plasma-induced graft polymerization |
US20090069790A1 (en) | 2007-09-07 | 2009-03-12 | Edward Maxwell Yokley | Surface properties of polymeric materials with nanoscale functional coating |
WO2009103718A1 (en) | 2008-02-18 | 2009-08-27 | Dsm Ip Assets B.V. | Coating compositon comprising an antimicrobial copolymer |
US8313985B2 (en) | 2010-10-21 | 2012-11-20 | Rf Micro Devices, Inc. | Atomic layer deposition encapsulation for power amplifiers in RF circuits |
-
2012
- 2012-10-31 US US13/665,314 patent/US8962097B1/en active Active
-
2013
- 2013-10-29 WO PCT/US2013/067280 patent/WO2014070750A1/en active Application Filing
-
2014
- 2014-12-22 US US14/579,464 patent/US20150103504A1/en not_active Abandoned
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4573768A (en) * | 1983-12-05 | 1986-03-04 | The Signal Companies, Inc. | Electrochromic devices |
US4729062A (en) * | 1986-06-16 | 1988-03-01 | Hughes Aircraft Company | Reworkable encapsulated electronic assembly |
US4921723A (en) * | 1987-10-16 | 1990-05-01 | The Curators Of The University Of Missouri | Process for applying a composite insulative coating to a substrate |
US5376400A (en) * | 1990-10-24 | 1994-12-27 | University Of Florida Research Foundation, Inc. | Combined plasma and gamma radiation polymerization method for modifying surfaces |
US5153986A (en) * | 1991-07-17 | 1992-10-13 | International Business Machines | Method for fabricating metal core layers for a multi-layer circuit board |
US5880518A (en) * | 1996-09-10 | 1999-03-09 | Mitsubishi Denki Kabushiki Kaisha | Semiconductor device including a two-layer protective insulating layer |
US5711987A (en) * | 1996-10-04 | 1998-01-27 | Dow Corning Corporation | Electronic coatings |
US20040195960A1 (en) * | 2001-08-20 | 2004-10-07 | Grzegorz Czeremuszkin | Coatings with low permeation of gases and vapors |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016198870A1 (en) * | 2015-06-10 | 2016-12-15 | Semblant Limited | Coated electrical assembly |
US20190090358A1 (en) * | 2015-06-10 | 2019-03-21 | Semblant Limited | Coated electrical assembly |
US10872478B2 (en) | 2015-09-14 | 2020-12-22 | Neology, Inc. | Embedded on-board diagnostic (OBD) device for a vehicle |
CN108141963A (en) * | 2015-09-24 | 2018-06-08 | 欧洲等离子公司 | Polymer coating and the method for deposited polymeric coatings |
US20180279483A1 (en) * | 2015-09-24 | 2018-09-27 | Europlasma Nv | Polymer coatings and methods for depositing polymer coatings |
US11419220B2 (en) * | 2015-09-24 | 2022-08-16 | Europlasma Nv | Polymer coatings and methods for depositing polymer coatings |
WO2017216544A1 (en) * | 2016-06-14 | 2017-12-21 | Surface Innovations Limited | Coating |
US11786930B2 (en) | 2016-12-13 | 2023-10-17 | Hzo, Inc. | Protective coating |
WO2019108730A1 (en) * | 2017-11-30 | 2019-06-06 | The Trustees Of Princeton University | Adhesion layer bonded to an activated surface |
Also Published As
Publication number | Publication date |
---|---|
WO2014070750A1 (en) | 2014-05-08 |
US8962097B1 (en) | 2015-02-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8962097B1 (en) | Surface properties of polymeric materials with nanoscale functional coating | |
JP5313671B2 (en) | Moisture and moisture barrier coating | |
JP5344177B2 (en) | Flexible plasma polymer products, corresponding articles and their use | |
KR101473021B1 (en) | Multilayer body | |
JP3637078B2 (en) | Gas barrier low moisture permeability insulating transparent electrode substrate and use thereof | |
KR101688239B1 (en) | Laminate, method for producing same, electronic device member, and electronic device | |
EP2289983B1 (en) | Composite film | |
JP5749678B2 (en) | Gas barrier film | |
JP6353828B2 (en) | GAS BARRIER LAMINATE, ELECTRONIC DEVICE MEMBER AND ELECTRONIC DEVICE | |
JP2004314599A (en) | Barrier film | |
TWI733777B (en) | Curable composition for forming primer layer, gas barrier laminated film and gas barrier laminated body | |
JP3974219B2 (en) | Gas barrier film | |
JP2009196318A (en) | Manufacturing method for laminated body and barrier type film board, barrier material, device, and optical member | |
US7354625B2 (en) | Gas barrier film | |
JP2008018679A (en) | Release film | |
US20100028526A1 (en) | Thin film coating method | |
JP3934895B2 (en) | Barrier film, laminated material using the same, packaging container, image display medium, and barrier film manufacturing method | |
EP2733233B1 (en) | Interlayer composite substrates | |
JP5223466B2 (en) | Gas barrier film and method for producing the same | |
JP2008080704A (en) | Gas barrier laminate | |
Friedrich | Tailoring of interface/interphase to promote metal‐polymer adhesion | |
JP4978066B2 (en) | Method for evaluating manufacturing conditions of gas barrier film laminate | |
JP4321706B2 (en) | Laminated body and method for producing the same | |
JP5332281B2 (en) | Gas barrier laminated film | |
JP4224330B2 (en) | Barrier film |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |