EP1328341A1 - Systemes et procedes de revetements combinatoires - Google Patents
Systemes et procedes de revetements combinatoiresInfo
- Publication number
- EP1328341A1 EP1328341A1 EP01944524A EP01944524A EP1328341A1 EP 1328341 A1 EP1328341 A1 EP 1328341A1 EP 01944524 A EP01944524 A EP 01944524A EP 01944524 A EP01944524 A EP 01944524A EP 1328341 A1 EP1328341 A1 EP 1328341A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- materials
- substrate
- delivery
- coating
- mask
- 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.)
- Withdrawn
Links
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- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- -1 oxides Chemical class 0.000 claims description 6
- 150000004767 nitrides Chemical class 0.000 claims description 5
- 229920001169 thermoplastic Polymers 0.000 claims description 5
- 229920001187 thermosetting polymer Polymers 0.000 claims description 5
- 239000004634 thermosetting polymer Substances 0.000 claims description 5
- 150000003568 thioethers Chemical class 0.000 claims description 5
- 238000009501 film coating Methods 0.000 claims 6
- 230000008016 vaporization Effects 0.000 claims 2
- 238000004458 analytical method Methods 0.000 abstract description 5
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
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- 239000003595 mist Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
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- 239000010703 silicon Substances 0.000 description 2
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- 230000003746 surface roughness Effects 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
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- 229920002678 cellulose Polymers 0.000 description 1
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- 238000004132 cross linking Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 239000010408 film Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000007737 ion beam deposition Methods 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
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- 239000012860 organic pigment Substances 0.000 description 1
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- 230000035699 permeability Effects 0.000 description 1
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- 229920003023 plastic Polymers 0.000 description 1
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- 229920000058 polyacrylate Polymers 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
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- 239000002243 precursor Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
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- 238000003892 spreading Methods 0.000 description 1
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- 238000004544 sputter deposition Methods 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 239000012720 thermal barrier coating Substances 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000011364 vaporized material Substances 0.000 description 1
Classifications
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0046—Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
- C23C14/0084—Producing gradient compositions
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/04—Coating on selected surface areas, e.g. using masks
- C23C14/042—Coating on selected surface areas, e.g. using masks using masks
- C23C14/044—Coating on selected surface areas, e.g. using masks using masks using masks to redistribute rather than totally prevent coating, e.g. producing thickness gradient
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3464—Sputtering using more than one target
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- B01J2219/00583—Features relative to the processes being carried out
- B01J2219/00603—Making arrays on substantially continuous surfaces
- B01J2219/00605—Making arrays on substantially continuous surfaces the compounds being directly bound or immobilised to solid supports
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- B01J2219/00677—Ex-situ synthesis followed by deposition on the substrate
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- B01J2219/00718—Type of compounds synthesised
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- B01J2219/00718—Type of compounds synthesised
- B01J2219/0072—Organic compounds
- B01J2219/00722—Nucleotides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2219/00745—Inorganic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2219/00718—Type of compounds synthesised
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- B01J2219/0075—Metal based compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2219/00718—Type of compounds synthesised
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2219/00718—Type of compounds synthesised
- B01J2219/00756—Compositions, e.g. coatings, crystals, formulations
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- C—CHEMISTRY; METALLURGY
- C40—COMBINATORIAL TECHNOLOGY
- C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
- C40B40/00—Libraries per se, e.g. arrays, mixtures
- C40B40/04—Libraries containing only organic compounds
- C40B40/14—Libraries containing macromolecular compounds and not covered by groups C40B40/06 - C40B40/12
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- C—CHEMISTRY; METALLURGY
- C40—COMBINATORIAL TECHNOLOGY
- C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
- C40B40/00—Libraries per se, e.g. arrays, mixtures
- C40B40/18—Libraries containing only inorganic compounds or inorganic materials
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- C—CHEMISTRY; METALLURGY
- C40—COMBINATORIAL TECHNOLOGY
- C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
- C40B60/00—Apparatus specially adapted for use in combinatorial chemistry or with libraries
- C40B60/14—Apparatus specially adapted for use in combinatorial chemistry or with libraries for creating libraries
Definitions
- This disclosure relates generally to methods and apparatus for generating and screening coating libraries, and more particularly, to methods and systems for the parallel deposition of layers of materials onto a substrate to form a coating library.
- Coatings are widely used in industry to enhance the functionality and add-on value of bulk materials.
- functional coating materials There are generally two types of functional coating materials: inorganic and organic coatings.
- Inorganic coatings have been used in both the semiconductor industry, for example in various thin film integrated circuit devices, as well as in conventional industry, such as thermal barrier coatings for steam turbines and aircraft engine airfoils.
- Organic coatings are also widely used in many industrial protective/decorative applications, such as in automobile top clear coatings, paints, etc.
- Other types of coatings include, for example, protective and anticorrosive coatings, adhesive and release coatings, environmental barrier coatings, electric conductive/optic transparent coatings, scratch resistance hard coatings, etc. Discovery of an advanced coating formula promises huge value for a manufacturer.
- the present invention provides systems and methods for high throughput fabrication and analysis of an array of coated materials.
- a system of one embodiment for making an array of coated materials includes a substrate having a surface with a plurality of predefined regions, where a plurality of materials are provided for coating the substrate.
- a delivery mechanism associated with the plurality of materials is positioned to simultaneously deliver each of the plurality of materials onto the surface of the substrate.
- a controller is utilized to control the delivery mechanism to selectively deliver each of the plurality of materials such that each of the plurality of predefined regions of the substrate has a predefined coating.
- a method of one embodiment for making an array of coated materials includes selectively delivering at least one of a plurality of materials to the surface of a substrate having a plurality of predefined regions to form a predefined coating on each of the regions. In the selective delivery of the materials, each of the plurality of materials is positioned for simultaneous delivery to the substrate.
- Fig. 1 is a schematic diagram of a system for making an array of coating materials
- Fig. 2 is a schematic diagram of a coating library formed from the system of Fig. 1;
- Fig. 3 is a schematic diagram of an envelope of a vaporized material being delivered from a delivery mechanism source to the surface of a substrate within a delivery area;
- Fig. 4 is a graph of a thickness profile distributed across a dimension of a delivery area from a normal, focused set up of the delivery mechanism
- Fig. 5 is a graph of a thickness profile distributed across a dimension of a delivery area from an angled, focused set up of the delivery mechanism source;
- Fig. 6 is a graph of a thickness profile distributed across a dimension of a delivery area from a normal, off-focus set up of the delivery mechanism source;
- Fig. 7 is a graph of a thickness profile distributed across a dimension of a delivery area from an angled, off-focus set up of the delivery mechanism source;
- Fig. 8 is a side view of one embodiment of a combinatorial coating system having two opposing delivery sources
- Fig. 9 is a top view of a coating library formed from the system of Fig. 8;
- Fig. 10 is a perspective view of one embodiment of a ternary combinatorial coating system
- Fig. 11 is a top view of a coating library formed from the system of Fig. 10;
- Fig. 12 is a schematic diagram of another embodiment of a combinatorial coating system
- Fig. 13 is a top view of a mask having a plurality of patterns, as may be utilized in the system of Fig. 12;
- Fig. 14 is a top view of a coating library formed using the mask of Fig. 13 in the system of Fig. 12;
- Fig. 15 is a side view showing the cross-section of one embodiment of a vapor deposition combinatorial coating system.
- a system 10 for making an array of coating materials that form a coating library includes a delivery mechanism 12 delivering one or a combination of a plurality of materials 14 to a surface 16 of a substrate 18 to form a coating 20.
- the substrate surface 16 has a plurality of predefined regions 22 that are positioned within a delivery area 24, which is preferably at a fixed location within the system 10.
- the delivery mechanism 12 and/or the plurality of materials 14 are positioned to simultaneously deliver, or deliver in parallel, each of the plurality of materials to the delivery area 24.
- a controller 26 controls the selection, quantity and sequence of delivery of each of the plurality of materials 14 such that the composition of the coating 20 may vary between each of the regions 22 on the substrate surface 16 to form a coating library 28.
- each of the plurality of predefined regions 22 is coated with one of a plurality of predefined coatings 30.
- the plurality of predefined coatings 30 include: a single layer coating of one of the plurality of materials 14; a single layer coating of a combination of the plurality of materials; a multiple layer coating, where each layer is one of the plurality of materials; and a multiple layer coating, where each layer is a combination of the plurality of materials.
- the system 10 may include a mask 32 in communication with the controller 26 to permit delivery of the materials 14 to different combinations of the plurality of predefined regions 22 form the plurality of predefined coatings 30.
- the system 10 may also include a curing source 34 for curing the plurality of materials 14, either as they are being delivered to the substrate 18 or once they have been deposited on the substrate. Further, the system 10 may include a testing device 36 to perform analytical tests on the coated substrate or coating library 28, to determine the properties of each of the plurality of predefined coatings 30.
- the mask 32 may be secured by a mounting device 35, which optionally may movably position the mask within the system 10.
- the substrate 18 may be secured by a holding device 37, which optionally may movably position the substrate within the system 10.
- the present invention provides a system and method for manufacturing and testing a coating library having an array of coatings established from a plurality of materials simultaneously focused, or focused in parallel, on a substrate.
- the delivery mechanism 12 is configured such that each of the plurality of materials 14 may be simultaneously delivered, or delivered in parallel, to the delivery area 24 from a variety of angles. As such, the delivery mechanism 12 is positioned or focused so that at least a portion of the delivered material reaches the delivery area 24, as is discussed in more detail below.
- the delivery mechanism 12 may be a single device, or it may be a plurality of individual devices each corresponding to one of the plurality of materials 14.
- the position of each of the one or more delivery mechanisms 12 is preferably fixed within the system 10 relative to the delivery area 24 and relative to the other delivery mechanisms.
- the delivery mechanism 12 projects each of the plurality of materials 14 to the delivery area 24 in a vaporized or atomized form.
- Suitable examples of a delivery mechanism 12 include: a spray nozzle or gun of any type, such as ultrasonic, air, thermal, airless guns, such as those using hydraulic force; microwave or radio frequency ("RF") delivery mechanisms; an ink jet print head; a vapor deposition device, including sputtering, thermal/electron/laser evaporation, chemical vapor deposition (CVD), molecular beam epitaxy, plasma spray; and ion beam deposition.
- RF radio frequency
- the plurality of materials 14 include inorganic materials and organic materials in various states, such as solid, liquid, gaseous and vaporized/atomized materials.
- Suitable examples of inorganic coatings include metals, alloys, ceramics, oxides, nitrides, and sulfides.
- Suitable examples of organic coatings include polymeric, oligomeric and small molecules, where small molecules are individual monomers that react to form a coating.
- the polymeric materials include, but are not limited to, polycarbonates, acrylics, silicones, cellulose esters, polyesters, alkyds, polyurethanes, and vinyl polymers and alike.
- the plurality of organic materials include organic polymeric materials, such as "architectural" materials derived from organic materials having protective or decorative functionality, especially including thermoplastic or thermosetting polymers.
- the plurality of inorganic 5 materials include oxides.
- the plurality of materials 14 preferably can be vaporized or atomized, individually or in combination, and directed to or deposited on a substrate, where the vaporized/atomized material coalesces and forms a continuous coating if a sufficient amount of the material is delivered to the substrate. Additionally, the material or combination of materials may form a coating having a
- the coating may be a multi-functional coating having an overall function dictated by a predefined functional role of each layer.
- the materials may be combined such that multiple organic materials, or multiple inorganic materials, or a combination of organic and inorganic are combined into a coating. Additionally, by providing these various combinations of materials, the interaction
- the coating 20 is a material or a combination of materials deposited on the substrate 18. These materials may remain as separate homogenous materials, or they may react, interact, diffuse, mix or otherwise combine to form a new homogeneous material, a mixture, a composite or a blend. As mentioned above, the coating 20 may
- coating 20 include a single layer or multiple layers.
- coating 20 has a lateral measure, i.e. a measured length across the surface of the substrate, much greater than a thickness, i.e. a measure of the coating normal to the surface of the substrate.
- each layer is a thin film layer.
- the coating 20 may vary in composition, optionally in a continuous manner, from one predefined region 22 to another to
- each of the array of coatings are distinguishable from each other based on their location. Further, each of the array of coatings may be processed under the same conditions and analyzed to determine their performance relative to functional or useful properties, and then compared with each other to determine their
- Each of the plurality of predefined regions 22 is a fixed area on the substrate 18 for receiving one or a combination of the plurality of materials 14 to form a single or multiple layer coating.
- Each of the predefined regions 22 may have any shape sufficient for receiving and analyzing the coating deposited thereon, such as rectangular, linear, arcuate, circular, elliptical, combinations thereof, etc.
- Each predefined region 22 typically has an area in the range of about 0.01 mm 2 to about 100 cm 2 , preferably in the range of about 1 mm 2 to about 1 cm 2 , and more preferably in the range of about 10 mm 2 to. about 50 mm 2 . Other areas may be utilized, and the area of each predefined region 22 may be determined by the capability of deposition and analytical devices and by a preferred density of the coating library.
- the substrate 18 is a rigid or semi-rigid material suitable for receiving and supporting at least one of the plurality of materials 14.
- the substrate 18 has at least one substantially flat surface 16 that includes the plurality of predefined regions 22. This substantially flat surface, however, may have raised portions to physically separate each of the plurality of predefined regions 22.
- the substrate 18 may be of any size and shape, but preferably is in a disk shape, plate shape, or elongated shape, such as in a tape or roll.
- the substantially flat surface 16 of the substrate 18, corresponding to the delivery area 24, typically has an area in the range of about 1 mm 2 to about 1 m 2 , preferably in the range of about 50 mm 2 to about 750 cm 2 , and more preferably in the range of about 1 cm 2 to about 500 cm 2 .
- the substrate 18 may be secured within the system 10 and positioned in the delivery area 24 by the holding device 37.
- the holding device 37 may movably position the substrate 18.
- the holding device 37 may include a tape pay-out device and a tape take-up device that are both rotatable and that support the tape, possibly in combination with rollers, in the delivery area 24.
- the holding device 37 may be a plate on which the substrate is placed and secured, where the plate is connected to a motor or other actuator-type device that controls the position of the plate relative to the delivery area 24.
- the controller 26 may control the movement of the holding device 37 to control the predefined regions 22 onto which the materials 14 are delivered.
- the .controller 26 may move the holding device 37 such that predetermined ones of the plurality of predefined regions 22 are outside of the delivery area 24 and therefore do not receive one or more of the materials 14.
- the delivery area 24 is an area at a fixed position within the system 10.
- the delivery area 24 may be of any shape or size and typically, but not necessarily, substantially corresponds in shape and size to the plurality of predefined regions 22 on the surface 16 of the substrate 18. However, the plurality of predefined regions 22 may be much larger or much smaller than the delivery area 24.
- the fixed positioning of the delivery area 24 provides a known, constant locale for the system 10 to deliver the plurality of materials 14 and the surface 16 of the substrate 18.
- the controller 26 is a computer system having inputs, outputs, a memory and a processor for receiving, sending, storing and processing signals and data to operate, monitor, record and otherwise functionally control the operation of the system 10.
- the controller 26 includes a computer system having an interface board for integrating all of the components of the system and a motion controller for controlling the movements of the mask 32 and substrate 18.
- the controller 26 may include a keyboard for inputting data and commands, a video display for displaying information, and a printer for printing information.
- the controller 26 may include software, hardware, firmware, and other similar components and circuitry for operating the system 10.
- the controller 26 may be a single device, or it may be a plurality of devices working in concert.
- the controller 26 is preferably in communication with all of the other components of the system 10, including the delivery mechanism 12, the plurality of materials 14, the substrate 18, the mask 32, the curing source 34, the testing device 36, the mounting device 35 and the holding device 37, to coordinate the operations of the system.
- the controller controls the delivery of the materials to the substrate, recording the exact combination of materials that make up the coating at each predefined region.
- the controller may control one or more of the material volume, the combination of materials, the projective power, the coating speed, the projective angle, the spacing between the delivery mechanism and the substrate, the masking, etc.
- the controller 26 controls, synchronizes, combines and records the r delivery and curing of the delivered materials, the testing of the coating library, and the analysis of the test results.
- the mask 32 is a material having one or more patterns of open areas and blocked areas, where the open areas allow delivery of the plurality of materials 14 to the substrate 18 and the blocked areas block the delivery.
- the pattern may be in any shape.
- the mask 32 is utilized to define the spatial variation of materials in the coating library 28.
- the mask includes a plurality of patterns that are sequentially arranged to allow delivery to alternating half areas on the substrate 18, as will be described below in more detail.
- the mask 32 may be positioned anywhere in between the plurality of materials 14 and the substrate 18, including positioned directly on top of and in contact with the substrate, along the line of delivery of the materials. By increasing the spacing between the mask 32 and the substrate 18, an effect called "shadowing" is produced which may be undesirable in some instances.
- the pattern of material delivered to the substrate is proportional to the pattern of the mask, but larger, as the spacing between the mask and the substrate allows the delivered pattern to expand until it reaches the substrate.
- the mask 32 may be formed of a rigid or semi-rigid material, or the mask may be a chemical formed on the surface of the substrate.
- the material of the mask insures that the mask is as flat as possible and resists bending and/or folding.
- Suitable examples of mask materials include: silicon, silicon oxide and glass for rigid or relatively non-bendable materials; plastics, metals and alloys for semi-rigid or relatively bendable materials in the form of sheets, films or foils; and lithographic- polyacrylate (“PMMA”) and other chemical materials that form negative and positive chemical masks.
- the mask 32 may be secured within the system 10 and positioned relative to the delivery area 24 by the mounting device 35.
- the mounting device 35 may movably position the mask 32.
- the mounting device 35 may include a tape pay-out device and a tape take-up device that are both rotatable and that support the tape, possibly in combination with rollers, relative to the delivery area 24.
- the mounting device 35 may be a platform or other supporting structure connected to a motor or other actuator-type device that controls the position of the platform and mask relative to the delivery area 24. This allows one pattern or a number of patterns to be utilized to mask different predefined regions 22 on the substrate 18 by movement of the mask 32.
- the controller 26 may control the movement of the mounting device 35 to control the predefined regions 22 onto which the materials 14 are delivered.
- the curing source 34 is a device in communication with each of the plurality of materials 14 to cause a reaction or a solvent evaporation with one or a combination of the materials.
- the reaction may be a polymerization, a cross-linking reaction, a small molecule reaction, an inorganic phase reaction, and other similar reactions appropriate for the delivered material(s).
- Suitable examples of a curing source 34 include a heating device in communication with the substrate 18, a radiation device in communication with the delivered materials or the deposited materials, a microwave device, a plasma device and combinations thereof.
- the testing device 36 is a system for analyzing the performance of each of the plurality of predefined coatings 30 on the substrate 18.
- the testing device 36 subjects the entire coating library 28 to the same conditions in order to determine the relative performance of each one of the predefined coatings 30.
- the testing device 36 is in communication with the controller 26 in order to compile and analyze the test data.
- Suitable examples of a testing device 36 include a thickness profiler, a surface analyzer, an ultra violet ("UN”) absorbance tester, a scratch resistance tester, a permeability tester, and other similar devices that test architectural, protective, decorative and other functional features of a coating.
- a source 38 of the delivery of the materials from the delivery mechanism 12 delivers one of the plurality of materials 14 in a vaporized or atomized state within an envelope 40 that preferably encompasses the delivery area 24 in order to obtain coating coverage over the entire delivery area.
- the source 12 is the point of exit of the material from the delivery mechanism.
- the source 12 may be the nozzle on , a spray gun. It may be desired in some cases, however, not to have coating coverage over the entire delivery area 24.
- the envelope 40 may only encompass a portion of the delivery area 24 when a portion of the predetermined regions 22 of the substrate 18 are not to be coated and a mask 32 is not being used to prevent delivery of the material to those regions.
- the envelope 5 40 may be of any convenient shape, including: conical with various cross-sections such as round, elliptical and rectangular; semi-conical with various cross-sections; and a thin line shape.
- the shape of the envelope 40 may be dictated by the shape of the delivery area 24, the shape of the surface 16 of the substrate 18, the delivery mechanism 12, the desired composition of each of the plurality of predefined coatings 10 30, the shape and number of the predetermined regions 22, the number of sources 38, the number of materials 14 being delivered to the substrate 18, and similar factors.
- the shape of the envelope 40 may be controlled by the shape of a nozzle on the delivery mechanism 12, by an air shroud associated with the delivery mechanism, or by other shape-defining structures or devices associated with the delivery mechanism.
- the source 38 in a normal focused set up 41, has a point of focus 42 for delivering the material 14 coinciding with a center point 44 of the delivery area 24.
- the source 38 is positioned to direct the material 14 along a delivery angle having a centerline 46 substantially perpendicular to the surface of the delivery area 24 at the center point 44.
- the thickness profile 48 therefore has an apex 52 coinciding with the centerline 46 above
- the source 38 is positioned at a vertical spacing 60 relative to the plane 49 of the delivery area 24 (Fig. 3).
- the vertical spacing 60 affects the total width 51 of the thickness profile 48 and thereby the thickness of the coating at any given point along the thickness profile distribution.
- 30 profile 48 is centered within the dimension 50 of the delivery area 24, the thickness being largest at the apex 52 and gradually reducing in all directions from the centerline 46.
- the source 38 in an angled focused set up 55, has the point of focus 42 for delivering the material 14 coinciding with the center point 44 of the delivery area 24, however, the source is positioned such that the centerline 46 of the material is at a delivery angle ⁇ between about 0 degrees and about 90 degrees relative to the plane 49 of the delivery area. Further, because of the angled but focused delivery, the source 38 is located at a horizontal spacing distance 53 from the center point 44.
- the horizontal spacing distance 53 is a distance in the plane of the source 38 parallel to the plane 49 of the delivery area and spaced away from the normal focused set up position.
- the horizontal spacing distance 53, vertical spacing distance 60, and delivery angle ⁇ are all mathematically interrelated and may be varied to position the thickness profile 48 within the delivery area 24.
- the thickness profile 48 has a distorted Gaussian distribution with an inclined tail 56 closer to the source 38 and an elongated tail end 58 trailing away from the source. Within the elongated tail 58 is typically a region where the thickness profile 48 varies substantially linearly with the length along the dimension 50. Thus, in this case, the thickness profile 48 is distorted within the dimension 50 of the delivery area 24, the thickness being largest toward the end of the dimension having the inclined tail 56 and reducing in thickness from the apex 52 toward the edge of the dimension corresponding to the elongated tail 58.
- the source 38 has the point of focus 42 for delivering the material 14 positioned at an offset distance 59 in the plane of the delivery area 24 along the dimension 50 from the center point 44.
- the offset distance 59 is substantially equivalent to the horizontal spacing of the source 38 from the normal focused set up position (Fig. 4).
- the point of focus for a delivery mechanism may be positioned within the delivery area or outside of the delivery area.
- the thickness profile 48 is offset within the dimension 50 of the delivery area 24, the thickness being largest at the offset position of the apex 52 and gradually reducing in all directions from the centerline 46.
- the source 38 has the point of focus 42 for delivering the material 14 positioned at the offset distance 59 along the dimension 50 from the center point 44, where the centerline 46 is at a delivery angle ⁇ between about 0 degrees and about 90 degrees relative to the plane 49 of the delivery area 24.
- the horizontal spacing 53 of the source 38 from the normal focused delivery point is greater than the offset distance 59 of the point of focus to the center point 44.
- the thickness profile 48 is even more distorted within the dimension 50 of the delivery area 24 than the set up of Fig. 5.
- the flatness of the thickness profile 48 within the delivery area 24 will vary depending on the vertical spacing 60 between the source 38, where the flatness will increase with increased spacing. Further, the flatness of the thickness profile 48 will vary within the delivery area 24 depending on the delivery angle ⁇ , horizontal spacing 53, and offset distance 59, where the smaller the angle and greater the horizontal spacing and offset distance will increase the flatness.
- the thickness profile 48 may be substantially flat in the dimension 50 of the delivery area 24 with the proper combination of delivery angle, horizontal spacing and offset distance.
- the thickness profile 48 in the dimension 50 of the delivery area 24 may gradually change from a largest thickness at the apex 52 to a smallest thickness at the edges of the dimension of the delivery area.
- a coating library having a substantially constant thickness is desired so that the thickness variable can be ruled out of the analysis of the plurality of predefined coatings 30 associated with each predefined region 22 in order to focus the study on the effect of the coating composition.
- a substantially constant thickness coating library is achieved by calibrating each delivery mechanism such that a linear thickness profile is distributed across the delivery area. When multiple delivery mechanisms are utilized, preferably the same portion of the thickness profile is positioned within the delivery area for each delivery mechanism.
- the present invention allows the manufacture of coating libraries having virtually infinite variations in compositions, layers and thicknesses of coating materials within the plurality of predefined regions 30 of the substrate 18 by varying the vertical spacing 60, the delivery angle ⁇ and the offset distance 59, for each source 38 of each of the plurality of materials 14.
- a continuously varying coating library 64 is formed on the substrate 18 by the simultaneous deposition of at least two (A and B) of the plurality of materials 14 from sources 38.
- the relative thickness and composition of each of the plurality of predefined coatings 30 may individually or both continuously vary as the result of the thickness profile 48 (see Figs. 4-7) of each of the materials A and B as they are delivered to the substrate 18.
- This continuous variation may be linear or non- linear, depending on variables such as the delivery angle ⁇ , the projective power of the delivery mechanism 12 (not shown) associated with each source 38, the coating speed or amount of material deposited per unit time, the feed rate and concentration of the material input into the delivery mechanism, the vertical spacing 60, the offset distance 59 of the source 38 relative to the center point 44, the horizontal spacing 53 of each source 38 to the center point 44, the shape of the envelope 40 (not shown), the atmosphere and power per area and pressure and species of gas in vapor deposition, and other similar factors.
- Each of these variables may be varied individually or in combination to produce a predefined coating in each predefined region 30.
- a mask 32 may be positioned between each of the sources 38 and the substrate 18, preferably adjacent to or touching the substrate to assist in forming the coating library.
- the delivery angle ⁇ may have a value in the range of about 0° to about 90°, more preferably from about 15° to about 75°, and most preferably from about 30° to about 60°.
- the vertical spacing 60 may vary from about
- the horizontal spacing 53 may vary from about 0 cm to about 60 cm, more preferably from about 3 cm to about 30 cm, and most preferably from about 10 cm to about 20 cm.
- the coating thickness may vary from about 1 nanometer to about 1 millimeter, more preferably from about 1 micrometer (or microns) to about 500 micron, and most preferably from about 5 microns to about 100 microns.
- one embodiment of the coating library 64 produced by the combinatorial coating system 62 includes opposing gradients of materials A and B, ranging continuously from about 100% to about 0% of material A and from about 0% to about 100% of material B moving laterally across the coating library from the side adjacent to the source 38 of material A.
- the coating library 64 may have a substantially constant or a variable thickness across the substrate.
- the sources of materials A and B have respective points of focus 42 having a predefined offset distance 53 from the center point 44 of the delivery area so that the thickness of the coating library is substantially constant across the substrate.
- each source 38 may be sequentially fed with new and different materials, which in combination with a laterally moving elongated substrate, results in a continuously varying coating along a longitudinal length of the substrate.
- each source 38 preferably is positioned within a delivery plane 65 that is substantially parallel to, but spaced a vertical distance 60 from, the plane 49 of the delivery area.
- the vertical spacing 60 of each source 38 may independently vary to provide a different thickness profile 48 within the delivery area 24.
- the system 62 of provides for the simultaneous delivery of at least two of a plurality of materials onto the substrate to obtain a continuously varying coating having gradients of the at least two materials.
- a ternay combinatorial coating system 68 provides a continuous ternary coating library 70.
- At least three materials (A, B and C) of a plurality of materials 14 (Fig. 1) may be simultaneously or sequentially delivered from sources 38.
- the sources 38 are each positioned in a substantially identical angled off focus setup 61 (Fig. 7), as described above.
- the sources 38 are preferably equally spaced about a circle 74 having a center 76 on the same axis 78 as center point 44.
- the circle 74 has a diameter larger than the diameter of the delivery area.
- the circle 74 preferably has a diameter of about 30 cm while the delivery area has a diameter in the range of about 10 cm to about 15 cm.
- the coating library 70 formed by system 68 may be a continuously varying combination of each of the three materials A, B and C, mimicking a ternary phase diagram. The same variables affecting the formation of the coating library 64 (Figs. 8-9), described above, similarly apply to the coating library 70 of the system 68.
- the relative composition of the coating library 70 at any point is a function of the horizontal spacing 53, offset distance 59, the delivery angle ⁇ , the shape of the envelope 40 of the spray of each material, the point of focus 42 of each source, etc.
- the preferred spacing and angles are the same as those described above with reference to Figs. 8-9.
- three airbrush guns were simultaneously focused to deliver a fine spray of three different materials to the substrate utilizing an angled, off-focus set up 61 (Fig. 7). All of the guns were positioned in a delivery plane parallel to and vertically spaced about 15 cm from the delivery area. Further, each gun was positioned to have a delivery angle ⁇ of about 45° and a horizontal spacing 53 of about 18 cm.
- the substrate 18 was a substantially circular disk of silicon wafer material having a diameter of about 8 cm.
- Each of the plurality of predefined regions were sized to form a coating library having 66 predefined coatings.
- the coating material included 2% polyethylmethal acrylate (PEMA) in iso-propanol solvent mixed with an organic pigment.
- PEMA polyethylmethal acrylate
- a ternary coating library having 66 distinct compositions was generated in a few minutes.
- the coating was about 2 microns in thickness, and the coating thickness scales linearly with the coating time. Referring to Figs.
- a combinatorial coating system 72 includes a plurality of co-focused or simultaneously focused delivery mechanisms 12 each fixedly positioned to simultaneously or sequentially deliver one of the plurality of materials 14 to the substrate 18 through a mask 32.
- Each of the plurality of delivery mechanisms 12 produces a mist of atomized material within an envelope 40 (Fig. 3) that intersects with the surface 16 of the substrate 18.
- Each source 38 is preferably positioned in an angled, off-focus set up 61 (Fig. 7).
- each delivery mechanism 12 is equally spaced about a circle 74 having a center 76 on the same axis 78 as center point 44. Further, each delivery mechanism 12 preferably has a horizontal spacing 53 (Fig.
- each delivery mechanism 12 radially from the center 76 a distance less than the distance from the center point 44 to the edge of the delivery area 24.
- the point of focus 42 (not shown) of each delivery mechanism 12 is focused a substantially equivalent offset distance 59 (Fig. 7) from the center point 44, thereby positioning the same portion of the thickness profile 48 (Fig. 7) for each material in the delivery area 24.
- the point of focus 42 for each delivery mechanism 12 is not required to be offset from the center point 44 or to have equivalent offset distances 53.
- each delivery mechanism 12 may have a unique point of focus 42, including one that results in the centerline 46 (Fig.
- the delivery mechanisms 12 need not be positioned about a circle, but may be in any relative position that allows the parallel or simultaneous delivery of a plurality of materials 14 to at least a portion of the delivery area 24.
- the mask 32 preferably comprises a plurality of patterns 80 (Fig. 13), which may be moved in and out of the line of delivery of the materials 14 in order to control the coating of different predefined regions 22 (Fig. 2) with different materials to form a coating library 82 (Fig. 13).
- a coating library 82 preferably the mask is a physical contact mask that is touching or in close proximity to the substrate to eliminate shadowing.
- the system 72 may produce a coating library 82 having sixteen predefined coatings 30 using four (A, B, C and D) of the plurality of materials 14 in combination with the first four patterns 80 of the mask 32 (Fig. 13).
- each delivery mechanism 12 is a sprayer nozzle that atomizes a liquid precursor material 14 into a fine spray and directs it individually or in combination with other nozzles/materials to the substrate 18 to make a coating layer.
- Compressed air, superheated steam, or an ultrasonic wave may be applied to the liquid material to generate the fine mist of the liquid material.
- a coating library 82 having multiple coating layers may be developed by sequencing the delivery of the materials 14 from the plurality of sprayers 12 in combination with a sequence of masking patterns and curing steps (if necessary) to provide a predetermined coating 30 in a predefined region 22 (Fig. 2) of the substrate.
- liquid coatings include polyacrylides, polycarbonates, vinyl polymer, silicones, and silica gel.
- suitable spray guns include those manufactured by SonoTech. If the materials require curing, then suitable examples of a curing source 34 (Fig.
- a coating library having a plurality of predefined multi-layer coatings is made in a parallel fashion, either by combining different masking patterns with different liquid precursor materials, or by a maskless "continuous phase spreading" of the materials, taking advantage of the variation in spacing and volume of the liquid precursor material being delivered from each sprayer nozzle to form the coating library.
- a vapor deposition combinatorial coating system 90 includes multiple delivery mechanisms 12 each co-focused, or simultaneously focused, for simultaneously or sequentially delivering one of a plurality of solid materials 14 to the substrate 18 positioned on a movable stage 92 within a deposition housing 94.
- the substrate comprises a stable high temperature material such as magnesium oxide or lanthanum aluminate (LaAIO 3 ).
- the deposition housing 94 is sealable to form a vacuum chamber 96 within its interior surfaces.
- the delivery mechanisms 12 are vapor deposition devices, such as sputter guns powered by RF power, preferably matched for optimum output.
- the stage 92 supports the substrate 18 in a known position, where the stage may adjust vertically, rotationally or linearly to position the substrate within the delivery area.
- a mask 32 Positioned between the delivery mechanisms 12 and the substrate 18 is a mask 32 having an array of different patterns 80.
- the mask 32 is preferably substantially in contact with the substrate 18 during vapor deposition, to minimize the "shadowing effect.”
- the mask 32 is movably positioned within a vacuum chamber 98 of a mask housing 100.
- the mask housing 100 is in communication with the main housing 94 in a manner to maintain the atmosphere of both vacuum chambers 96 and 98. Further, the mask housing 100 includes a gear box 102 and micrometer 104 for moving and measuring, respectively, the position of the mask patterns 80 with respect to the substrate 18.
- the system 90 may optionally may include a shutter 106 having one or more apertures 108 to select one or more materials for simultaneous or sequential delivery and prevent intermixing of materials.
- the shutter 106 is movably connected to a rotor 110 that rotates the shutter and aperture 108 to select the solid material 14 to vaporize, while the mask pattern 80 is changed in-vacu with linear motion vacuum feed-through.
- the quantity of deposition of the materials 14 is monitored with a thickness monitoring device 112, such as a quartz crystal oscillator.
- the vacuum atmosphere within the vacuum chambers 96 and 98 are maintained by a back-pump station 114 connected to a turbo-molecular pump 116.
- the back-pump station 114 may provide a vacuum of about 10 "3 torr, while the turbo-molecular pump 116may provide a vacuum of 10 "6 torr.
- the pumps 114 and 116 are in communication with the vacuum chamber 96 through a gate valve 118.
- this system 90 may generate coating libraries of any ceramic, metallic and/or semiconductor materials, with surface roughness and accuracy of thickness measured in nanometers.
- other suitable delivery mechanisms 12 include laser ablation, electron beam evaporation, CND, etc., that may be used with the masking system to generate inorganic coating libraries.
- a co-focusing multiple source thermal evaporation apparatus coupled with a masking system may be set up. The same system may be utilized to fabricate small molecule libraries such as for use in organic light emitting diode (“LED”) devices.
- LED organic light emitting diode
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- Mechanical Engineering (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Spray Control Apparatus (AREA)
- Physical Vapour Deposition (AREA)
- Details Or Accessories Of Spraying Plant Or Apparatus (AREA)
Abstract
L'invention concerne des systèmes et des procédés permettant la production et l'analyse rapides d'un ensemble de matières de revêtement. Les procédés consistent à appliquer au moins une matière (14) faisant partie d'une pluralité de matières sur la surface (16) d'un substrat (18) comprenant une pluralité de régions (22) prédéfinies afin de former un revêtement (30) prédéfini sur chacune de ces régions. Dans un procédé de distribution sélective des matières, une pluralité de matières sont disposées de manière à pouvoir être distribuées simultanément sur le substrat. Les systèmes (10) comprennent un substrat (18) qui présente une surface (16) comprenant une pluralité de régions (22) prédéfinies, et une pluralité de matières (14) appliquées de manière à un revêtement sur le substrat. Un mécanisme (12) de distribution associé à cette pluralité de matières est positionné de manière à distribuer simultanément chaque matière de cette pluralité sur la surface du substrat. Une unité (26) de commande permet en outre de commander le mécanisme de distribution de manière que ce dernier distribue sélectivement chaque matière et que chaque région prédéfinie du substrat présente un revêtement (30) prédéfini.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US66832300A | 2000-09-22 | 2000-09-22 | |
US668323 | 2000-09-22 | ||
PCT/US2001/019159 WO2002024321A1 (fr) | 2000-09-22 | 2001-06-14 | Systemes et procedes de revetements combinatoires |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1328341A1 true EP1328341A1 (fr) | 2003-07-23 |
Family
ID=24681881
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01944524A Withdrawn EP1328341A1 (fr) | 2000-09-22 | 2001-06-14 | Systemes et procedes de revetements combinatoires |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP1328341A1 (fr) |
JP (1) | JP2004508927A (fr) |
KR (1) | KR20030038760A (fr) |
CN (1) | CN1461234A (fr) |
AU (1) | AU2001266929A1 (fr) |
BR (1) | BR0114076A (fr) |
CA (1) | CA2421520A1 (fr) |
MX (1) | MXPA03002455A (fr) |
RU (1) | RU2270881C2 (fr) |
WO (1) | WO2002024321A1 (fr) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7491677B2 (en) * | 1999-01-15 | 2009-02-17 | Basf Catalysts Llc | Combinatorial synthesis |
US8944002B2 (en) * | 2004-01-14 | 2015-02-03 | Honda Motor Co., Ltd. | High throughput physical vapor deposition system for material combinatorial studies |
US7857946B2 (en) | 2007-04-26 | 2010-12-28 | Canon Anelva Corporation | Sputtering film forming method, electronic device manufacturing method, and sputtering system |
EP2002886A1 (fr) * | 2007-05-08 | 2008-12-17 | HTE Aktiengesellschaft The High Throughput Experimentation Company | Plateforme de revêtement et procédé pour la préparation de revêtements minces |
CN103314464B (zh) * | 2011-01-19 | 2016-05-25 | 夏普株式会社 | 被成膜基板、有机el显示装置和蒸镀方法 |
JP6077906B2 (ja) * | 2013-03-28 | 2017-02-08 | 株式会社アツミテック | スパッタリング装置 |
GB2529608B (en) * | 2014-06-10 | 2018-07-18 | Monitor Coatings Ltd | A method of coating a sheet of steel |
CN105618020A (zh) * | 2014-10-28 | 2016-06-01 | 睿泽企业股份有限公司 | 光催化剂基材的制作方法及制作设备 |
US10644239B2 (en) | 2014-11-17 | 2020-05-05 | Emagin Corporation | High precision, high resolution collimating shadow mask and method for fabricating a micro-display |
CN104762590B (zh) * | 2015-03-20 | 2017-05-10 | 京东方科技集团股份有限公司 | 蒸镀掩膜板 |
TWI633197B (zh) | 2016-05-24 | 2018-08-21 | 美商伊麥傑公司 | 高精準度蔽蔭遮罩沉積系統及其方法 |
US10386731B2 (en) * | 2016-05-24 | 2019-08-20 | Emagin Corporation | Shadow-mask-deposition system and method therefor |
KR102377183B1 (ko) | 2016-05-24 | 2022-03-21 | 이매진 코퍼레이션 | 고정밀 섀도 마스크 증착 시스템 및 그 방법 |
RU2669259C2 (ru) * | 2016-12-09 | 2018-10-09 | Федеральное государственное автономное образовательное учреждение высшего образования "Уральский федеральный университет имени первого Президента России Б.Н. Ельцина" | Устройство для получения пленок |
KR102378672B1 (ko) * | 2017-05-17 | 2022-03-24 | 이매진 코퍼레이션 | 고정밀 섀도 마스크 증착 시스템 및 그 방법 |
WO2019070665A1 (fr) * | 2017-10-04 | 2019-04-11 | Ih Ip Holdings Limited | Motifs de dépôt dans la fabrication de réactifs |
CN113275149B (zh) * | 2021-06-01 | 2022-01-18 | 丰县通亚电子科技有限公司 | 环保型电动车喷漆装置 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6045671A (en) * | 1994-10-18 | 2000-04-04 | Symyx Technologies, Inc. | Systems and methods for the combinatorial synthesis of novel materials |
US6364956B1 (en) * | 1999-01-26 | 2002-04-02 | Symyx Technologies, Inc. | Programmable flux gradient apparatus for co-deposition of materials onto a substrate |
US6911129B1 (en) * | 2000-05-08 | 2005-06-28 | Intematix Corporation | Combinatorial synthesis of material chips |
-
2001
- 2001-06-14 CA CA002421520A patent/CA2421520A1/fr not_active Abandoned
- 2001-06-14 EP EP01944524A patent/EP1328341A1/fr not_active Withdrawn
- 2001-06-14 MX MXPA03002455A patent/MXPA03002455A/es unknown
- 2001-06-14 CN CN01815959A patent/CN1461234A/zh active Pending
- 2001-06-14 RU RU2003111467/02A patent/RU2270881C2/ru not_active IP Right Cessation
- 2001-06-14 KR KR10-2003-7004133A patent/KR20030038760A/ko not_active Application Discontinuation
- 2001-06-14 JP JP2002528383A patent/JP2004508927A/ja not_active Withdrawn
- 2001-06-14 BR BR0114076-0A patent/BR0114076A/pt not_active IP Right Cessation
- 2001-06-14 AU AU2001266929A patent/AU2001266929A1/en not_active Abandoned
- 2001-06-14 WO PCT/US2001/019159 patent/WO2002024321A1/fr active Application Filing
Non-Patent Citations (1)
Title |
---|
See references of WO0224321A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO2002024321A1 (fr) | 2002-03-28 |
RU2270881C2 (ru) | 2006-02-27 |
AU2001266929A1 (en) | 2002-04-02 |
CA2421520A1 (fr) | 2002-03-28 |
KR20030038760A (ko) | 2003-05-16 |
JP2004508927A (ja) | 2004-03-25 |
MXPA03002455A (es) | 2003-06-19 |
CN1461234A (zh) | 2003-12-10 |
BR0114076A (pt) | 2003-07-29 |
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