Method for replicating microstructure pattern

Abstract

To solve a problem in which, after microstructure replication, a thin film etching process becomes difficult to control.SOLUTION: A method includes the steps of preparing a first multilayer structure including a substrate, a thin film, and a first photoresist layer, preparing a second multilayer structure including a mold having a microstructure pattern and a second photoresist layer, combining the first multilayer structure and the second multilayer structure such that the first photoresist layer contacts the second photoresist layer, and applying pressure and temperature. Articles including the microstructure pattern are also disclosed.SELECTED DRAWING: Figure 1A

Description

[Technical Field]

[0001] [Related Applications] This application is based on priority from U.S. Patent Application No. 17 / 338,144, filed June 3, 2021. No. 60 / 699,999, filed on Dec. 1, 2003, the entire disclosure of which is incorporated herein by reference.

[0002] The present disclosure generally relates to a first multi-layer structure including a substrate, a thin film, and a first photoresist layer. and preparing a mold having a microstructure pattern and a second photoresist. providing a second multilayer structure including a photoresist layer, and the first photoresist layer is a first multilayer structure and a second multilayer structure are combined so as to contact the resist layer; and applying pressure and temperature. Also disclosed is an article including a turn. [Background technology]

[0003] The polymer-on-glass replication or stamping process is a When an etching process is followed, it can be used to create a user structure. , the zero-based portion of the polymer layer or a negligible thickness (e.g., a few hundred nanometers) It is desirable to have a base portion of the substrate (the substrate itself). In this case, the etching process window is centered around the microstructure depressions / protrusions in the polymer layer. It is difficult to control the base of the polymer layer after replication, and subsequent This makes it difficult to control the etching process of thin films such as high refractive index materials. [Brief explanation of the drawings]

[0004] Features of the present disclosure are illustrated by way of example, and not by way of limitation, in the following figures: Like numbers refer to like elements, i.e. [Figure 1A] 1A and 1B are a first multilayer structure and a second multilayer structure according to one embodiment of the present invention. [Figure 1B] 1A-1C illustrate steps of combining a first multi-layer structure and a second multi-layer structure according to one embodiment of the present invention. [Figure 1C] 10A-10C illustrate the step of removing the mold from the combined first and second multilayer structures. [Figure 1D] FIG. 10 illustrates the steps of irradiating the combined photoresist stack with a flood exposure from a collimated light source and developing the photoresist stack to expose a surface portion of the thin film. [Figure 1E] FIG. [Figure 2A] FIG. [Figure 2B] 2B shows a step of applying a third photoresist layer onto the mold of FIG. 2A. FIG. [Figure 2C] FIG. 10 illustrates the step of applying a fourth photoresist layer. [Figure 2D] FIG. 1B shows the first multilayer structure of FIG. 1A. [Figure 3A] 1A-1C illustrate steps for disposing a thin film on a substrate. [Figure 3B] 1B illustrates the step of applying a photoresist layer onto the thin film to form the second multi-layer structure of FIG. 1A. Summary of the Invention

[0005] In one aspect, a method for replicating a microstructured pattern is disclosed, the method comprising: providing a multilayer structure including a micropattern and a positive tone photoresist; providing a thermally conductive mold having a structured pattern; and applying a conductive mold to the multilayer structure, wherein the fine grains of the thermally conductive mold are The structural pattern is replicated on a multilayer positive photoresist.

[0006] In another aspect, an article is disclosed that includes a substrate and a thin film having a microstructured pattern.

[0007] Additional features and advantages of various embodiments are set forth in part in the description that follows and in part in the accompanying drawings. In particular, these features will be apparent from the description or may be learned by practice of various embodiments. Objectives and other advantages of various embodiments will become apparent from the following detailed description of the present invention, which is set forth in the accompanying drawings, in which: It is realized and achieved through combination. DETAILED DESCRIPTION OF THE INVENTION

[0008] For purposes of simplicity and illustration, the present disclosure will be described primarily with reference to examples thereof. In the description, numerous specific details are set forth in order to provide a thorough understanding of the present disclosure. However, it is understood that the present disclosure may be practiced without limitation to these specific details. In other instances, some of the above may be omitted in order to avoid unnecessarily obscuring the present disclosure. The methods and structures are not described in detail.

[0009] Additionally, the elements depicted in the accompanying figures may include additional components, and these Some components depicted in the figures may be removed or remodeled without departing from the scope of the present disclosure. Additionally, elements depicted in the figures may be drawn to scale. Therefore, elements may be sized and dimensioned differently than shown in the figures. and / or may have a configuration.

[0010] Both the foregoing general description and the following detailed description are exemplary and explanatory only. It should be understood that the present invention is intended to provide a description of various embodiments of the present teachings. In a wide variety of embodiments, disclosed herein are articles, as well as methods for manufacturing articles. Methods of manufacture and use.

[0011] The present disclosure provides a first multilayer structure including a substrate 14, a thin film 12, and a first photoresist layer 10a. Preparing a layer structure 16 and a mold having a microstructure pattern 20a 18, and the step of preparing a second multi-layer structure 17 including a second photoresist layer 10b. and the first photoresist layer 10a is placed in contact with the second photoresist layer 10b. , combining the first multilayer structure 16 and the second multilayer structure 17, and applying pressure and and applying a temperature.

[0012] The second microstructure layer 17 has a microstructure pattern 20a and a second photoresist layer 10. The mold 18 may include a mold 18 having a microstructure pattern 20a. The material can be made of a material that can provide protection and retention. Non-limiting examples of materials include: Examples include metals, semiconductors, nickel, silicon, dielectrics such as fused silica, glass, quartz, and combinations thereof. In one embodiment, the mold 18 is made of a conductive material. Alternatively, the mold 18 may be made of a thermally conductive material. do.

[0013] The microstructure pattern 20a can be a random or periodic pattern. In an embodiment, the microstructure pattern 20a may be a binary pattern. In another embodiment, the microstructure pattern 20a is a grayscale non-binary pattern. The microstructure pattern 20a can have various shapes, forms, images, etc. The microstructure pattern 20a may include dimples, protrusions, and combinations thereof. For example, as shown in FIG. 1A, The structural pattern 20a is a triangular depression that is uniformly separated from each other by a flat portion. It includes separate parts of.

[0014] In one embodiment, the mold 18 is applied as a coating onto the microstructured pattern 20a. The release agent may include a low surface energy fluoropolymer. The release agent may be a hydrophobic self-assembled monolayer such as a polymer or a hydrophobic silane. is an optional step of depositing a release agent into the recesses / protrusions etc. of the microstructure pattern 20a. The mold can be applied by a deposition process such as: These include spin coating, dip coating, chemical vapor deposition, sputtering or thermal evaporation. and buffing the surface of the microstructure pattern 20a with a release agent. Examples include physical application of

[0015] The second photoresist layer 10b of the second multilayer structure 17 has a replicated microstructure pattern. 20b, and the base portion 22 of the second photoresist layer 10b is replicated. The replicated microstructure pattern 20b does not have the mold microstructure pattern 20b. The microstructure pattern 20a of the microstructure pattern 18 may be an inverse pattern. The microstructure pattern 20a includes three distinct portions of triangular depressions, while the microstructure pattern 2 0b includes three distinct portions of triangular shaped protrusions. The mold layer 10b is adjacent to (shares a common boundary with) and overlies the mold 18, and and / or can be nested with mold 18.

[0016] The first photoresist layer 10a and the second photoresist layer 10b are made of the same material. In one embodiment, the first photoresist The photoresist layer 10a and the second photoresist layer 10b can be made of the same material, They may have different viscosities before being applied as layers.

[0017] The first multilayer structure 16 comprises a substrate 14, a thin film 12, and a first photoresist layer 10a. The thin film 12 can include any of a single layer of material, and / or a multi-layer stack. In one embodiment, the thin film 12 is a high refractive index material thin film, i.e., a refractive index of about 2 to about 4. The thin film 12 may be made of a material having a refractive index. , a gradient or continuous change in refractive index, or a periodic refractive index profile in the material The thin film 12 can be about 1 micron to about 20 microns, for example, about 1 micron to about 20 microns. For example, the thickness may range from about 15 microns to about 10 microns. The thin film can be deposited on the surface of the substrate 14 and / or on the first photoresist layer 10. It can be present on the surface of a.

[0018] In another embodiment, the thin film 12 can be a multi-layer stack. The material may include one or more layers of magnetic material, dielectric material, and absorbing material.

[0019] Substrate 14 can be any material capable of accepting multiple layers. In embodiments, the substrate 14 can be a transparent material. Non-limiting examples of suitable substrate materials include: Polycarbonate, polymethyl methacrylate, polyethylene terephthalate, Glass and polymers such as polyethylene, amorphous polyester, and polyvinyl chloride Liquid silicone rubber, cyclic olefin copolymer, ionomer resin, transparent polypropylene ethylene, fluorinated ethylene propylene, styrene methyl methacrylate, styrene acrylonitrile Nitrile resin, polystyrene, and methyl methacrylate-acrylonitrile-butadiene The substrate 14 has a thickness of about 50 microns to about 2000 microns. For example, about 100 microns to about 1500 microns, and as a further example, about 150 microns It can be present in a thickness range of up to about 1000 microns.

[0020] As shown in FIGS. 1A and 1B, the first multilayer structure 16 and the second multilayer structure 17 are The first multi-layer structure 16 can be combined with the second multi-layer structure 17 so that they are in contact with each other. In one embodiment, the outer surface of the second photoresist layer 10b of the second multi-layer structure 17 is adjacent to the outer surface of the first photoresist layer 10a of the multi-layer structure 16 and / or The multi-layer structure 16 may be formed on the outer surface of the first photoresist layer 10a.

[0021] The method involves applying pressure and temperature to a first multi-layer structure 16 while in contact with a second multi-layer structure 17. The pressure may be about 1 PSI to about 20 PSI, for example about In the range of 1 PSI to about 15 PSI, and as a further example, in the range of about 3 PSI to about 10 PSI The temperature can be in the range of about 60°C to about 90°C, for example, about 65°C to about 85°C. The contact time can range from about 1 minute to about 60 minutes, for example about 2 minutes. For example, the time may range from about 5 minutes to about 55 minutes, and as a further example, from about 5 minutes to about 50 minutes. do.

[0022] As shown in FIG. 1C, the method can include removing the mold 18. The first photoresist layer 10a and the second photoresist layer 10b are bonded together to form a layer, e.g. For example, there should be no air pockets or bubbles between the first multi-layer structure 16 and the second multi-layer structure 17. A thin photoresist stack 10c can be formed. c has a replicated microstructure pattern 20b and a replicated microstructure pattern 20b The second photoresist layer 10b may include a base portion 22 of the (old) second photoresist layer 10b.

[0023] As shown in FIG. 1D, the method applies a coating of a photoresist to the combined photoresist stack 10c. The step of providing a flood exposure using a collimated light source 24 may include providing a Light 24 is incident on the replicated microstructure pattern 20b and the replicated microstructure pattern 20b. The base portion 22 of the photoresist stack 10c is exposed to light without the collimated light source. 24 is a photomask aligner lamp, a dedicated i-line UV exposure tool, or UV-LE D / It can be a light source that emits collimated light, such as a laser setup. In an embodiment, the collimated light source is a lens or mirror that receives diffuse light and emits collimated light. The light source can be a light source that emits collimated light, such as a laser. The surface portion 26 of the thin film 12 is located several hundred nanometers below the replicated microstructure pattern 20b. The photoresist is then placed on the surface of the photoresist so that it can be fully exposed or present from the surface to a few microns. Subsequent development of the base portion 22 of the resist stack 10c to completion or near completion. In one aspect, after the irradiation with collimated light, a subsequent development step can be performed. Through the process, the structure is formed by bonding the substrate 14, the thin film 12, and the thin film 12 adjacent to or on the surface thereof. In one embodiment, the photoresist stack 10 includes a microstructure pattern 20b replicated in the photoresist stack 10. As shown in FIG. 1E, the method also includes the step of forming a photoresist film on the substrate 20. Etching the stack 10c and the thin film 12 removes the thin film from the photoresist stack 10c. 12 includes a step of forming an etching microstructure pattern 20b. After etching, The film 12 has a portion with a replicated microstructure pattern 20c and / or a portion of the thin film 12. This includes the portion with the original thickness, and the portion without the thin film 12, i.e., the thin film 12 is not present. The etching step separates the photoresist material from the underlying thin film 12. The etching can be performed using any technique that simultaneously etches the Non-limiting examples of techniques include reactive ion etching (RIE), inductively coupled plasma-reactive reactive ion etching (ICP-RIE), and ion milling.

[0024] The etched microstructure pattern 20c in the thin film 12 is a microstructure pattern of the mold 18. It may have an inverse pattern to the turn 20a and may have the same aspect ratio. , or may not have. Replicated microstructure pattern 2 in photoresist stack 10c 0b may have an inverse pattern to the microstructure pattern 20a of the mold 18, substantially The etched microstructure pattern 20c in the thin film 12 may be the same as the photoresist pattern 20c. It may have the same properties as the replicated microstructure pattern 20b of the resist stack 10c. , and may or may not have the same aspect ratio.

[0025] The method also includes creating a second multi-layer structure 17. As discussed herein 2A, the mold 18 has a microstructure pattern 2 on the surface of the mold, for example, as shown in FIG. A release coating (not shown) is applied to the surface of the mold 18, including the Oa. The applied release coating may include a release agent. Release agents are disclosed herein. The coating is treated with ultraviolet light, ozone or mil to make the surface of the release coating hydrophilic. This can be done by applying a process such as oxygen plasma to the photoresist on the mold. This may be done to facilitate application of layer 10d.

[0026] As shown in FIG. 2B, the method further comprises depositing a third photoresist layer 10d on the release coating. The third photoresist layer 10d can be formed on the mold 1. 8 and / or release coating surface to achieve a coverage of approximately 50% to approximately 100%. The third photoresist layer 10 can be applied to a thickness sufficient to cover the d is about 1 micron to about 20 microns, for example, about 1 micron to about 15 microns, and For example, the coating thickness can be in the range of about 2 microns to about 10 microns. The photoresist layer 10d can be applied by a deposition process. Non-limiting examples of processes include spin coating processes, spray coating processes, and desoldering processes. Examples of suitable processes include a dip coating process.

[0027] In particular, the third photoresist layer 10d covers all recesses / The protrusions can be applied to the third photoresist layer 10d. The photoresist layer 10d includes a surface that conforms to the microstructure pattern 20a of the mold. and a fourth photoresist layer 10e. can include a side surface that is planar.

[0028] After application, the third photoresist layer 10d is heated at a temperature in the range of about 50°C to about 90°C for about 1 It can be heated / baked for a time ranging from 2 seconds to about 30 minutes. This can be done in a furnace or oven. In one embodiment, the third photoresist layer 10d The resulting solution can be spin-coated and baked on a hotplate at 75°C for approximately 2 minutes.

[0029] After heating / baking the third photoresist layer 10d, a fourth photoresist layer 10e is formed as shown in FIG. 2C. A photoresist layer 10e can be applied onto the surface of the third photoresist layer 10d. The third photoresist layer 10d and the fourth photoresist layer 10e may be made of the same material or The fourth photoresist layer 10e provides a flat outer surface. The fourth photoresist layer 10e can be applied to a thickness of about 1 micron to about 20 microns, for example, about 1 micron to about 15 microns, and as a further example, about 2 microns to The fourth photoresist layer 10e can be applied to a thickness in the range of about 10 microns. , can be applied by a vapor deposition process. Non-limiting examples of vapor deposition processes include: These include spin coating, spray coating, and dip coating processes. A fourth photoresist layer 10e is then spin-coated and heated on a hot plate. A bake at 75° C. for approximately 2 minutes can be performed to form the photoresist stack 10b. The photoresist intermediate layers (10d and 10e) were baked for 30 seconds to 5 minutes and 10 seconds, respectively. and any combination of heating / baking time and temperature in the range 60°C to 95°C. This can be done.

[0030] After application of the fourth photoresist layer 10e, the structure (with optional release coating) is The mold 18, the third photoresist layer 10d, and the fourth photoresist layer 10e are (including) is heated at a temperature in the range of about 50°C to about 90°C for a time in the range of about 1 second to about 30 minutes. Heating / baking can be done on a hot plate or in an oven. In this way, the second multilayer structure 17 can be formed.

[0031] The method may also include forming a first multi-layer structure 16. As shown in FIG. The thin film 12 may be disposed on the surface of a substrate 14. The thin film 12 and the substrate 14 are referred to herein as As shown in FIG. 3B, a first photoresist layer 1 is formed on the surface of the thin film 12. 0a can be applied to form a first multi-layer structure 16. First Photoresist Layer 10a is as described herein. In one embodiment, each layer of the first multi-layer structure 16 is flat. Surface and / or smooth.

[0032] The article can include a substrate and a thin film that includes a replicated microstructured pattern.

[0033] From the above description, those skilled in the art will appreciate that the present teachings can be embodied in a variety of forms. Accordingly, these teachings are described with reference to specific embodiments and examples thereof. While the teachings herein have been provided in various forms, the true scope of the present teachings should not be so limited. Various changes and modifications can be made without departing from the scope of the invention.

[0034] The present disclosure is intended to be broadly construed. The present disclosure includes the coatings, devices, and compositions disclosed herein. Disclosed are equivalents, means, systems, and methods for accomplishing the functions, actions, and mechanical actions. Each of the disclosed coatings, devices, layers, articles, methods, and means , mechanical elements or mechanisms, the present disclosure relates to many aspects disclosed herein. Also encompassed within the disclosure are equivalents, means, systems and methods for implementing the mechanisms and devices. Furthermore, the present disclosure is intended to teach a method and a method formed by the method. The present disclosure relates to the article and its many aspects, features and elements. and the use of articles such as optical devices and their many aspects consistent with the description and spirit of their functions. The present invention is intended to encompass any equivalents, means, systems, and methods for use in the present invention. The scope of the invention in many embodiments herein is to be construed broadly as well. , are merely exemplary in nature and, therefore, variations that do not depart from the gist of the invention are to be construed as falling within the spirit and scope of the invention. Such variations are not intended to depart from the spirit and scope of the present invention. is not considered to be

Claims

1. 1. A method comprising the steps of: Providing a first multi-layer structure including a substrate, a thin film, and a first photoresist layer and, a second multilayer structure including a mold having a microstructure pattern and a second photoresist layer; preparing a structure; The first photoresist layer is in contact with the second photoresist layer. combining the layer structure and the second multi-layer structure; applying pressure and temperature; A method comprising:

2. 10. The method of claim 1, wherein the second photoresist layer comprises a replicated microstructure. a pattern and a base portion that does not have a replicated microstructure pattern; method.

3. 10. The method of claim 1, wherein the thin film is a thin film of a high refractive index material.

4. 10. The method of claim 1, wherein the mold having the microstructure pattern is peeled off. The method of claim 1, wherein the surface of the substrate is coated with an agent.

5. 10. The method of claim 1, further comprising removing the mold. method.

6. 2. The method of claim 1, wherein the first photoresist layer and the second photoresist layer are The photoresist layers combine to form a photoresist stack that is free of air pockets.

7. 7. The method of claim 6, wherein the photoresist stack comprises: a structured pattern, and the base portion not having the replicated microstructured pattern; , a method having

8. 7. The method of claim 6, further comprising: using a collimated light source to illuminate the photoresist. irradiating the photoresist stack with a flood exposure; and developing the photoresist stack. and The collimated light is incident on the replicated microstructure pattern and the replicated microstructure pattern. irradiating the base portion of the photoresist stack that does not contain a laser beam; Law.

9. 9. The method of claim 8, further comprising: etch the microstructure etched from the photoresist stack into the thin film. A method comprising forming a structured pattern.

10. 10. The method of claim 9, wherein the etched microstructure pattern of the thin film comprises: having an inverse pattern but the same aspect ratio as the microstructure pattern of the mold; may or may not have The replicated microstructure pattern of the photoresist stack has an inverse pattern. and The microstructure patterns etched in the thin film have the same pattern, but having the same aspect ratio as the replicated microstructure pattern in the photoresist stack. A method that may or may not have

11. 10. The method of claim 1, wherein the second multi-layer structure comprises a release coating attached to the mold. and applying a release coating to the coated film to make the surface of the release coating hydrophilic. A method formed by subjecting a sample to a treatment that results in:

12. 12. The method of claim 11, further comprising: applying a third photoresist layer to the stripping coat. The method comprises applying the composition onto a coating.

13. 13. The method of claim 12, further comprising, after applying the third photoresist layer: , heating at a temperature ranging from about 50° C. to about 90° C. for a time ranging from about 1 second to about 30 minutes. A method comprising:

14. 14. The method of claim 13, further comprising, after heating the third photoresist layer, applying a fourth photoresist layer onto the third photoresist layer. ,method.

15. 15. The method of claim 14, further comprising, after applying the fourth photoresist layer: , heating at a temperature ranging from about 50° C. to about 90° C. for a time ranging from about 1 second to about 30 minutes. A method comprising:

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