RU2270881C2 - System for making bulk of materials with coat (versions) - Google Patents

Abstract

FIELD: metallurgy; combination systems for application of coats; mechanical engineering; manufacture of materials possessing protective and decorative properties.

SUBSTANCE: systems (10) include substrate (18) having surface (16) with many areas for many materials (14). Feed mechanism (12) connected with many materials is provided for simultaneous delivery of each material to substrate surface. Control unit (26) is used for control of feed mechanism for selective delivery of each material; thus, each area of substrate has definite coat determined beforehand.

EFFECT: increased productivity; possibility of performing analysis of materials with coats.

3 cl, 15 dwg

Description

The present invention relates to a system for obtaining and selecting coating libraries and, more particularly, to systems for parallel deposition of layers of materials on a substrate to obtain a coating library.

Coatings are widely used in industry to enhance functionality and increase the value of the substrate material. In general, there are two types of functional coating materials: inorganic and organic coatings. Inorganic coatings were used both in the semiconductor industry, for example, in various thin-film integrated circuits, and in traditional industry, for example, in the form of coatings that create a thermal barrier for steam turbines and aerodynamic surfaces of aircraft engines. Organic coatings are also widely used in many industrial applications for protective or decorative purposes, such as automotive overcoat, paints, etc. Other types of coatings include, for example, protective and anti-corrosion coatings, adhesive and anti-adhesive coatings, environmental barrier coatings, electrically conductive or optically transparent coatings, hard scratch-resistant coatings, etc. The discovery of advanced coating formulations is of great importance to the manufacturer.

However, the development of common approaches to accelerate the development of methods for producing various coating systems can be even more important, since the search and optimization of improved coatings is more an art than a science. The power of the theoretical approach to finding and optimizing improved coatings is limited in large part because of the complexity of typical coating systems and the variety of quality requirements that they must meet. Typically, industrial coating formulations must meet multiple functional requirements, and many compatible functional groups or mixtures are required to obtain a balanced formulation. In addition, the properties of the coating system depend not only on the formulation or composition, but also on the process conditions and coating method. For example, the degree of heterogeneity of thickness and surface roughness, which depends on the method of coating application and processing, are important for the quality and reproducibility of the coating. Further, various processing conditions, including curing under the influence of ultraviolet light or an electron beam; varying temperature or pressure and the sequence of application of each layer of multilayer coatings are extremely important factors in determining the structure or composition of the final coating. In addition, the structure or composition of the final coating affects the functionality of the coating. Thus, due to the magnitude of the variable parameters, most of the used industrial coating systems developed to date have been the result of the random success of experimental methods conducted by trial and error.

SUMMARY OF THE INVENTION

Therefore, there is a need for an approach that accelerates the speed of creating and studying functional coatings for various industrial applications. Thus, the aim of the present invention is to provide a system for high-performance manufacturing and analysis of an array of coated materials.

This goal is achieved in that the system for manufacturing an array of coated materials comprises a substrate having a surface with a plurality of predetermined areas, a plurality of materials for coating the substrate, a feed mechanism associated with a plurality of materials and adapted to simultaneously supply each material to the surface of the substrate, and regulating a device controlling the feeding mechanism for selectively feeding each material so that each predetermined region of the substrate has a predetermined coating term.

The feed mechanism may further include multiple sources, each of which is designed to supply one material and has a different fixed location within the system.

A predetermined coating associated with at least one region may include a thin film coating having multiple layers.

The system may further include a mask having a plurality of patterns and located adjacent to the surface of the substrate, wherein each pattern is located on top of the substrate and is unique to provide materials to various combinations of a plurality of predetermined regions of the substrate.

Each material can be selected from the group consisting of metals, alloys, ceramic materials, oxides, nitrides and sulfides.

Each material can be selected from the group consisting of polymeric materials, oligomeric materials, small molecules, thermoplastic polymers and thermosetting polymers.

The feed mechanism may further include a vapor deposition device.

The feed mechanism may further include a shutter having a plurality of positions corresponding to each material, and a control device adapted to control the position of the shutter to selectively expose the substrate surface to at least one material.

The feed mechanism may further include a plurality of spraying devices corresponding to a plurality of materials, each of which is vaporized by a corresponding single spraying device.

The system may further include a mask having a plurality of masking patterns, and a movable fixing device associated with the adjusting device, and having a holder for fixing the mask, while the adjusting device is adapted to control the movement of the fixing device to the position of one masking pattern over the substrate in combination with the feed, at least one material per substrate.

The system may further include a movable clamping device associated with the regulating device and having a clamp for supporting the substrate, while the regulating device is able to control the speed of movement of the supporting device for locating at least a portion of the substrate within the feed zone for feeding at least one material.

The fastening device can move at a substantially constant speed.

This goal is achieved by the fact that the system for manufacturing an array of coated materials includes a feed zone fixedly located inside the system, a substrate having a surface with many predetermined areas and located inside the feed zone, a plurality of materials for coating the substrate, a feed mechanism associated with many materials and adapted for the simultaneous supply of each material from various fixed positions to the feed zone, and an adjusting device that controls the mechanics m filing for selectively supplying at least one material in the feeding zone so that each predetermined area of the substrate has a predetermined coating at least one material.

A predetermined coating associated with at least one region may include a thin film coating having multiple layers.

The system may further include a mask having a plurality of patterns and located adjacent to the feed region between the plurality of materials and the surface of the substrate, and each pattern is located within the feed zone and is unique to allow materials to be supplied to various combinations of the plurality of predetermined regions of the substrate.

Each material can be selected from the group consisting of metals, alloys, ceramic materials, oxides, nitrides and sulfides.

The feed mechanism may further include a vapor deposition device.

The feed mechanism may further include a shutter having a plurality of positions corresponding to each material, while the adjusting device is able to control the location of the shutter for the selective action of at least one material in the feed zone.

Each material can be selected from the group consisting of polymeric materials, oligomeric materials, small molecules, thermoplastic polymers and thermosetting polymers.

The feed mechanism may further include a plurality of spraying devices corresponding to a plurality of materials, each of which is vaporized by one respective spraying device.

The system may further include a movable securing device associated with the adjusting device and having a holder for securing the mask, while the adjusting device is able to control the movement of the fixing device to the position of one pattern above the feed zone in combination with the supply of at least one material to the feed zone.

The system may further include a movable clamping device associated with the adjusting device and having a clamp for supporting the substrate, while the adjusting device is able to control the speed of movement of the supporting device to locate at least a portion of the substrate within the feed zone, in combination with the feed of at least , one material per feed zone.

The fastening device can be moved at a substantially constant speed.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 is a schematic diagram of a system for manufacturing an array of coated materials.

Figure 2 is a schematic diagram of a coating library obtained from the system shown in figure 1.

Figure 3 is a schematic diagram of the envelope surface of the vaporized material supplied from the source of the feed mechanism to the surface of the substrate within the feed zone.

Figure 4 is a profile curve of the thickness distributed along the size of the feed zone, with a perpendicular focused layout of the feed mechanism.

5 is a profile curve of a thickness distributed along the size of the feed zone, with the layout focused at an angle of the feed mechanism.

Fig.6 is a curve of the profile of the thickness distributed along the size of the feed zone, with a perpendicular, out-of-focus layout of the feed mechanism.

Fig.7 is a profile curve of the thickness distributed along the size of the feed zone, with an off-focus layout at an angle of the feed mechanism.

Fig. 8 is a side view of one embodiment of a combinatorial coating system having two opposed feed sources.

Fig.9 is a top view of the library coatings obtained from the system shown in Fig.8.

10 is a perspective view of one embodiment of a triple combinatorial coating system.

11 is a top view of a coating library obtained from the system shown in FIG. 10.

12 is a schematic diagram of another embodiment of a combinatorial coating system.

FIG. 13 is a plan view of a mask having a plurality of patterns and used in the system of FIG. 12.

Fig. 14 is a top view of the coating library obtained using the mask shown in Fig. 13 in the system shown in Fig. 12.

15 is a side view showing a cross section of one embodiment of a combinatorial vapor deposition coating system in practice.

DETAILED DESCRIPTION OF THE INVENTION

1 and 2, a system 10 for manufacturing an array of coated materials that form a coating library includes a feed mechanism 12 that delivers one or a combination of a plurality of materials 14 to a surface 16 of a substrate 18 to produce a coating 20. The surface 16 of the substrate has a plurality of certain areas 22 that are located within the feed zone 24, which is preferably in a fixed position within the system 10. The feed mechanism 12 and / or a plurality of materials 14 are arranged to simultaneously feed or fed in parallel, each of the plurality of materials in the feed zone 24. The adjusting device 26 controls the selection, quantity, and feed sequence of each of the plurality of materials 14 so that the composition of the coating 20 can vary in each of the areas 22 on the surface of the substrate 16 to obtain a coating library 28. Essentially, each of the plurality of predetermined areas 22 is coated with one of the plurality of predetermined coatings 30. The plurality of predetermined coatings 30 includes a single layer coating with one of a plurality of materials 14, a single layer coating with a combination of many materials, a multi-layer coating, each layer of which is one of many materials, and a multilayer coating, each layer of which is a combination of many materials. In addition, the system 10 may include a mask 32 associated with the adjusting device 26 to provide materials 14 to various combinations from a plurality of predetermined areas 22 to obtain a plurality of predetermined coatings 30. The system 10 may also include a curing source 34 for curing a plurality of materials 14 when they are fed to the substrate 18, or as soon as they have been deposited on the substrate. The system 10 may include a testing device 36 for conducting analytical tests on a coated substrate or coating library 28, to determine the properties of each predetermined coating 30. The mask 32 may be fixed by a fixing device 35, which may selectively move the mask within the system 10. Similarly, the substrate 18 may be secured with a clamping device 37, which can selectively position the substrate within the system 10. Thus, the present invention provides systems and a method for manufacturing and testing a coating library having an array of coatings, which is obtained from a plurality of simultaneously focused materials or parallelly focused onto a substrate.

The feed mechanism 12 is designed so that each material 14 can be fed simultaneously or fed in parallel to the feed zone 24 at different angles. As such, the feed mechanism 12 is positioned or focused so that at least a portion of the feed material reaches the feed zone 24, as discussed in more detail below. The feed mechanism 12 may be a single device or may be a plurality of individual devices, each of which corresponds to a single material 14. The location of each or more of the feed mechanisms 12 is preferably stationary within the system 10 with respect to the feed zone 24 and with respect to other feed mechanisms. Preferably, the feed mechanism 12 projects each of the plurality of materials 14 to the feed zone 24 in vaporous or atomized form. Suitable options for the feed mechanism 12 include spray nozzles or spray guns of any type, such as ultrasonic, air, thermal, airless spray guns, for example, hydraulically powered spray guns, microwave or radio frequency feed mechanisms, inkjet heads, a vapor deposition apparatus including spraying , thermal / electronic / laser evaporation, chemical vapor deposition, molecular beam epitaxy, plasma sputtering and ion beam deposition.

Many materials 14 include inorganic materials and organic materials in various states, for example, in the form of solid, liquid, gaseous, and vaporized / atomized materials. Relevant examples of inorganic coatings include metals, alloys, ceramic materials, oxides, nitrides, and sulfides. Suitable examples of organic coatings include polymeric, oligomeric and small molecules, where the small molecules are individual monomers that react to form a coating. Polymeric materials include, but are not limited to, polycarbonates, acrylates, organosilicon compounds, cellulose esters, polyesters, alkyds, polyurethanes, vinyl polymers and the like. Preferably, many organic materials include organic polymeric materials, such as "architectural" materials derived from organic materials having protective or decorative functionalities, in particular including thermoplastic and thermosetting polymers. Preferably, a variety of inorganic materials include oxides. Further, the plurality of materials 14 can preferably be vaporized or sprayed individually or in combination and directed to the substrate or deposited on the substrate, where the vaporized / atomized material is combined to form a continuous coating if sufficient material is supplied to the substrate. In addition, the material or combination of materials can form a coating having many layers, where the coating can be a multifunctional coating having a total function due to the predetermined functional role of each layer. The materials may 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 into a coating. In addition, by providing data on a variety of material combinations, the interaction and compatibility of various material combinations can be determined.

Coating 20 is a material or a combination of materials deposited on a substrate 18. These materials can remain as separate homogeneous materials or they can react, interact, diffuse, mix or otherwise combine to produce a new homogeneous material, mixture, composite or composition. As indicated above, coating 20 may include one layer or multiple layers. Typically, coating 20 has a transverse dimension, i.e. the length measured along the surface of the substrate is much larger than the thickness, i.e. coating size perpendicular to the surface of the substrate. Preferably, each layer is a thin film layer. Coating 20 may vary in composition, selectively continuous from one predetermined area 22 to another, thereby forming an array of coatings that defines a plurality of predefined coatings 30 of the coating library 28. Each array of coatings differs from each other depending on its location. In addition, each coating array can be processed under the same conditions and analyzed to determine their characteristics with respect to functional or useful properties, and then compared with each other to determine relative utility.

Each of the plurality of predetermined regions 22 is a fixed zone on the substrate 18 to produce one or a combination of a plurality of materials 14 to form a single layer or multilayer coating. Each of the predefined areas 22 can be of any shape sufficient to obtain and analyze a coating deposited on it, for example, rectangular, elongated in a line, arcuate, round, elliptical, their combinations, etc. Each predetermined region 22 typically has an area in the range of about 0.01 mm ² to 100 cm ² , preferably in the range of about 1 mm ² to 1 cm ^2, and more preferably in the range of about 10 mm ² to 50 mm ² . Other areas may be used, and the area of each of the predetermined areas 22 may be determined by the ability of the deposition devices and analytical instruments, as well as the preferred density of the coating library.

Substrate 18 is a rigid or semi-rigid material suitable for applying at least one of a plurality of materials 14 and functioning as a substrate. The substrate 18 has at least one substantially flat surface 16 that includes a plurality of predetermined regions 22. However, this substantially flat surface may have embossed portions to physically separate each of the plurality of predetermined regions 22. The substrate 18 may have any size and shape, but preferably has a disk shape, a plate shape or an elongated shape, for example, the shape of a tape or roll. The substantially flat surface 16 of the substrate 18 corresponding to the feed zone 24 typically has an area in the range of about 1 mm ² to 1 m ² , preferably in the range of about 50 mm ² to 750 cm ^2, and more preferably in the range of about 1 cm ² up to 500 cm ² .

The substrate 18 can be fixed inside the system 10 and is located in the feed zone 24 with the clamping device 37. The clamping device 37 can movably set the substrate 18 to a predetermined position. For example, for an elongated ribbon-shaped substrate 18, the fixture 37 may include a ribbon unwinder and a ribbon receiving device, both of which rotate and support the ribbon, possibly in combination with rollers, in the feed zone 24. In another example, the fixture 37 may represent a plate on which a substrate is placed and fixed, where the plate is connected to an engine or other device such as a drive mechanism, which control the position of the plate relative to the feed zone 24. Essentially, the adjusting device 26 can adjust the movement of the clamping device 37 to control the predetermined areas 22 to which the materials 14 are fed. For example, the adjusting device 26 can move the clamping device 37 so that one predetermined of the plurality of predetermined areas 22 is outside zone 24 feed and therefore does not receive one or more materials 14.

The feed zone 24 is a stationary zone within the system 10. The feed zone 24 may be of any shape or size and typically, but not necessarily substantially in shape and size, to a plurality of predetermined regions 22 on the surface 16 of the substrate 18. However, a plurality of predetermined areas can be significantly larger or significantly smaller than the feed zone 24. The fixed arrangement of the feed zone 24 provides a known, permanent place for the system 10 to feed a plurality of materials 14 to the surface 16 of the substrate 18.

The control device 26 is a computing system having input devices, output devices, memory and a processor for receiving, sending, storing and processing signals and data in order to function, monitor, record and otherwise functionally control the operation of the system 10. The control device 26 includes a computing system having an interface board for combining all system components and a motion controller for controlling the movements of the mask 32 and the substrate 18. The control device 26 may include a key A profile for entering data and commands, a monitor for displaying information and a printer for printing information. The control device 26 may include a software product, hardware, software and other similar components and circuits for operating the system 10. The control device 26 may be a single device or may be a plurality of devices working in conjunction. Preferably, the adjusting device 26 is connected to all other components of the system 10, including the feeding mechanism 12, the plurality of materials 14, the substrate 18, the mask 32, the curing source 34, the testing device 36, the fixing device 35, and the clamping device 37 for coordinating the operation of the system. For example, a control device controls the flow of materials to the substrate, recording the exact combination of materials that covers each predefined area. By controlling the flow, the control device can control the volume of one or more materials, the combination of materials, projection power, coating speed, projection angle, the space between the feed mechanism and the substrate, masking, etc. Further, the control device 26 monitors, synchronizes, combines and records the supply and curing of the supplied materials, testing the coating library and analyzing the test results.

The mask 32 is a material having one or more patterns of open zones and blocked zones, where the open zones make it possible to supply a plurality of materials 14 to the substrate 18, and the blocked zones block the flow. The drawing can be of any shape. A mask 32 is used to determine spatial variations of materials in the coating library 28. For example, in a dual masking system, a mask includes a plurality of patterns that are arranged sequentially to allow feeding to varying half-zones on the substrate 18, as will be described in more detail below. The mask 32 may be located anywhere between the plurality of materials 14 and the substrate 18, including the arrangement directly on top and in contact with the substrate, in the direction of the material supply line. By increasing the space between the mask 32 and the substrate 18, an effect called “shading” occurs, which may be undesirable in some cases. During shading, the image of the material supplied to the substrate is proportional to the pattern of the mask, but more, since the space between the mask and the substrate allows the image to expand until it reaches the substrate. The mask 32 can be obtained from a rigid or semi-rigid material, or the mask can be obtained chemically on the surface of the substrate. Preferably, the mask material ensures that the mask is as flat as possible and resistant to bending and / or bending. Suitable examples of mask materials include silicon, silicon dioxide and glass for hard or relatively flexible materials, plastics, metals and alloys for semi-rigid or relatively flexible materials in the form of sheets, films or foils and lithographic polyacrylate and other chemical materials that form negative and positive chemical masks.

The mask 32 can be fixed in the system 10 and positioned relative to the feed zone 24 by the fixing device 35. The fixing device 35 can move the mask 32 movably. For example, for the mask 32 in the form of an elongated semi-rigid material having many patterns, the fixing device 35 may include an unwinding device the tape and the tape receiving device, both of which rotate and support the tape, possibly in combination with rollers, relative to the feed zone 24. In another example, for the mask 32 in the form of a rigid material, the securing device 35 may be a platform or other supporting structure connected to an engine or other device such as a drive mechanism that controls the position of the platform and mask relative to the feed zone 24. This makes it possible to use a single pattern or a series of patterns to mask various predetermined areas 22 on the substrate 18 by movement of the mask 32. Essentially, the adjusting device 26 can adjust the movement of the fixing device 35 to control the predetermined areas 22 to which the materials 14 are supplied.

The curing source 34 is a device associated with each of the plurality of materials 14 for initiating a reaction or evaporation of a solvent involving one or a combination of materials. For example, the reaction may be a polymerization, a crosslinking reaction, a reaction of small molecules, an inorganic phase reaction, and other similar reactions suitable for the material (s) to be supplied. Suitable examples of the curing source 34 include a heating device associated with the substrate 18, a radiating device associated with the feed materials or 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 a plurality of predetermined coatings 30 on the substrate 18. The testing device 36 exposes the entire coating library to the same conditions to determine the relative effectiveness of each of the predetermined discoveries 30. The testing device 36 is connected with a control device 26 to compile and analyze test data. Suitable examples of testing device 36 include a thickness profiler, surface analyzer, UV absorbance meter, scratch hardness tester, permeability meter, and other similar devices that test the architectural, protective, decorative, and other functional features of the coating.

As shown in FIG. 3, a material supply 38 from a supply mechanism 12 feeds one of a plurality of materials 14 in an evaporated or sprayed state into an envelope surface 40 that preferably spans a supply zone 24 to provide a coating layer over the entire supply zone. Source 12 is the exit point of the material from the feed mechanism. For example, source 12 may be a nozzle on a spray. However, in some cases, it may be desirable not to have a coating layer over the entire supply zone 24. For example, the envelope surface 40 may cover only part of the supply zone 24, when part of the predetermined areas 22 of the substrate 18 should not be covered, and the mask 32 is not used to prevent the supply of material to these areas. Envelope surface 40 may be of any suitable shape, including a conical shape with various cross sections, such as a circle, an ellipse, and a rectangle, a semiconical shape with various cross sections, and a thin line shape. The shape of the envelope surface 40 may be determined by the shape of the feed zone 24, the shape of the surface 16 of the substrate 18, the feed mechanism 12, the desired composition of each of the plurality of predetermined coatings 30, the shape and number of predetermined areas 22, the number of sources 38, the number of materials supplied to the substrate 18 14 and similar factors. The shape of the envelope surface 40 can be controlled by the shape of the nozzle on the feed mechanism 12 with an air casing associated with the feed mechanism, or other shape-defining structures or devices associated with the feed mechanism.

As shown in FIGS. 3, 4, in the perpendicular focused arrangement 41, the source 38 has a focal point 42 for feeding the material 14, which coincides with the center point 44 of the feeding zone 24. The source 38 is positioned so as to guide the material 14 along a feed angle having an axial line 46 substantially perpendicular to the surface of the feed zone 24 at a center point 44. As shown in FIG. 4, the thickness profile 48 is in cross section in one of dimensions 50 (e.g. transverse to the dimension shown in FIG. 3) of the coating feed zone 24 provided in the arrangement shown in FIG. 3, wherein the feed angle α is substantially perpendicular to the plane 49 of the feed zone, typically has a two-dimensional substantially normal distribution or Gaussian distribution but. Therefore, the thickness profile 48 has an upper point 52 coinciding with the center line 46 above the center point 44 with two equal, mirror-reflected tails 54 on each side of the center line. In addition, the source 38 is located at a distance of 60 vertically relative to the plane 49 of the supply zone 24 (figure 3). The vertical distance 60 affects the total width 51 of the thickness profile 48 and thereby the coating thickness at any given point along the distribution of the thickness profile. Thus, in this case, the thickness profile 48 is centered within the size 50 of the feed zone 24, the thickness being maximum at the top point 52 and gradually decreasing in all directions from the center line 46.

As shown in FIG. 5, in the focused arrangement at an angle of 55, the source 38 has a focal point 42 for supplying material 14, which coincides with the center point 44 of the supply area 24, however, the source is positioned so that the material center line 46 is at an angle of supply α, approximately equal to between 0 degrees and 90 degrees relative to the plane 49 of the feed zone. Further, due to the inclined but focused feed, the source 38 is placed at a horizontal distance 53 from the center point 44. The horizontal distance 53 is the distance in the plane of the source 38 parallel to the plane 49 of the feed zone and offset from the position perpendicular to the focused layout. The horizontal distance 53, the vertical distance 60, and the feed angle α are mathematically interconnected and can vary to accommodate the thickness profile 48 within the feed zone 24. In this embodiment, in practice, the thickness profile 48 has a distorted Gaussian distribution with an inclined tail 56 closer to the source 38 and elongated end section 58, stretching from the source. Inside the elongated tail 58, there is typically a region where the thickness profile 48 substantially linearly changes in length along the size 50. Thus, in this case, the thickness profile 48 is distorted within the size 50 of the feed zone 24, the thickness being the largest towards the end portion of the size having an inclined tail 56, and decreases in thickness from the top point 52 towards the edge of the size corresponding to the extended tail 58.

As shown in FIG. 6, in the perpendicular arrangement out of focus 57, the source 38 has a focal point 42 for feeding material 14 located at a distance 59 of the offset from the center point 44 in the plane of the supply zone 24 along the size 50. In this case, the center line 46 is below the feed angle α is substantially perpendicular to the plane 49 of the feed zone 24, the offset distance 59 is substantially equal to the horizontal distance of the source 38 from the position of the perpendicular focus arrangement (FIG. 4). In addition, it is noted that the focal point for the feed mechanism may be located inside the feed zone or outside the feed zone. Thus, in this case, the thickness profile 48 is offset within the size 50 of the feed zone 24, the thickness being greatest in the offset position of the upper point 52 and gradually decreasing in all directions from the center line 46.

As shown in FIG. 7, in the arrangement at an angle out of focus 61, the source 38 has a focal point 42 for supplying material 14, located at an offset distance 59 along a size 50 from the center point 44, the center line 46 is at an supply angle α of approximately 0 degrees to 90 degrees relative to the plane 49 of zone 24 of the feed. In this case, due to the feed angle α and outside the focal point of the focal point 42, the horizontal distance 53 of the source 38 from the perpendicularly focused feed point is greater than the distance 59 of the shift of the focal point to the center point 44. Thus, in this case, the thickness profile 48 is even more distorted inside the size 50 of the feed zone 24, than with the arrangement shown in Fig.5.

In each of the arrangements of FIGS. 4-7, the flatness of the thickness profile 48 inside the feed zone 24 will vary depending on the vertical distance 60 between the source 38, and the flatness will increase with increasing distance. Further, the flatness of the thickness profile 48 will vary within the feed zone 24 depending on the feed angle α, the horizontal distance 53 and the offset distance 59, with a smaller angle, a larger horizontal distance and the offset distance will increase the flatness. For example, as shown in FIG. 4, the thickness profile 48 can be substantially flat in size 50 of the feed zone 24 with the appropriate combination with the feed angle, horizontal distance, and offset distance. However, at a closer distance, the thickness profile 48 in size 50 of the feed zone 24 will gradually change from the largest thickness at the upper point 52 to the smallest thickness at the edges of the feed zone size. A coating library having a substantially constant thickness is preferably desired so that a change in thickness can be excluded from the analysis of the plurality of predetermined coatings 30 associated with each predetermined area 22 in order to focus the study on the effect of the coating composition. In use, a coating library with a substantially constant thickness is achieved by calibrating each feed mechanism so that a linear thickness profile is distributed through the feed zone. When multiple feed mechanisms are used, preferably the same portion of the thickness profile is located within the feed zone for each feed mechanism. Therefore, the present invention makes it possible to produce coating libraries having virtually indeterminate variations in the compositions, layers, and thicknesses of coating materials within a plurality of predetermined regions 30 of the substrate 18 by changing the vertical distance 60, the feed angle α, and the offset distance 59 for each source 38 of each of the plurality materials 14.

As shown in FIGS. 8, 9, in one embodiment of the combinatorial coating system 62, a continuously changing coating library 64 on the substrate 18 is obtained by simultaneously depositing at least two materials A and B from a plurality of materials 14 from sources 38. The relative thickness and the composition of each of the many predetermined coatings 30 can be individually or jointly continuously changed in the form of a thickness profile 48 (FIGS. 4-7) of each of materials A and B, as they are fed to the substrate 18. This continuous change could b linear or non-linear, depending on variables such as feed angle α, design capacity of feed mechanism 12 (not shown) associated with each source 38, coating rate or amount of material deposited per unit time, feed rate and material concentration entering the feed mechanism, the vertical distance 60, the distance 59 of the source 38 displacement relative to the central point 44, the horizontal distance 53 from each source 38 to the central point 44, the shape of the envelope surface 40 (not proved), the atmosphere, the energy to the area, pressure, gas composition during vapor deposition, and other similar factors. Each of these variable parameters may be individually or in combination to give a predetermined coverage in each of the predetermined areas 30. Further, although not shown, a mask 32 may be located between each of the sources 38 and the substrate 18, preferably adjacent to or in contact with the substrate to facilitate the production of a library of coatings.

In addition, as shown in FIG. 8, the feed angle α can have a value in the range of about 0 ° to 90 °, more preferably about 15 ° to 75 °, and most preferably, about 30 ° to 60 °. The vertical distance 60 can vary from about 0 cm to 90 cm, more preferably from about 3 cm to 30 cm, and most preferably from about 10 cm to 20 cm. The horizontal distance 53 can vary from about 0 cm to 60 cm, more preferably from about 3 cm to 30 cm, and most preferably from about 10 cm to 20 cm. The coating thickness may vary from about 1 nanometer to 1 millimeter, more preferably from about 1 micrometer (or micron) to about 500 microns, and most preferably from about 5 microns to approx RNO 100 microns.

As shown in FIG. 9, one embodiment of the practice of the coating library 64 obtained by the combinatorial coating system 62 (FIG. 8) includes counter gradients of materials A and B continuously varying from about 100% to 0% of material A, and about from 0% to 100% of material B, moving in the transverse direction through the library of coatings from the side adjacent to the source 38 of material A. Depending on the parameters discussed above regarding the supply of materials to the substrate, the library 64 of coatings can have essentially a constant hydrochloric or variable thickness across the substrate width. Preferably, the sources of materials A and B have corresponding focal points 42 having a predetermined offset distance 53 from the center point 44 of the feed zone so that the thickness of the coating library is substantially constant across the width of the substrate. In addition, by providing sufficient time for diffusion of materials A and B by controlling the evaporation rate, it is possible to obtain new material in place by diffusion or by mixing or reacting A and B. Alternatively, the substrate 18 shown in FIG. 18 can be movable, for example, rotate, move longitudinally and the transverse direction to obtain many variations in the composition of each of the predefined coatings 30. In addition, the sources 38 can sequentially submit new and different materials, which in combination with the driving The transverse direction of the elongated substrate results in a continuously changing coating along the longitudinal direction of the substrate. Moreover, each source 38 is preferably located within the supply plane 65, i.e. essentially parallel, but placed at a distance of 60 vertically from the plane 49 of the feed zone. However, in an alternative embodiment, in practice, the vertical distance 60 to each source 38 may be independently varied to provide a different thickness profile 48 within the feed zone 24. Thus, system 62 allows for the simultaneous supply of at least two of a plurality of materials to a substrate in order to obtain a continuously changing coating having gradients of at least two materials.

As shown in FIGS. 10-11, in another embodiment, similar to that shown in FIGS. 8-9, the triple combinatorial coating system 68 offers a continuous three-component coating library 70. At least three materials A, B and C from the plurality of materials 14 (FIG. 1) can be simultaneously or sequentially supplied from sources 38. Each of the sources 38 is located in the off-focus arrangement 61 at substantially equal angles (FIG. 7), as described above. Preferably, the sources 38 are arranged at equal intervals in a circle 74 with a center 76 on the same axis 78 as the center point 44. Preferably, the circle 74 has a larger diameter than the diameter of the feed zone. For example, the circle 74 preferably has a diameter of about 30 cm while the feed zone has a diameter in the range of about 10 cm to 15 cm. The coating library 70 obtained by system 68 may be a continuously changing combination of each of the three materials A , B and C, simulating a three-phase diagram. The same variables described above affecting the formation of the coating library 64 (Figs. 8-9) are similarly applied to the coating library 70 of system 68. For example, the relative composition of the coating library 70 at any point is a function of horizontal distance 53, distance 59 bias, feed angle α, shape of the envelope surface 40 of each spray material, focal point 42 of each source, etc. Moreover, preferred distances and angles are the same as those described above with reference to FIGS. 8-9. In one working example, three paint sprays are simultaneously focused to deliver a fine aerosol of three different materials to the substrate using the layout at an angle out of focus 61 (FIG. 7). All nebulizers are located in the feed plane parallel to the feed zone and with a vertical spacing of approximately 15 cm from the feed zone. Further, each nozzle is positioned to have a feed angle α of about 45 ° and a horizontal distance 53 of about 18 cm. The substrate 18 is a substantially circular silicon wafer having a diameter of about 8 cm. Each of the plurality of advance certain areas are sized to obtain a coating library having sixty-six predefined coatings. The coating material comprises 2% polyethyl methacrylate in an isopropanol solvent mixed with organic pigment. After deposition through a triple or triangular mask (not shown) and thermal curing in a few minutes, a three-component coating library is obtained having sixty-six different compositions. The coating thickness is about 2 microns, and the coating thickness varies linearly with the coating time.

As shown in FIGS. 12-14, in another embodiment, the combinatorial coating system 72 includes a plurality of jointly focused or simultaneously focused feeding mechanisms 12, each of which is stationary to simultaneously or sequentially feed one of the plurality of materials 14 to the substrate 18 through a mask 32. Each of the plurality of supply mechanisms 12 creates a mist of atomized material within the envelope surface 40 (FIG. 3), which contacts the surface 16 of the substrate 18. Preferably, each source nickname 38 is located in the layout at an angle out of focus 61 (Fig.7). Preferably, each feed mechanism 12 is arranged at equal intervals in a circle 74 with a center 76 on the same axis 78 as the center point 44. Further, each feed mechanism 12 preferably has a horizontal spacing 53 in the radial direction from the center 76, and this distance is less than the distance from the center point 44 to the edge of the feed zone 24. Preferably, the focal point 42 (not shown) of each feed mechanism 12 is focused at a substantially equal offset distance 59 (FIG. 7) from the center point 44, whereby having the same portion of the thickness profile 48 (FIG. 7) for each material zone 24 feed. However, it is not required that the focal point 42 for each feed mechanism 12 be offset from the center point 44 or have equal offset distances 53. In fact, each feed mechanism 12 can have a single focal point 42, including a point that leads to an axial line 46 (FIG. 3) that is perpendicular or tilted relative to surface 16 while the feed mechanism is in line with the center point 44 or radially offset from the central point 44 until the envelope of the surface 40 (FIG. 3) of the feed material 14 is aligned with at least part of the feed zone 24 and therefore with the surface 16 of the substrate 18. Moreover, no need gence positioning feeder 12 circumferentially, it may simply be in any relative position that allows parallel or simultaneously apply a plurality of materials 14 to at least a portion of the feed zone 24.

The mask 32 preferably includes a plurality of patterns 80 (FIG. 13) that can be moved to and from the material supply line 14 to control the coverage of various predetermined areas 22 (FIG. 2) with different materials to produce a library 82 of coatings (FIG. 13) . Although it is shown in FIG. 12 located far from the substrate 18, preferably the mask is in physical contact, i.e. touches or is close to the substrate to prevent shading. For example, referring to FIG. 14, system 72 may provide a coating library 82 having sixteen predetermined coatings 30 using four (A, B, C, and D) of a plurality of materials 14 in combination with the first four patterns 80 of mask 32 (FIG. 13).

In the working version of the system 72, each supply mechanism 12 is a nozzle nozzle that sprays the liquid source material 14 into the finely divided atomized material and directs it individually or in combination with other nozzles / materials to the substrate 18 to create a coating layer. To create a fine mist of liquid material, the liquid material can be affected by compressed air, superheated steam or ultrasonic waves. A coating library 82 having a multilayer coating can be created by specifying a feed sequence 14 from a plurality of nozzles 12 in combination with a sequence of masking patterns and curing steps (if necessary) to provide a predetermined coating 30 in a predetermined area 22 (FIG. 2) the substrate. This may be desirable, for example, when searching for coatings having multifunctional properties, where each layer or combination of coating layers gives at least one of the functional properties. In this particular example, which should not be construed as limiting, eight different liquid coatings A, B, C, D, I, F, G, H are fed to eight individually controlled sprayers. For example, suitable liquid coating materials include polyacrylates, polycarbonates, vinyl polymers, organosilicon compounds, and silica gel. Further suitable sprayers include, for example, sprayers manufactured by SonoTech (Sonotech). If the materials require curing, then suitable examples of the curing source 34 (FIG. 1) include a heating plate and an ultraviolet lamp capable of curing materials at temperatures from about 80 ° C to 200 ° C and more preferably from about 100 ° C to 150 ° C for periods of time from about 10 minutes to 10 hours, and more preferably from about 1 hour to 4 hours. Thus, a coating library having a plurality of predetermined multi-layer coatings is made in parallel by combining various masking patterns with various liquid source materials or by maskless “continuous phase application” of materials, taking advantage of changes in the placement and volume of liquid source material supplied from each nozzle nozzles to obtain a library of coatings.

As shown in FIG. 15, in another embodiment, in practice, the vapor deposition combinatorial system 90 includes a plurality of feeding mechanisms 12, each of which is jointly focused or simultaneously focused, for simultaneously or sequentially supplying one of the plurality of solid materials 14 to the substrate 18 located on the movable platform 92 inside the housing 94 for deposition. To withstand high temperature during vapor deposition, the substrate includes a high temperature resistant material such as magnesium oxide or lanthanum aluminate (LaAlO ₃ ). The deposition case 94 is sealed to provide a vacuum chamber 96 inside its inner surface. In this case, the feed mechanisms 12 are vapor deposition devices, such as spray guns driven by radio frequency energy, preferably matched for optimal output. The platform 92 supports the substrate 18 in a known position, where the platform can be adjusted by vertical, rotational or linear movement to position the substrate within the feed zone. Between the feeding mechanisms 12 and the substrate 18, there is a mask having an array of different patterns 80. Preferably, the mask 32 is substantially in contact with the substrate 18 during vapor deposition to minimize the “shading effect”. The mask 32 is movably located inside the vacuum chamber 98 of the mask body 100. The mask body 100 is connected to the main body 94 in such a way as to maintain an atmosphere in both vacuum chambers 96, 98. In addition, the mask body 100 includes a gearbox 102 and a micrometer 104 for moving and monitoring the position of the mask patterns 80 relative to the substrate 18, respectively.

In addition, system 90 may optionally include a shutter 106 having one or more openings 108 to select one or more materials for simultaneous or sequential feeding and to prevent mixing of materials. The shutter 106 is movably connected to the rotor 110, which rotates the shutter and the hole 108 to select solid material 14 for evaporation, while the mask pattern 80 is changed in a vacuum by linear movement by vacuum. The amount of deposited materials 14 is controlled by a thickness control device 112, such as a quartz resonator. Evaporation of various solid starting materials from the vapor phase through various mask patterns in one day can produce a substrate with more than 100 different coating compositions / layer compositions without having to break the vacuum to replace solid materials and / or mask patterns.

The vacuum atmosphere in the vacuum chambers 96 and 98 is supported by a fore-vacuum apparatus 114 connected to a turbomolecular pump 116. For example, a fore-vacuum apparatus 114 can create a vacuum of about 10 ^-3 torr, while a turbomolecular pump 116 can create a vacuum of about 10 ^{- 6} torr. Pumps 114 and 116 are connected to a vacuum chamber 96 via a vacuum shutter 118.

This system 90 can create coating libraries from any ceramic, metal, and / or semiconductor materials with surface roughness and precision in thickness, measured in nanometers. In addition to the spray devices described above, other suitable delivery mechanisms 12 include laser ablation, electron beam evaporation, chemical vapor deposition, etc., which can be used with masking systems to create libraries of inorganic coatings. To produce a library of organic coatings, a thermal evaporation device with a plurality of co-focused sources connected to a masking system can be installed. The same system can be used to make a library of small molecules, for example, to use organic LEDs in devices.

It is clear that the present invention provides a combinatorial system and coating method. While the invention has been specifically shown and described in combination with its preferred embodiments, it will be appreciated that changes and modifications may be made by one skilled in the art without departing from the scope of the invention. In addition, you must understand that the principles described here for the location of the mechanisms of supply and supply of materials for the formation of profiles of the thickness of the coatings are used in a similar way, where applicable, in all embodiments in practice.

Claims (23)

1. A system for manufacturing an array of coated materials, comprising a substrate having a surface with a plurality of predetermined areas, a plurality of materials for coating the substrate, a feed mechanism associated with the plurality of materials and adapted to simultaneously feed each material to the surface of the substrate, and a control device controlling a feeding mechanism for selectively feeding each material so that each predetermined region of the substrate has a predetermined coating. 2. The system according to claim 1, in which the feed mechanism further includes a plurality of sources, each of which is designed to supply one material and has a different fixed location inside the system. 3. The system of claim 1, wherein the predetermined coating associated with the at least one region includes a thin film coating having a plurality of layers. 4. The system according to claim 1, which further includes a mask having a plurality of patterns and located adjacent to the surface of the substrate, wherein each pattern is located on top of the substrate and is unique to provide materials to various combinations of a plurality of predetermined regions of the substrate. 5. The system according to claim 1, in which each material is selected from the group consisting of metals, alloys, ceramic materials, oxides, nitrides and sulfides. 6. The system according to claim 1, in which each material is selected from the group consisting of polymeric materials, oligomeric materials, small molecules, thermoplastic polymers and thermosetting polymers. 7. The system according to claim 1, in which the feed mechanism further includes a vapor deposition device. 8. The system according to claim 7, in which the feed mechanism further includes a shutter having a plurality of positions corresponding to each material, and the adjusting device is adapted to control the position of the shutter to selectively expose the substrate surface to at least one material. 9. The system of claim 1, wherein the supply mechanism further includes a plurality of spraying devices corresponding to a plurality of materials, each of which is a vaporizable respective single spraying device. 10. The system according to claim 1, which further includes a mask having many masking patterns, and a movable fixing device associated with the adjusting device and having a holder for fixing the mask, while the adjusting device is adapted to control the movement of the fixing device to the position of one masking pattern over the substrate in combination with the supply of at least one material to the substrate. 11. The system according to claim 1, which further includes a movable clamping device associated with the regulating device and having a clamp to support the substrate, while the regulating device is able to control the speed of movement of the supporting device to locate at least a portion of the substrate inside the feed zone for implementation supply of at least one material. 12. The system according to claim 11, in which the fixing device is capable of moving essentially at a constant speed. 13. A system for manufacturing an array of coated materials, comprising a feed zone fixedly located within the system, a substrate having a surface with a plurality of predetermined areas and located inside the feed zone, a plurality of coating materials on the substrate, a feed mechanism associated with the plurality of materials and adapted to simultaneously feed each material from various fixed positions to the feed zone, and a control device controlling the feed mechanism for selective feeding, at least one material in the feed zone so that each predetermined region of the substrate has a predetermined coating of at least one material. 14. The system of claim 13, wherein the predetermined coating associated with the at least one region includes a thin film coating having a plurality of layers. 15. The system of claim 13, which further includes a mask having a plurality of patterns and located adjacent to the feed region between the plurality of materials and the surface of the substrate, and each pattern is located within the feed zone and is unique to allow materials to be supplied to various combinations of the plurality of predetermined regions the substrate. 16. The system according to item 13, in which each material is selected from the group consisting of metals, alloys, ceramic materials, oxides, nitrides and sulfides. 17. The system according to clause 16, in which the feed mechanism further includes a vapor deposition device. 18. The system of claim 17, wherein the feed mechanism further includes a shutter having a plurality of positions corresponding to each material, wherein the control device is able to control the location of the shutter for selective exposure by at least one material in the feed zone. 19. The system of claim 13, wherein each material is selected from the group consisting of polymeric materials, oligomeric materials, small molecules, thermoplastic polymers and thermosetting polymers. 20. The system of claim 19, wherein the supply mechanism further includes a plurality of spraying devices corresponding to a plurality of materials, each of which is vaporized by one respective spraying device. 21. The system according to item 13, which further includes a movable securing device associated with the adjusting device and having a holder for securing the mask, while the adjusting device is able to control the movement of the fixing device to the position of one pattern above the feed zone in combination with the supply of at least , one material per feed zone. 22. The system according to item 21, which further includes a movable clamping device associated with the regulating device and having a clamp for supporting the substrate, while the regulating device is able to control the speed of movement of the supporting device for locating at least part of the substrate inside the feed zone in combination with the supply of at least one material in the feed zone. 23. The system of claim 22, wherein the securing device is capable of moving at substantially constant speed.

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