JP2004508927A - Combinatorial coating apparatus and method - Google Patents

Abstract

Apparatus and method for high-throughput preparation and analysis of arrayed coating materials. Such a method includes selectively delivering one or more of a plurality of materials (14) to a surface (16) of a substrate (15) having a plurality of predetermined regions (22) to provide a predetermined coating (30) on each of the regions. ). Upon selective delivery of the materials, the plurality of materials are arranged such that each is delivered to the substrate simultaneously. The apparatus (10) includes a substrate (18) having a surface (16) partitioned into a plurality of predetermined regions (22), and a plurality of materials (14) are prepared for coating the substrate. . A delivery mechanism (12) with a plurality of materials is arranged to simultaneously deliver each of the plurality of materials to the surface of the substrate. Further, by controlling the delivery mechanism with the controller (26), each of the plurality of materials is selectively delivered such that each of the plurality of predetermined regions of the substrate has a predetermined coating (30).
[Selection diagram] FIG.

Description

[0001]
TECHNICAL BACKGROUND OF THE INVENTION
The present invention relates generally to a method and apparatus for creating and screening a coating library, and more specifically to a method and a method for forming a coating library by depositing material layers in parallel on a substrate. Related to the device.
[0002]
Coatings are widely used industrially to enhance the functionality and added value of materials. Generally, there are two types of functional coating materials, inorganic coatings and organic coatings. Inorganic coatings are used in the semiconductor industry as well as in conventional industries, such as thermal barrier coatings for steam turbines and aircraft engine airfoils, for example, for various thin film integrated circuit devices. Organic coatings are also widely used in many industrial protective / decorative applications such as transparent top coatings for automobiles and paints. Other types of coatings include, for example, protective and anticorrosion coatings, adhesive and release coatings, environmental barrier coatings, conductive / optically clear coatings, mar resistant hardcoats, and the like. The discovery of improved coating formulations is expected to be of enormous value to manufacturers.
[0003]
However, the search and optimization of improved coatings is a technical rather than a scientific issue, so developing a general purpose tool to facilitate the discovery process for various coating systems may be of greater value. There is. Due to the complexity of typical coating systems and the high quality requirements to be met, the power of theoretical guidance in the search and optimization of improved coatings is limited. Typically, an industrial coating formulation must meet a number of functional requirements, requiring a large number of compatible functional groups or blends to obtain a balanced formulation. Furthermore, the properties of the coating system depend not only on the formulation / composition, but also on the processing conditions and the method of applying the coating. For example, the degree of thickness uniformity and surface roughness, which depend on the coating application method and treatment, is important for coating quality and reproducibility. In addition, various processing conditions, including exposure to ultraviolet (UV) / electronic curing, various temperatures / pressures, and the order in which each layer of the multilayer coating is applied, are extremely critical in determining the structure / composition of the final coating. It is an important factor. Moreover, the structure / composition of the final coating affects the functionality of the coating. Because of the large number of variables, many of the available industrial coating systems developed to date have been the result of lucky trial and error experimental procedures.
[0004]
Summary of the Invention
Therefore, there is a need for an approach to increase the speed of forming and studying functional coatings for various manufacturing applications. Thus, the present invention provides an apparatus and method for high-throughput preparation and analysis of ordered coating materials.
[0005]
One embodiment of an apparatus for making an arrayed coating material includes a substrate having a surface partitioned into a plurality of predetermined areas, and a plurality of materials are provided for coating the substrate. A delivery mechanism with multiple materials is arranged to simultaneously deliver each of the multiple materials to the surface of the substrate. Further, by controlling the delivery mechanism with a controller, each of the plurality of materials is selectively delivered such that each of the plurality of predetermined regions of the substrate has a predetermined coating.
[0006]
One embodiment of a method of making an arrayed coating material comprises selectively delivering one or more of a plurality of materials to a surface of a substrate having a plurality of predetermined regions to form a predetermined coating on each of the regions. including. Upon selective delivery of the materials, the plurality of materials are arranged such that each is delivered to the substrate simultaneously.
[0007]
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 is a schematic diagram of an apparatus for producing an array of coating materials;
FIG. 2 is a schematic diagram of a coating library formed with the apparatus of FIG.
FIG. 3 is a schematic illustration of an envelope of vaporized material delivered from a delivery source of a delivery mechanism to a surface of a substrate in a delivery area;
FIG. 4 is a graph showing the thickness profile distributed in one dimension in the delivery area, resulting from the vertical focusing arrangement of the delivery mechanism;
FIG. 5 is a graph showing the thickness profile distributed in one dimension in the delivery area, resulting from the oblique focusing arrangement of the delivery source of the delivery mechanism;
FIG. 6 is a graph showing the thickness profile distributed in one dimension in the delivery area, resulting from the vertical off-focus arrangement of the delivery source of the delivery mechanism;
FIG. 7 is a graph showing a thickness profile distributed in one dimension in the delivery area, resulting from a tilted off-focus arrangement of the delivery source of the delivery mechanism;
FIG. 8 is a side view of one embodiment of a combinatorial coating device having two opposing delivery sources;
FIG. 9 is a top view of a coating library formed with the apparatus of FIG.
FIG. 10 is a perspective view of one embodiment of a ternary combinatorial coating device,
FIG. 11 is a top view of a coating library formed with the apparatus of FIG.
FIG. 12 is a schematic diagram of another embodiment of a combinatorial coating device;
FIG. 13 is a top view of a mask having a plurality of patterns that can be used in the apparatus of FIG. 12,
FIG. 14 is a top view of a coating library formed using the mask of FIG. 13 with the apparatus of FIG. 12,
FIG. 15 is a side view showing a cross section of one embodiment of a vapor deposition type combinatorial coating apparatus.
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
With reference to FIGS. 1 and 2, an apparatus 10 for making an array of coating materials forming a coating library delivers one or a combination of a plurality of materials 14 to a surface 16 of a substrate 18 to form a coating 20. And a delivery mechanism 12 for performing the operation. The substrate surface 16 has a plurality of predetermined regions 22 that are preferably located within a delivery area 24 that is in place within the device 10. The delivery mechanism 12 and / or the plurality of materials 14 are arranged to deliver each of the plurality of materials simultaneously or in parallel. The controller 26 controls the selection, amount and delivery order of each of the plurality of materials 14 so that the composition of the coating 20 can be varied between each region 22 on the substrate surface 16 to form a coating library 28. I do. As a result, each of the plurality of predetermined regions 22 is covered with one of the plurality of predetermined coatings 30. The plurality of predetermined coatings 30 include a single-layer coating made of one of a plurality of materials 14, a single-layer coating made of a combination of a plurality of materials 14, a multi-layer coating made of one of a plurality of materials, and a plurality of layers. A multilayer coating consisting of a combination of the following materials is included. In addition, the device 10 may include a mask 32 in communication with the controller 26 to allow delivery of the material 14 to various combinations of the plurality of predetermined regions 22 to form a plurality of predetermined coatings 30. Apparatus 10 may also include a curing source 34 for curing the plurality of materials 14 during delivery of the plurality of materials 14 to substrate 18 or after they have been deposited on the substrate. Further, the apparatus 10 may include a test apparatus 36 for performing an analytical test on the coated substrate or the coating library 28 and determining the properties of each of the plurality of predetermined coatings 30. The mask 32 can be secured by a mounting device 35, which can optionally movably position the mask within the device 10. Similarly, the substrate 18 can be secured by a holding device 37, and optionally the holding device 37 can movably position the substrate within the device 10. Thus, the present invention provides an apparatus and method for manufacturing and testing a coating library having an array of coatings formed from a plurality of materials focused simultaneously or in parallel on a substrate.
[0009]
The delivery mechanism 12 is configured to deliver each of the plurality of materials 14 to the delivery area 24 simultaneously or in parallel from various angles. That is, as described in more detail below, the delivery mechanism 12 is positioned or focused such that at least a portion of the delivered material reaches the delivery area 24. The delivery mechanism 12 may be a single device or 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 device 10 with respect to the delivery area 24 and other delivery mechanisms. Preferably, the delivery mechanism 12 delivers each of the plurality of materials 14 to the delivery area 24 in an evaporated or sprayed state. Suitable examples of delivery mechanism 12 include any type of spray nozzle or gun, such as an ultrasonic gun, an air gun, a thermal gun, or an airless gun (such as those using hydraulic pressure), a microwave or radio frequency (RF) delivery mechanism. , Inkjet printing heads, and vapor deposition devices such as sputtering, thermal / electron / laser vapor deposition, chemical vapor deposition (CVD), molecular beam epitaxy, plasma spraying, and ion beam vapor deposition.
[0010]
The plurality of materials 14 include various states of inorganic and organic materials such as solids, liquids, gases or evaporative / spray materials. Suitable examples of inorganic coatings include metals, alloys, ceramics, oxides, nitrides and sulfides. Suitable examples of organic coatings include polymeric materials, oligomeric materials and small molecules, where small molecules are the individual monomers that react to form a coating. Polymer materials include, but are not limited to, polycarbonate, acrylic resins, silicones, cellulose esters, polyesters, alkyd resins, polyurethanes and vinyl polymers. Preferably, the plurality of organic materials include organic polymer materials such as "building" materials derived from organic materials having protective or decorative functionality, especially including thermoplastic or thermoset polymers. I do. Preferably, the plurality of inorganic materials include an oxide. Further, it is preferable that the plurality of materials 14 be vaporized or sprayed individually or in combination to induce or form a film on the substrate. Here, if a sufficient amount of material is delivered to the substrate, the evaporated / sprayed material will agglomerate to form a continuous coating. Further, the material or combination of materials can form a coating having a plurality of layers, wherein the coating can be a multi-functional coating having an overall function determined by the predetermined functional role of each layer. The materials can be combined such that a plurality of organic materials or a plurality of inorganic materials or a combination of organic and inorganic materials are combined to form a coating. Further, by providing various combinations of such materials, the interaction and suitability of various combinations of materials can also be determined.
[0011]
The coating 20 is a material or combination of materials deposited on the substrate 18. These materials may exist as separate homogeneous materials or may react, interact, diffuse, mix or otherwise combine to form a new homogeneous material, mixture, composite or blend. May be. As mentioned above, the coating 20 may be comprised of a single layer or multiple layers. Generally, the coating 20 has a lateral scale (ie, the length measured across the surface of the substrate) that is much greater than the thickness (ie, a measure of the coating perpendicular to the surface of the substrate). Preferably, each layer is a thin film layer. The composition of the coating 20 is optionally continuously varied from one predetermined area 22 to another predetermined area, thereby forming an array of coatings that define a plurality of predetermined coatings 30 of the coating library 28. be able to. Each coating in the array can be distinguished from each other based on its location. In addition, each coating in the array can be treated under the same conditions and then analyzed to determine its performance in terms of functional or practical properties, and then compared to each other to determine its relative utility.
[0012]
Each of the plurality of predetermined regions 22 is an area on the substrate 18 for receiving one or a combination of the plurality of materials 14 to form a single or multilayer coating. Each of the predetermined regions 22 can have any shape sufficient to receive and analyze the coating deposited thereon, such as rectangular, linear, arcuate, circular, oval, combinations thereof, and the like. Each predetermined area 22 is typically about 0.01 mm²~ 100cm², Preferably about 1 mm²~ 1cm², More preferably about 10 mm²~ 50mm²Have an area in the range of Although other areas can be used, the area of each predetermined region 22 can be determined by the capabilities of the film forming apparatus and the analyzing apparatus and the desired density of the coating library.
[0013]
The substrate 18 is a rigid or semi-rigid material suitable for receiving and supporting one or more of the plurality of materials 14. The substrate 18 has one or more substantially planar surfaces 16 including a plurality of predetermined regions 22. However, the substantially flat surface may have raised portions for physically separating each of the plurality of predetermined regions 22. The substrate 18 can have any size and shape, but is preferably a disk, a plate, or an elongated shape such as a tape or a roll. The substantially flat surface 16 of the substrate 18, corresponding to the delivery area 24, is typically about 1 mm²~ 1m², Preferably about 50 mm²~ 750cm², More preferably about 1 cm²~ About 500cm²Have an area in the range of
[0014]
The substrate 18 can be secured in the device 10 and placed in the delivery area 24 by the holding device 37. The holding device 37 can movably arrange the base material 18. For example, for an elongated tape-shaped substrate 18, both holding devices 37 are rotatable and, in some cases, in cooperation with rollers, a tape feeding device and a tape winding device for supporting the tape in the delivery area 24. It may have a taking device. In another example, the holding device 37 may be a plate on which the base material is placed and fixed. In this case, such a plate is connected to a motor or other actuator type device that adjusts the position of the plate with respect to the delivery area 24. As a result, the controller 26 can control the movement of the holding device 37 to adjust the predetermined area 22 for delivering the material 14. For example, the controller 26 can move the retaining device 37 such that a predetermined one of the plurality of predetermined regions 22 is located outside the delivery area 24 and thus does not receive one or more materials 14.
[0015]
The delivery area 24 is a range that is in a fixed position within the device 10. The delivery area 24 can have any shape or size, and typically, but not necessarily, has a shape and size substantially corresponding to the plurality of predetermined regions 22 on the surface 16 of the substrate 18. However, the plurality of predetermined areas 22 can be significantly larger or smaller than the delivery area 24. The fixed position of the delivery area 24 provides the device 10 with a known constant site for delivering the plurality of materials 14 to the surface 16 of the substrate 18.
[0016]
The controller 26 has input devices, output devices, memories and processors to receive, transmit, store and process signals and data to operate, monitor, record and otherwise operate the operation of the device 10. It is a computer system for controlling the computer. The controller 26 includes a computer system with an interface for integrating all components of the apparatus and a motion controller for controlling the movement of the mask 32 and the 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. Controller 26 may also include software, hardware, firmware, and other similar components and circuits for operating device 10. The controller 26 may be a single device or a plurality of devices working in concert. The controller 26 controls 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 Preferably, it is in communication with all of the components. For example, a controller controls the delivery of the material to the substrate and records the exact combination of materials that make up the coating for each given area. By controlling the delivery, the controller can adjust one or more of the material volume, material combination, delivery force, coating speed, delivery angle, spacing between the delivery mechanism and the substrate, masking, and the like. In addition, the controller 26 controls, synchronizes, integrates, and records the delivery and curing of the delivery material, testing of the coating library, and analysis of the test results.
[0017]
The mask 32 is a material having one or more patterns including an open area and a closed area. Here, the open area allows for delivery of the plurality of materials 14 to the substrate 18 and the closed area prevents delivery. The pattern can have any shape. The use of the mask 32 creates a spatial variation of the material in the coating library 28. For example, in a binary masking system, as described in more detail below, the mask 32 includes a plurality of patterns arranged sequentially to allow delivery to alternating bisections on the substrate 18. . The mask 32 can be positioned anywhere between the plurality of materials 14 and the substrate 18 along the material delivery line, including when positioned directly over and in close contact with the substrate. Increasing the distance between the mask 32 and the substrate 18 produces an effect called "shadowing," which may be undesirable in some cases. In shadowing, the pattern of material delivered to the substrate is proportional to the pattern of the mask, but until the mask reaches the substrate, the spacing between the mask and the substrate increases as the pattern being delivered expands . The mask 32 may be formed of a rigid or semi-rigid material, or may be a chemical formed on the surface of the substrate. Preferably, the material of the mask is such that the mask is as flat as possible and resists bending and / or bending. Suitable examples of mask materials include silicon, silicon oxide and glass for rigid or relatively non-flexible materials, and plastics, metals for semi-rigid or relatively flexible materials in sheet, film or foil form. And lithographic polyacrylate (PMMA) and other chemicals that form negative and positive chemical masks.
[0018]
The mask 32 can be secured within the device 10 and positioned relative to the delivery area 24 by a mounting device 35. The attachment device 37 can movably arrange the mask 32. For example, for a mask 32 of elongate semi-rigid material having a plurality of patterns, the mounting device 35 may be rotatable, possibly supporting the tape against the delivery area 24 in cooperation with rollers. May be provided with a tape feeding device and a tape winding device. In another example, for a mask 32 of a rigid material, the mounting device 35 may be a platform or other support structure. In this case, such a platform or other support structure is connected to a motor or other actuator-type device that adjusts the position of the platform and mask relative to the delivery area 24. In this manner, by moving the mask 32, various predetermined regions 22 on the base material 18 can be shielded using one pattern or a plurality of patterns. As a result, the controller 26 can control the movement of the mounting device 35 to adjust the predetermined area 22 for delivering the material 14.
[0019]
The curing source 34 is a device in communication with each of the plurality of materials 14 to cause a reaction or solvent evaporation for one or a combination of the materials. For example, such a reaction can be a polymerization, cross-linking reaction, small molecule reaction, inorganic phase reaction or other similar reaction appropriate for the delivery material. Suitable examples of the curing source 34 include a heating device in communication with the substrate 18, a radiation device in communication with the delivery or deposition material, a microwave device, a plasma device, and combinations thereof.
[0020]
The test device 36 is a device for analyzing the performance of each of the plurality of predetermined coatings 30 on the substrate 18. The test device 36 exposes the entire coating library 28 to the same conditions to determine the relative performance of each given coating 30. Test equipment 36 is in communication with controller 26 to collect and analyze test data. Suitable examples of the test device 36 include a thickness profiler, a surface analyzer, an ultraviolet (UV) absorbance tester, a scratch resistance tester, a permeability tester, and the architectural, protective and decorative properties of the coating. And other similar devices for testing other functional properties.
[0021]
Referring to FIG. 3, the source 38 of material from the delivery mechanism 12 is in a vaporized or nebulized state, preferably within an envelope 40 surrounding the delivery area 24 so that the coating covers the entire delivery area. One of the plurality of materials 14 is delivered. Delivery source 38 is the point of ejection of the material from the delivery mechanism. For example, delivery source 12 may be a spray gun nozzle. However, it may be desired that the coating does not cover the entire delivery area 24. For example, if a portion of predetermined area 22 of substrate 18 is not covered and mask 32 is not used to prevent delivery of material to such area, envelope surface 40 only surrounds a portion of delivery area 24. It is not necessary. The envelope surface 40 may have any appropriate shape, including a conical surface having various cross-sections such as a circle, an ellipse, and a rectangle, a semi-cone surface having various cross-sections, and a thin linear surface. I can do it. The shape of the envelope surface 40 depends on 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 predetermined coatings 30, the number of materials 14 to be delivered to the substrate 18, and It can be determined by similar factors. The shape of the envelope surface 40 can be adjusted by the shape of the nozzle of the delivery mechanism 12, the air shroud associated with the delivery mechanism, or other shape-determining structures or devices associated with the delivery mechanism.
[0022]
Referring to FIGS. 3 and 4, in a vertical focusing arrangement 41, a focal point 42 for delivering material 14 from a delivery source 38 coincides with a center point 44 of the delivery area 24. The delivery source 38 is arranged to deliver the material 14 along a delivery angle having a centerline 46 substantially perpendicular to the surface of the delivery area 24 at a center point 44. Referring to FIG. 4, for a coating delivered from the arrangement of FIG. 3 where the delivery angle α is substantially perpendicular to the plane 49 of the delivery area, one dimension of the delivery area 24 (eg, the lateral direction of FIG. 3) The cross-sectional thickness profile 48 along the dimension) typically has a two-dimensional substantially Gaussian or normal distribution. Thus, the thickness profile 48 has an apex 52 that coincides with the center line 46 above the center point 44 and has two equal mirror image tails on either side of the center line. Further, the delivery source 38 is located at a vertical separation 60 with respect to a plane 49 of the delivery area 24 (FIG. 3). The vertical separation 60 affects the overall width 51 of the thickness profile 48, thereby affecting the thickness of the coating at any given point along the thickness profile distribution. Thus, in this case, the thickness profile 48 is centrally located within the dimension 50 of the delivery area 24 and the thickness is greatest at the apex 52 and gradually decreases from the centerline 46 in all directions.
[0023]
Referring to FIG. 5, in a tilted focusing arrangement 55, the focal point 42 for delivering the material 14 from the delivery source 38 coincides with the center point 44 of the delivery area 24. However, the delivery source is positioned such that the material centerline 46 forms a delivery angle α in the range of about 0 degrees to about 90 degrees with respect to the plane 49 of the delivery area. Further, the delivery source is located at a horizontal separation 53 from the center point 44 for tilted focused delivery. The horizontal separation distance 53 is the distance in the plane of the delivery source 38 parallel to the plane 49 of the delivery area, away from the position of the vertical focusing arrangement. The horizontal separation 53, the vertical separation 60 and the delivery angle α are all mathematically correlated and can be varied to place the thickness profile 48 within the delivery area 24. In this embodiment, the thickness profile 48 has a distorted Gaussian distribution with an inclined tail positioned close to the delivery source 38 and an elongated tail end 58 extending away from the delivery source. Elongated tail 58 typically has an area where thickness profile 48 varies substantially linearly with length along dimension 50. Thus, in this case, the thickness profile 48 is distorted within the dimension 50 of the delivery area 24 and the thickness is greatest near the end of the dimension with the sloping tail 56 and the dimension corresponding to the elongated tail 58 from the vertex 52 Decreases toward the end of the
[0024]
Referring to FIG. 6, in a vertical off-focus arrangement 57, the focal point 42 for delivering material 14 from the delivery source 38 is at an offset distance 59 along the dimension 50 from the center point 44 in the plane of the delivery area 24. is there. In this case, if the centerline 46 has a delivery angle α substantially perpendicular to the plane 49 of the delivery area 24, then the offset distance 59 will be the horizontal separation of the delivery source 38 from the position of the vertical focusing arrangement (FIG. 4). It is substantially equivalent to the distance. Also note that the focal point for the delivery mechanism may be inside or outside the delivery area. Thus, in this case, the thickness profile 48 is offset within the dimension 50 of the delivery area 24 and the thickness is greatest at the offset of the apex 52 and gradually decreases from the centerline 46 in all directions. .
[0025]
Referring to FIG. 7, in a tilted off-focus arrangement 61, the focal point 42 for delivering the material 14 from the delivery source 38 is at an offset distance 59 along the dimension 50 from the center point 44. Here, centerline 46 has a delivery angle α in the range of about 0 degrees to about 90 degrees with respect to plane 49 of delivery area 24. In this case, because of the delivery angle α and the offset focus 42, the horizontal separation 53 of the delivery source 38 from the vertical focus delivery point is greater than the focus offset distance 59 with respect to the center point 44. Thus, in this case, the thickness profile 48 is more warped within the dimensions 50 of the delivery area 24 than the arrangement of FIG.
[0026]
In each of the arrangements of FIGS. 4-7, the flatness of the thickness profile 48 within the delivery area 24 varies depending on the vertical separation from the delivery source 38, and the flatness increases as the separation increases. . Furthermore, the flatness of the thickness profile 48 in the delivery area 24 also changes according to the delivery angle α, the horizontal separation distance 53 and the offset distance 59, and the smaller the delivery angle and the larger the horizontal separation distance and the offset distance. Flatness is improved. For example, referring to FIG. 4, the thickness profile 48 can be substantially flattened within the dimensions 50 of the delivery area 24 with an appropriate combination of delivery angle, horizontal separation and offset distance. However, as the separation decreases, the thickness profile 48 within the dimensions 50 of the delivery area 24 may gradually change from a maximum thickness at the apex 52 to a minimum thickness at both ends of the dimensions of the delivery area. Preferably, a coating having a substantially constant thickness to exclude thickness variables from the analysis of the plurality of predetermined coatings 30 associated with each predetermined region 22 so that the discussion focuses on the effect of the coating composition. A library is desired. In effect, calibrating each delivery mechanism such that a linear thickness profile is distributed across the delivery area results in a coating library of substantially constant thickness. If multiple delivery mechanisms are used, preferably the same portion of the thickness profile for each delivery mechanism is located in the delivery area. Thus, the present invention provides a virtually infinite variation in the composition, layers and thickness of the coating material by varying the vertical separation 60, the delivery angle α and the offset distance 59 for each delivery source 38 of each of the plurality of materials 14. Can be manufactured in a plurality of predetermined regions 30 of the substrate 18.
[0027]
Referring to FIGS. 8 and 9, in one embodiment of a combinatorial coating apparatus 62, a continuously changing coating is achieved by simultaneously depositing two or more (A and B) of the plurality of materials 14 from the delivery source 38. Library 64 is formed on substrate 18. The relative thickness and composition of each of the plurality of predetermined coatings 30 can be continuous individually or together as a result of the thickness profile 48 (FIGS. 4-7) of each of the materials A and B delivered to the substrate 18. Can change. Such continuous changes include the delivery angle α, the delivery force of the delivery mechanism 12 (not shown) associated with each delivery source 38, the coating rate or amount of material deposited per unit time, the material introduced into the delivery mechanism. Supply speed and concentration, the vertical separation distance 60, the offset distance 59 of the delivery source 38 with respect to the center point 44, the horizontal separation distance 53 of each delivery source 38 with respect to the center point 44, the shape of the envelope surface 40 (not shown), It may be linear or non-linear depending on such variables as atmosphere, power per area, pressure, gas type, and other similar factors. By varying each of these variables individually or in combination, a given coating can be created in each given area 30. Further, although not shown, a mask 32 can be placed between each of the delivery sources 38 and the substrate 18 (preferably adjacent to or in close contact with the substrate) to assist in creating a coating library. .
[0028]
Still referring to FIG. 8, the delivery angle α may have a value in the range of about 0 ° to about 90 °, more preferably about 15 ° to about 75 °, and most preferably about 30 ° to about 60 °. . The vertical separation 60 can vary from about 0 cm to about 90 cm, more preferably from about 3 cm to about 30 cm, and most preferably from about 10 cm to about 20 cm. Horizontal separation 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 thickness of the coating can vary from about 1 nanometer to about 1 millimeter, more preferably from about 1 micrometer (or micron) to about 500 microns, and most preferably from about 5 microns to about 100 microns.
[0029]
Referring to FIG. 9, one embodiment of a coating library 64 formed with a combinatorial coating apparatus 62 (FIG. 8) includes gradients of materials A and B opposing each other. These gradients can be used to move from about 100% to about 0% of material A and from about 0% to about 100% of material B while moving laterally across the coating library from the side adjacent to source 38 of material A. It changes continuously within the range. Depending on the variables described above in relation to the delivery of the material to the substrate, the coating library 64 may have a substantially constant or varying thickness along the substrate. Preferably, the focal point 42 of each of the delivery sources of materials A and B is at a predetermined offset distance 53 from the center point 44 of the delivery area such that the thickness of the coating library is substantially constant along the substrate. Have. Further, if the evaporation rate is adjusted to allow sufficient time for the diffusion of materials A and B, new substances can be generated by in situ diffusion / mixing or reaction of A and B. Alternatively, the substrate 18 of FIG. 8 may be movable in a rotational direction, a longitudinal direction, a lateral direction, etc., in order to vary the composition of each predetermined coating 30. In addition, the delivery source 38 may be supplied with new and different materials sequentially. Combining this with a laterally moving elongated substrate results in a coating that varies continuously along the length of the substrate. In addition, it is preferred to place each source 38 in a delivery plane 65 that is substantially parallel to the plane 49 of the delivery area, but separated therefrom by a vertical separation distance 60. However, in another embodiment, the vertical separation 60 of each delivery source 38 may be independently varied to achieve a different thickness profile 48 within the delivery area 24. In this way, the device 62 simultaneously delivers two or more of the plurality of materials onto the substrate, thereby enabling to obtain a continuously changing coating having a gradient of the two or more materials.
[0030]
Referring to FIGS. 10-11, in another embodiment similar to the embodiment of FIGS. 8-9, a ternary combinatorial coating apparatus 68 provides a continuous ternary coating library 70. Three or more (A, B, and C) of the plurality of materials 14 (FIG. 1) can be delivered from the delivery source 38 simultaneously or sequentially. Each of the delivery sources 38 is arranged in a substantially identical tilted off-focus arrangement 61 (FIG. 7) as described above. The delivery sources 38 are preferably equally spaced around a circle 74 having a center 76 on the same axis 78 as the center point 44. Preferably, circle 74 has a diameter greater than the diameter of the delivery area. For example, 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 the device 68 can be a continuous changing combination of each of the three materials A, B and C that mimics a ternary diagram. The same variables that affect the formation of the coating library 64 (FIGS. 8-9) as described above apply to the coating library 70 of the device 68 as well. For example, the relative composition of the coating library 70 at any point is a function of the horizontal separation 53, offset distance 59, delivery angle α, shape of the fog envelope 40 of each material, focal point 42 of each delivery source, etc. is there. Further, the preferred separation distances and angles are the same as described above with respect to FIGS. In one example, three airbrush guns were simultaneously focused to deliver a fine mist of three materials to the substrate using a tilted off-focus arrangement 61 (FIG. 7). All guns were located in a delivery plane parallel to the delivery area and about 15 cm vertically from the delivery area. Further, each gun was arranged to have a delivery angle α of about 45 ° and a horizontal separation 53 of about 18 cm. Substrate 18 was a substantially circular disk of silicon wafer material having a diameter of about 8 cm. The dimensions of each of the plurality of predetermined regions were determined to form a coating library having 66 predetermined coatings. The coating material contained 2% polyethylmethacrylate (PEMA) in isopropanol solvent mixed with organic pigment. When deposited through a ternary or triangular mask (not shown) and thermally cured, a ternary coating library with 66 different compositions was formed in minutes. Although the coating had a thickness of about 2 microns, the coating thickness increased and decreased linearly with coating time.
[0031]
With reference to FIGS. 12-14, in another embodiment, the combinatorial coating apparatus 72 is positioned in place so that each of them simultaneously or sequentially delivers one of the plurality of materials 14 through the mask 32 to the substrate 18. A plurality of co-focusing or simultaneous focusing delivery mechanisms 12. Each of the plurality of delivery mechanisms 12 creates a mist of spray material within an envelope (FIG. 3) that intersects the surface 16 of the substrate 18. Each delivery source 38 is preferably arranged in a tilted off-focus arrangement 61 (FIG. 7). Preferably, each delivery mechanism 12 is equally spaced around a circle 74 having a center 76 on the same axis 78 as the center point 44. Further, each delivery mechanism 12 preferably has a horizontal separation 53 (FIG. 7) along the radial direction from the center 76 that is less than the distance from the center point 44 to the end of the delivery area 24. Preferably, the focal point 42 (not shown) of each delivery mechanism 12 is focused at a substantially equivalent offset distance 59 (FIG. 7) from the center point 44, so that within the delivery area 24 there is a thickness for each material. The same part of the profile (FIG. 7) is located. However, the focal point 42 for each delivery mechanism 12 need not be offset from the center point 44 and need not have an equivalent offset distance 53. In fact, each delivery mechanism 12 can have a unique focus 42. Such an inherent focus is that center line 46 (FIG. 3) is relative to surface 16 as long as envelope surface 40 (FIG. 3) of delivery material 14 matches at least a portion of surface 16 of delivery area 24 and thus substrate 18. Included are those that are vertical or inclined and that result in the delivery mechanism being aligned with the center point 44 or spaced apart from it along the radial direction. Further, the delivery mechanism 12 need not be arranged around a circle, but may be in any relative position as long as it is possible to deliver the plurality of materials 14 to at least a portion of the delivery area 24 in parallel or simultaneously. I can do it.
[0032]
The mask 32 preferably has a plurality of patterns 80 (FIG. 13) for covering various predetermined regions 22 (FIG. 2) with various materials to form a coating library 82 (FIG. 13). The material 14 can be moved in and out of the delivery line. Although shown in FIG. 12 as being spaced from the substrate 18, the mask is preferably a physical contact mask in contact with or in proximity to the substrate to eliminate shadowing. For example, referring to FIG. 14, an apparatus 72 uses the four of the plurality of materials 14 (A, B, C and D) together with the first four patterns 80 of the mask 32 (FIG. 13) to apply 16 predetermined coatings 30. A coating library 82 can be formed.
[0033]
In an embodiment of the apparatus 72, each delivery mechanism 12 sprays the liquid precursor material 14 into a fine mist, which is delivered individually or with other nozzles / materials to the substrate 18 to form a coating layer. Spray nozzle. By applying compressed air, superheated steam or ultrasonic waves to the liquid material, fine mist of the liquid material can be generated. By sequentially delivering the material 14 from the plurality of sprayers 12 while using a series of masking patterns and (if necessary) curing steps to form the predetermined coating 30 within the predetermined region 22 (FIG. 2) of the substrate, A coating library 82 having a plurality of coating layers can be created. This may be desirable, for example, when searching for coatings with multifunctional properties such that each or a combination of coating layers provides one or more functional properties. In this particular example, which should not be considered limiting, eight liquid paints (A-H) are supplied to eight individually controlled spray guns. Suitable liquid paints include, for example, polyacrylides, polycarbonates, vinyl polymers, silicones and silica gels. Further, suitable spray guns include, for example, those manufactured by SonoTech. If the material requires curing, suitable examples of curing source 34 (FIG. 1) include a temperature of about 80 to about 200, more preferably about 100 to about 150, and about 10 minutes to about 10 hours, more preferably There are hot plates and UV lamps that can cure the material in a time of about 1 hour to about 4 hours. Thus, using different spacings and volumes of liquid precursor material delivered from each spray nozzle to form a coating library, using different mask patterns in conjunction with different liquid precursor materials, Alternatively, by performing maskless "continuous phase diffusion" of the material, a coating library having a plurality of predetermined multilayer coatings is created in parallel.
[0034]
Referring to FIG. 15, in another embodiment, a vapor deposition combinatorial coating apparatus 90 simultaneously or sequentially deposits one of a plurality of solid materials 14 on a substrate 18 disposed on a movable stage 92 within a vapor deposition housing 94. For delivery, it comprises a plurality of delivery mechanisms 12, each co-focused or co-focused. To withstand high deposition temperatures, the substrate is made of magnesium oxide or lanthanum aluminate (LaAlO).₃) Is made of a stable high-temperature material. The deposition housing 94 is sealable to form a vacuum chamber 96 inside its inner surface. The delivery mechanism 12 in this case is a vapor deposition device, such as a sputter gun, preferably operated with high frequency power matched for optimum output. The stage 92 supports the substrate 18 in a known position and adjusts the stage in a vertical, rotational, or linear direction to position the substrate in the delivery area. A mask 32 having an array of various patterns 80 is disposed between the delivery mechanism 12 and the substrate 18. Preferably, the mask 32 is substantially in contact with the substrate 18 during deposition to minimize "shadowing effects". The mask 32 is movably arranged in a vacuum chamber 98 of the mask housing 100. The mask housing 100 is in communication with the main housing 94 so as to maintain the atmosphere in both vacuum chambers 96 and 98. Further, the mask housing 100 includes a gearbox 102 and a micrometer 104, which respectively help to move and measure the position of the mask pattern 80 with respect to the substrate 18.
[0035]
Further, device 90 may optionally include a shutter 106 having one or more openings 108 to select one or more materials to be delivered simultaneously or sequentially to prevent mixing of the materials. The shutter 106 changes the mask pattern 80 in a vacuum using a linear motion type vacuum feedthrough, and at the same time, movably moves the shutter and the opening 108 to the rotor 110 which selects the solid material 14 to be evaporated. Are linked. The deposition amount of the material 14 is monitored by a thickness monitor 112 such as a quartz oscillator. By depositing different solid precursors through different mask patterns, substrates having more than 100 coating compositions / layer structures can be obtained without the need to break vacuum to change the solid material and / or mask pattern. Can be manufactured in days.
[0036]
The vacuum atmosphere in the vacuum chambers 96 and 98 is maintained at a back pump station 114 connected to a turbo molecular pump 116. For example, the back pump station 114 has about 10^-3Torr vacuum, while the turbo molecular pump 116^-6Torr vacuum may result. Pumps 114 and 116 are in communication with vacuum chamber 96 via gate valve 118.
[0037]
For example, the device 90 can create a coating library of any ceramic, metal and / or semiconductor material having surface roughness and thickness accuracy measured in nanometers. In addition to the sputtering apparatus described above, other suitable delivery mechanisms 12 include laser ablation, electron beam evaporation, CVD, etc., which can be used with a masking apparatus to create an inorganic coating library. For the creation of the inorganic coating library, a co-focused multi-source thermal evaporation device coupled to a masking device can be configured. The same device can also be used to create small molecule libraries, such as those used in organic light emitting diode (LED) devices.
[0038]
Thus, it is apparent that there has been provided a combinatorial coating apparatus and method according to the present invention. Although the present invention has been illustrated and described in detail in connection with preferred embodiments, it will be readily apparent that those skilled in the art can make various changes and modifications without departing from the scope of the invention. Further, it is understood that the principles of the arrangement of the delivery mechanism and the formation of the coating thickness profile by delivery of the material described herein apply to all embodiments as far as applicable. Should.
[Brief description of the drawings]
FIG.
1 is a schematic diagram of an apparatus for producing an array of coating materials.
FIG. 2
2 is a schematic diagram of a coating library formed by the apparatus of FIG. 1.
FIG. 3
4 is a schematic illustration of an envelope of evaporative material delivered from a delivery source of a delivery mechanism to a surface of a substrate in a delivery area.
FIG. 4
FIG. 4 is a graph showing a one-dimensionally distributed thickness profile of a delivery area obtained with a vertical focusing arrangement of the delivery mechanism.
FIG. 5
Fig. 4 is a graph showing a one-dimensionally distributed thickness profile of the delivery area obtained with a tilted focusing arrangement of the delivery source of the delivery mechanism.
FIG. 6
FIG. 4 is a graph showing a one-dimensionally distributed thickness profile of a delivery area obtained with a vertical off-focus arrangement of a delivery source of a delivery mechanism.
FIG. 7
FIG. 4 is a graph showing a one-dimensionally distributed thickness profile of a delivery area obtained with a tilted off-focus arrangement of a delivery source of a delivery mechanism.
FIG. 8
1 is a side view of one embodiment of a combinatorial coating device having two opposed delivery sources.
FIG. 9
FIG. 9 is a top view of the coating library formed by the apparatus of FIG.
FIG. 10
1 is a perspective view of one embodiment of a ternary combinatorial coating device.
FIG. 11
FIG. 11 is a top view of a coating library formed by the apparatus of FIG.
FIG.
5 is a schematic diagram of another embodiment of a combinatorial coating device.
FIG. 13
13 is a top view of a mask having a plurality of patterns that can be used in the apparatus of FIG.
FIG. 14
FIG. 13 is a top view of a coating library formed using the mask of FIG. 13 with the apparatus of FIG. 12.
FIG.
It is a side view showing a cross section of one embodiment of a vapor deposition type combinatorial coating device.
[Explanation of symbols]
Apparatus for making coating materials arranged in 10mm
12 delivery mechanism
14 material
16mm surface
18mm base material
20mm coating
22 Predetermined area
24 delivery area
26 controller
28 Coating Library
30mm prescribed coating
32 mask
34 ° curing source
35 mounting device
36mm test equipment
37 holding device
38 delivery source
38 delivery source
42 focus
44 ° center point
72 combinatorial coating equipment
74 yen
76 center
78 ° axis

Claims (46)

An apparatus (10) for producing an array of coating materials, comprising:
A substrate (18) having a surface (16) partitioned into a plurality of predetermined regions (22);
A plurality of materials (14) for coating the substrate,
A delivery mechanism (12) with a plurality of materials, the delivery mechanism (12) arranged to simultaneously deliver each of the plurality of materials to a surface of a substrate, and each of a plurality of predetermined regions of the substrate. A controller (26) for controlling a delivery mechanism to selectively deliver each of the plurality of materials with a predetermined coating (30).
An apparatus (10) comprising: The delivery mechanism further includes a plurality of delivery sources (38), each of the delivery sources for delivering one of the plurality of materials, each of the plurality of delivery sources having a different home position within the device. The device of claim 1. The apparatus of claim 1, wherein the predetermined coating associated with one or more of the plurality of regions comprises a thin film coating having a plurality of layers. The apparatus further includes a mask (32) having a plurality of patterns, the mask being disposed adjacent to a surface of the substrate, each of the plurality of patterns being positionable above the substrate, wherein each of the plurality of patterns is disposed. The device of claim 1, wherein the device is unique to being capable of delivering material to various combinations of a plurality of predetermined regions of the substrate. The apparatus of claim 1, wherein each of the plurality of materials comprises a material selected from the group consisting of metals, alloys, ceramics, oxides, nitrides, and sulfides. The device of claim 1, wherein each of the plurality of materials comprises a material selected from the group consisting of a polymer material, an oligomer material, a small molecule, a thermoplastic polymer, and a thermosetting polymer. The device of claim 1, wherein the delivery mechanism further comprises a deposition device. The delivery mechanism further includes a shutter having a plurality of positions corresponding to each of the plurality of materials, wherein a controller controls the position of the shutter to selectively expose one or more of the plurality of materials to a surface of the substrate. Item 8. The apparatus according to Item 7. The device of claim 1, wherein the delivery mechanism further comprises a plurality of spray devices corresponding to the plurality of materials, each of the plurality of materials being capable of being vaporized by a corresponding one of the plurality of spray devices. The device further comprises:
A movable mounting device (35) having a mask having a plurality of masking patterns and a mounting table for holding the mask, the movable mounting device being in communication with a controller, wherein the controller controls the movement of the mounting device so that one type of a plurality of materials is provided. A movable mounting device for delivering the above to a substrate and arranging one of a plurality of masking patterns above the substrate;
The device of claim 1 comprising: The apparatus further includes a movable holding device (37) in communication with the controller having a fixture for supporting the substrate, wherein the controller controls the speed of movement of the supporting device to control one or more of the plurality of materials. The device of claim 1, wherein at least a portion of the substrate is disposed within the delivery area for receiving delivery. The device of claim 11, wherein the holding device is movable at a substantially constant speed. An apparatus (10) for producing an array of coating materials, comprising:
A delivery area (24) occupying a fixed position in the device,
A substrate (18) having a surface (16) partitioned into a plurality of predetermined regions (22), wherein the surface of the substrate is positionable within a delivery area;
A plurality of materials (14) for coating the substrate,
A delivery mechanism (12) with a plurality of materials, the delivery mechanism (12) arranged to simultaneously deliver each of the plurality of materials from a different home position into the delivery area; and a plurality of predetermined regions of the substrate. (26) for controlling a delivery mechanism to selectively deliver one or more of the plurality of materials such that each has one or more predetermined coatings (30) of the plurality of materials.
An apparatus (10) comprising: 14. The apparatus of claim 13, wherein the predetermined coating associated with one or more of the plurality of regions comprises a thin film coating having a plurality of layers. The apparatus further includes a mask having a plurality of patterns, wherein the mask is disposed adjacent the delivery area between the plurality of materials and the surface of the substrate, each of the plurality of patterns being positionable within the delivery area. 14. The apparatus of claim 13, wherein each of the plurality of patterns is unique to being capable of delivering material to a different combination of a plurality of predetermined regions of the substrate. 14. The apparatus of claim 13, wherein each of the plurality of materials comprises a material selected from the group consisting of metals, alloys, ceramics, oxides, nitrides, and sulfides. 17. The device of claim 16, wherein the delivery mechanism further comprises a deposition device. 20. The delivery mechanism further includes a shutter having a plurality of positions corresponding to each of the plurality of materials, and a controller controls the position of the shutter to selectively expose one or more of the plurality of materials to the delivery area. The described device. 14. The device of claim 13, wherein each of the plurality of materials comprises a material selected from the group consisting of a polymer material, an oligomer material, a small molecule, a thermoplastic polymer, and a thermoset polymer. 20. The device of claim 19, wherein the delivery mechanism further comprises a plurality of spray devices corresponding to the plurality of materials, each of the plurality of materials being capable of being vaporized by a corresponding one of the plurality of spray devices. The apparatus further includes a movable mounting device (35) in communication with the controller having a mounting for holding the mask, the controller controlling movement of the mounting device to deliver one or more of the plurality of materials. 14. The apparatus of claim 13, wherein the plurality of patterns are delivered and one of the plurality of patterns is positioned above the delivery area. The apparatus further includes a movable holding device (37) in communication with the controller having a fixture for supporting the substrate, the controller controlling the speed of movement of the supporting device to transfer one or more of the plurality of materials. The device of claim 1, wherein the device delivers to the delivery area and places at least a portion of the substrate within the delivery area. 23. The device of claim 22, wherein the holding device is movable at a substantially constant speed. A method of making an array of coating materials, comprising:
Preparing a substrate (18) having a surface (16) partitioned into a plurality of predetermined regions (22);
One or more of the plurality of materials (14) are selectively delivered to a surface of the substrate to form a predetermined coating (30) on each of a plurality of predetermined regions of the substrate, wherein each of the plurality of materials is A method comprising being arranged for simultaneous delivery to a substrate. 25. The method of claim 24, wherein selectively delivering one or more of the plurality of materials further comprises delivering each of the plurality of materials from a different home position. The method of claim 24, wherein the predetermined coating comprises a thin film coating. The method of claim 24, wherein the predetermined coating comprises a thin film coating having a plurality of layers. 25. The method of claim 24, further comprising placing a mask (32) between a surface of the substrate and one or more delivery materials. 29. The method of claim 28, wherein disposing a mask further comprises selectively disposing one of a plurality of mask patterns between a surface of the substrate and one or more delivery materials. The method of claim 24, wherein each of the plurality of materials comprises a material selected from the group consisting of metals, alloys, ceramics, oxides, nitrides, and sulfides. 25. The method of claim 24, wherein each of the plurality of materials comprises a material selected from the group consisting of a polymer material, an oligomer material, a small molecule, a thermoplastic polymer, and a thermoset polymer. 25. The method of claim 24, wherein selectively delivering one or more of the plurality of materials further comprises evaporating the materials. 25. The method of claim 24, wherein selectively delivering one or more of the plurality of materials further comprises positioning a shutter opening between the selected material and the substrate. 25. The method of claim 24, further comprising moving the substrate while delivering one or more of the plurality of materials to the substrate. 25. The method of claim 24, further comprising placing one of the plurality of patterns of the mask between the selected material and the substrate. A method of making an array of coating materials, comprising:
A substrate (18) having a surface (16) partitioned into a plurality of predetermined regions (22) is arranged such that the surface of the substrate is within a delivery area (24), wherein the delivery area is in a fixed position. None,
One or more of the plurality of materials (14) are selectively delivered to the delivery area, each from a different home position, and one or more predetermined coatings (30) of the plurality of materials are applied to each of the plurality of predetermined regions of the substrate. A method comprising forming a. 37. The method of claim 36, wherein the predetermined coating comprises a thin film coating. 37. The method of claim 36, wherein the predetermined coating comprises a thin film coating having a plurality of layers. 37. The method of claim 36, further comprising placing a mask (32) between a surface of the substrate and one or more delivery materials. 40. The method of claim 39, wherein placing the mask further comprises selectively placing one of the plurality of mask patterns between the surface of the substrate and the one or more delivery materials. 37. The method of claim 36, wherein each of the plurality of materials comprises a material selected from the group consisting of metals, alloys, ceramics, oxides, nitrides, and sulfides. 37. The method of claim 36, wherein each of the plurality of materials comprises a material selected from the group consisting of a polymeric material, an oligomeric material, a small molecule, a thermoplastic polymer, and a thermoset polymer. 37. The method of claim 36, wherein selectively delivering one or more of the plurality of materials further comprises evaporating the materials. 37. The method of claim 36, wherein selectively delivering one or more of the plurality of materials further comprises positioning a shutter opening between the selected material and the substrate. 37. The method of claim 36, further comprising moving the substrate while delivering one or more of the plurality of materials to the substrate. 46. The method of claim 45, further comprising placing one of the plurality of patterns of the mask between the selected material and the substrate.

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