JP2019010776A - Stamper for forming pattern structure, manufacturing method of the same, and manufacturing method of the pattern structure - Google Patents

Abstract

To provide a stamper capable of realizing a high-definition pattern of a pattern structure and controlling on/off of pattern transfer by turning on/off light of the stamper, and to provide a method of manufacturing the same and a method of manufacturing a pattern structure using the stamper, making it possible to form a high definition pattern consisting of one or more compositions at once.SOLUTION: The stamper for forming a pattern structure, includes: a transparent base material; a transparent resin layer on the transparent base material; and a convex pattern on the transparent resin layer. The convex pattern includes single or plural kinds of inorganic materials as raw materials constituting a pattern of the pattern structure. Using the stamper, in a state in which the stamper and the base material for the pattern structure are brought into contact with each other such that the convex pattern of the stamper and the base material for the pattern structure face each other, by uniformly irradiating laser light, the convex pattern is transferred to the base material for the pattern structure to produce the pattern structure.SELECTED DRAWING: Figure 1

Description

The present invention relates to a stamper for pattern formation, a manufacturing method thereof, and a method of manufacturing a pattern structure using the stamper. In particular, the present invention relates to a stamper for forming a pattern capable of transferring one or a plurality of types of high-definition patterns by a laser, a manufacturing method thereof, and a manufacturing method of a pattern structure.

  In recent years, electronic circuits and wiring structures using a very simple process applying printing technology have been realized. For example, the wiring structure disclosed in Patent Document 1 is formed by applying functional ink to a convex portion of a plate having a concavo-convex pattern on the surface and transferring the ink by pressing the convex portion of the plate against a substrate. ing. This method is called the micro contact printing method.

  In the micro contact printing method, liquid functional ink (conductive ink, insulating ink, semiconductor ink, etc.) is transferred. At this time, since the end portion of the pattern bleeds out, the pattern does not become a high-definition pattern. In particular, in a fine pattern, a defect such as a short circuit of the wiring may occur. In Patent Document 2, in order to avoid such problems, the surface free energy of the substrate is changed in advance corresponding to the transfer pattern, and the wettability of the ink is changed. A method of forming is disclosed. As a result, ink bleeding is prevented, and then the ink is transferred by the micro contact printing method to realize a fine and high-definition pattern. In Patent Document 3, ultraviolet light is irradiated from the surface of a transfer destination base material using a stamper as a mask, and the wettability of the base material surface to ink is changed by utilizing a photo-induced reaction between oxygen in the air and the base material surface. Thus, a technique for reducing ink bleeding is disclosed.

  Regarding the method of forming a thin film pattern by transfer, there are the following known documents. Patent Document 4 discloses a method in which after a thin film is temporarily bonded to a support structure, the thin film side of the support structure is brought into contact with a transfer destination substrate having a bonding material layer, and the thin film is transferred to the transfer destination substrate. Have been described. Patent Document 4 mentions polydimethylsiloxane or silicon rubber-based polymer as a material for the support structure.

JP 2009-028947 A JP 2010-147408 A JP 2014-013868 A JP 2010-062527 A

  In the conventional printing technology, in order to avoid bleeding of ink on the transfer destination substrate surface, it is necessary to provide a separate processing step such as patterning the wettability of the transfer destination substrate surface in advance, which increases the cost of the process.

  A conventional microcontact printing stamper has been assumed to attach a specific ink to a convex portion of a concavo-convex structure formed on the stamper surface and transfer the ink to a transfer material. Therefore, with a conventional stamper, it is impossible to transfer a pattern composed of two or more types of ink in a single transfer process. In order to transfer a pattern composed of a plurality of inks with such a stamper, it is necessary to continue a plurality of transfer processes after a single transfer process, with high precision alignment at a pattern resolution level of micrometer or nanometer. Therefore, the conventional stamper is not suitable for forming a complicated pattern such as a pattern composed of a plurality of inks.

  In addition, it is necessary to form a micro- or nanometer-sized concavo-convex structure on the surface of a conventional stamper, and the micro- or nanometer concavo-convex pattern (master) produced by photo / electron beam lithography is copied onto rubber-like plastics. A stamper is produced. In the step of releasing the stamper from the master, a chipping of the structure easily occurs, so that release agents suitable for various master or stamper materials are often used. Even in that case, it was difficult to completely prevent the lack of structure. The lack of convex portions in the stamper directly leads to a defect in the transfer pattern on the substrate to be transferred, which causes a deterioration in the quality of the transfer pattern.

  The present invention is intended to solve these problems, and does not require a concavo-convex structure forming step on the stamper surface and a liquid ink application step on the convex shape, and a convex portion made of a transfer target material directly on the stamper surface. It is an object of the present invention to provide a stamper for forming a pattern structure, a method for manufacturing the same, and a method for manufacturing the pattern structure, which can produce a pattern. It is another object of the present invention to provide a stamper for forming a pattern structure, a method for manufacturing the same, and a method for manufacturing the pattern structure, which enable batch transfer of a plurality of substances.

  In order to achieve the above object, the present invention has the following features.

(1) A stamper for forming a pattern structure, comprising a transparent substrate, a transparent resin layer on the transparent substrate, and a convex pattern on the transparent resin layer, wherein the convex pattern is A stamper comprising a single material or a plurality of types of inorganic materials constituting a pattern of a pattern structure.
(2) The stamper according to (1), wherein the convex pattern has substantially no solvent.
(3) The stamper according to (1) or (2), wherein the convex pattern includes at least one layer.
(4) The stamper according to any one of (1) to (3), wherein the convex pattern is made of at least one of an inorganic thin film and a coating film.
(5) The stamper according to any one of (1) to (4), wherein the transparent resin layer has elasticity.
(6) The stamper according to any one of (1) to (5), wherein the transparent resin layer is polydimethylsiloxane having a highly adhesive surface.
(7) The stamper according to any one of (1) to (6), wherein the stamper is a laser transfer stamper for forming a pattern structure.
(8) A method for producing a stamper for forming a pattern structure, comprising: preparing a first base material on which a raw material film as a pattern raw material is formed; and a transparent base material provided with a transparent resin layer, In a state where the first base material and the transparent base material are in contact with each other so that the raw material film and the transparent resin layer face each other, laser light is emitted from the first base material or the transparent resin layer side. A stamper is formed by performing laser transfer to irradiate the raw material film and transfer and deposit only a portion of the raw material film irradiated with laser light on the transparent resin layer side. Manufacturing method.
(9) In the laser transfer step of transferring and depositing on the transparent resin layer side, the laser energy is equal to or higher than the laser energy that causes melting or evaporation of at least a part of the raw material film, and the molten material or evaporated material is scattered. The stamper manufacturing method as described in (8) above, wherein the transfer is performed by a laser beam set in an energy range smaller than the laser energy at which two or more transfer patterns are generated from the irradiation section.
(10) A method for manufacturing a pattern structure using the stamper according to any one of (1) to (7), wherein the stamper and the substrate for a pattern structure are formed by using a convex portion of the stamper. The pattern is transferred to the pattern structure substrate by uniformly irradiating a laser beam in a state where the pattern and the pattern structure substrate are in contact with each other. Manufacturing method of structure.
(11) The convex pattern is irradiated with a laser beam from the transparent resin layer side of the stamper, and the convex pattern is transferred to the pattern structure substrate disposed oppositely by turning on / off the light. The method for producing a pattern structure according to (10), wherein:
(12) A method for producing a pattern structure, comprising: preparing a first base material on which a raw material film as a pattern raw material is formed; and a transparent base material provided with a transparent resin layer; In a state where the material and the transparent base material are in contact with each other so that the raw material film and the transparent resin layer face each other, laser light is applied to the raw material film from the first base material or the transparent resin layer side. Irradiating, performing a laser transfer to transfer and deposit only a portion of the raw material film irradiated with laser light on the transparent resin layer side, and manufacturing the stamper, and using the stamper, the stamper and the pattern structure The convex pattern is used for the pattern structure by uniformly irradiating the body substrate with a laser beam in a state where the convex pattern of the stamper is in contact with the pattern structure base material. The process of transferring to the substrate. A method for producing a pattern structure, comprising:

  According to the stamper of the present invention and the method for producing a pattern structure using the stamper, ink containing a solvent is not used at the time of transfer. There is no ink bleeding on the surface of the material. Therefore, according to the present invention, a pattern structure having a high-definition fine pattern can be realized.

  According to the stamper manufacturing method of the present invention, a stamper having a high-definition pattern can be realized.

  Further, according to the method for producing a patterned structure of the present invention, transfer occurs on the transferred substrate side only when the pattern-shaped convex portion of the stamper is irradiated with light. Therefore, on / off of the transfer can be controlled by turning on / off the light to the stamper. Therefore, a pattern can be freely formed with high definition on a curved surface as well as a flat surface.

  In addition, according to the stamper manufacturing method of the present invention, a high-definition pattern made of a material having a plurality of compositions including an inorganic substance can be formed on the surface of the stamper. Therefore, according to the method for manufacturing a pattern structure using the stamper of the present invention, even a complicated pattern having a plurality of compositions can be transferred to a transfer substrate without requiring high-precision alignment.

  As described above, according to the present invention, a normal electronic device can be easily formed in a vacuum and solvent-free, and a fine pattern can be formed on a flexible substrate having a bend or a curved surface. For example, the present invention can be used for manufacturing a wearable device. In addition, if a biocompatible inorganic oxide or the like is used as a pattern material, it can be used as a coating technique for medical members such as implants.

It is a schematic diagram of the example of the structure of the stamper in embodiment of this invention. It is a figure which shows the manufacturing process of the stamper in embodiment of this invention. It is a figure which shows the manufacturing process of the pattern structure using a stamper in embodiment of this invention. It is an example of the raw material film for stamper manufacture in embodiment of this invention. 2 is a laser confocal micrograph for Example 1. FIG. (A) and (b) are stampers having convex portions made of silver on the PDMS layer, and (c) and (d) are silver pattern structures transferred and formed on a quartz glass substrate using the stamper. It is a figure of the laser confocal microscope picture of the ITO pattern structure body which was prepared by Example 2, and was transfer-formed on the quartz glass substrate. 6 is a diagram of a laser confocal micrograph in the case of Comparative Example 1. FIG. (A) is an Ag raw material film after laser transfer, and (b) is a transferred Ag pattern.

  Hereinafter, embodiments of the present invention will be described in detail.

  The inventor makes a transparent base material having a transparent and highly adhesive resin layer in contact with a support film surface on which a raw material film, which is a solid film containing an inorganic substance such as metal or metal oxide, is formed. When the pulse laser beam having a light intensity pattern is irradiated from the support (the raw material film back side) or the resin layer side (the raw material film surface side), at least part of the resin layer is melted and evaporated by light absorption of the raw material film. It has been found that a fine pattern of a raw material film corresponding to a light intensity pattern can be transferred and deposited with high accuracy on a transparent substrate having the above. Furthermore, this transparent resin layer / transparent substrate laminate having a fine pattern of the raw material film is used as a stamper for forming a fine pattern, brought into contact with a desired transfer destination substrate, and pulsed laser light is uniformly irradiated from the stamper side. As a result, it was found that light absorption of inorganic convex portions and subsequent melting and evaporation of at least a portion of the convex portions were caused, and it was possible to transfer and deposit on a transfer destination base material, and the following present invention was completed. .

[Pattern for forming pattern structure]
A stamper for forming a pattern structure according to an embodiment of the present invention includes a transparent substrate, a transparent resin layer on the transparent substrate, and a convex pattern on the transparent resin layer, and the convex pattern is And an inorganic material as a raw material of the pattern structure.

  FIG. 1 is a diagram schematically showing a stamper according to an embodiment of the present invention. As shown in FIG. 1A, the stamper includes a stamper transparent substrate 106, a transparent resin layer 105 on the transparent substrate 106, and a convex pattern 109 on the transparent resin layer 105.

  FIG. 1A is an example having a convex pattern 109 made of a single substance on the transparent resin layer 105. FIG. 1B is an example having a convex part pattern made of two kinds of substances, and an example having a convex part pattern 115 containing an inorganic substance A and a convex part pattern 116 containing an inorganic substance B different from the inorganic substance A. In this way, a convex pattern made of two or more kinds of substances can be provided on one stamper. FIG. 1C shows an example in which the convex pattern is composed of a convex pattern 117 of a multilayer film.

  The transparent base material for the stamper may be any base material that is transparent and can support the convex pattern. In the present specification, “transparent” means that the laser transfer process using a stamper can transmit at least the wavelength of the pulse laser used. The material of the transparent substrate is preferably an inorganic material such as quartz glass, borosilicate glass, sapphire, yttria stabilized zirconia, or a polymer film. In particular, a dimensional-stable inorganic material substrate and a dimensional-stable polymer material substrate that is preferably used for electronic devices such as polyimide, polyethylene terephthalate, and polyethylene naphthalate are more preferable. A transparent base material for a stamper can be appropriately selected according to the shape such as whether the final pattern structure is a flat surface or a curved surface.

Since the convex pattern of the pattern structure forming stamper is a film that is transferred to the transfer destination base material in the laser transfer process using the stamper, the inorganic material constituting the film of the pattern structure pattern that is the final product is used. Including. As an example of the convex pattern of the stamper for forming a pattern structure, there is no particular limitation as long as it is made of a film capable of laser transfer in laser transfer by uniform laser irradiation using a stamper. That is, as will be described in detail later, laser ablation is caused in a part of the light absorption layer that has absorbed the laser pulse in the vicinity of the interface between the transparent resin layer and the stamper surface protrusion, and the stamper surface protrusion is transferred along with the laser ablation. Any film can be used as long as it can be transferred and deposited on a target substrate. For example, it may be a solid film. It may be a solid film made of an inorganic material or a solid film containing an organic material whose main component is an inorganic material. Here, the main component means a case of 50% by volume or more. Furthermore, it is more preferable if it is 80 volume% or more. A thin film or a coating film may be used. Here, it does not include a conventional technique in which ink is applied to a stamper and transfer printing is simply performed. Further, the coating film may contain 5% or less of other solvent in addition to the inorganic material of the final pattern. Specific examples of the coating film include an Ag nano paste film and a carbon nanotube film. As an inorganic substance, a metal or alloy made of any one or more of Au, Ag, Cu, Mo, Cr, etc., a metal oxide made of any one or more of ITO, ZnO, TiO _2, Al ₂ O ₃ , BaTiO ₃ , etc. Is mentioned. More preferably, the convex pattern of the pattern structure forming stamper does not substantially contain a solvent.

  As a material of the transparent resin layer 105 of the stamper for forming the pattern structure, a polymer material transparent to the laser light wavelength used in the present invention is used. Examples thereof include polydimethylsiloxane (PDMS), polyurethane, polyacrylic acid, polymethacrylic acid, polyimide, polyethylene terephthalate, and polyethylene naphthalate. The material of the transparent resin layer is preferably PDMS having high adhesion and elasticity among the polymer materials. In addition, if there is a gap between the resin layer and the raw material film, when a part of the raw material film is deposited on the resin layer of the laser ablation species, it is scattered according to the gap distance while having a certain spread angle. Bleeding may occur. From this, in order to make the gap between the resin layer and the raw material film as zero as possible, the adhesiveness of the resin layer is important. In addition, during laser irradiation, when a fine pattern structure is transferred and deposited from the raw material film to the transparent resin layer, or from the transparent resin layer to the final transfer destination substrate, with the driving force by laser ablation, the adhesion force to the transfer destination Therefore, if the transfer source or transfer destination is not elastic, the transfer structure is likely to be crushed. Therefore, the elasticity of the transparent resin layer is also an important factor for forming a high quality pattern.

  A manufacturing method of a stamper for forming a pattern structure and a manufacturing method of a pattern structure by laser transfer using the stamper will be described below with reference to FIGS. 2A, 2B, and 3. FIG. 2A is a diagram showing a stamper manufacturing process. FIG. 2B is a diagram illustrating a manufacturing process of a pattern structure that is laser-transferred using a stamper.

[Method for producing stamper for forming pattern structure]
The manufacturing of the stamper for forming the pattern structure mainly includes the following steps.
(Process A1) The process of preparing the 1st base material which formed the raw material film | membrane used as the raw material of a pattern, and a transparent base material provided with a transparent resin layer.
(Step A2) In the state where the first base material and the transparent base material are in contact with each other so that the raw material film and the transparent resin layer face each other, the first base material or the transparent resin layer side Irradiating the raw material film with laser light, and performing laser transfer to transfer and deposit only the portion of the raw material film irradiated with the laser light on the transparent resin layer side.
(Step A3) A step of separating the first base material and the transparent base material to obtain a stamper having a convex pattern.

  In step (a) of FIG. 2A illustrating (step A1), the transparent resin layer 105 on the stamper transparent substrate 106 is formed on the first substrate 101 using the same material as the pattern structure. 102 and oppositely arranged.

  FIG. 3 is an example of a raw material film for manufacturing a stamper that can be used in (Step A1). In the example shown in FIG. 3A, a raw material film 102 made of an inorganic substance that absorbs the laser beam is formed on the surface of the first substrate 101 that is a support transparent to the laser beam wavelength used in the stamper manufacturing process. It has the structure which formed film. FIG. 3B shows an example in which the raw material film 102 made of an inorganic substance does not necessarily have to absorb laser light. A sacrificial layer 103 is provided between the first substrate 101 which is a transparent support and the raw material film 102, and the sacrificial layer 103 which absorbs laser light and evaporates most of the laser beam irradiation. The raw material film 102 laminated on the sacrificial layer 103 is formed on the surface of the transparent base material for the stamper by a propulsive force due to instantaneous evaporation (hereinafter simply referred to as “laser ablation”) of the sacrificial layer 103 by laser pulse irradiation. The pattern is laminated. FIG. 3C shows an example in which a multilayer film material 104 composed of two or more types of layers is provided on the first substrate 101 that is a transparent support. When referred to as the lower layer from the first substrate 101 side, pattern lamination is performed on the surface of the transparent substrate for the stamper by collecting a part of the upper multilayer film including the layer by laser ablation of a part of the lower layer in the multilayer film material 104 it can. By using the multi-layer laminated structure of the raw material film shown in FIG. 3 (c), it is possible to form a convex pattern consisting of the multi-layer film, and to transfer and form the pattern of the multi-layer film structure of the pattern structure which is the final product can do.

  The first substrate 101 may be transparent or not transparent. Examples of the transparent substrate include inorganic materials and polymer films that are transparent at the laser wavelength used, and examples include quartz glass, borosilicate glass, sapphire, and yttria-stabilized zirconia. In (Step A2), when laser irradiation is performed from the transparent base material side for the stamper, the first base material 101 does not need to be transparent.

  The source film 102 made of an inorganic substance can be formed by a vapor phase method such as a sputtering method, a vapor deposition method, or a pulse laser deposition method, or a liquid phase method such as a coating method. The sacrificial layer can also be formed by a vapor phase method such as a sputtering method, a vapor deposition method, and a pulse laser deposition method, or a liquid phase method such as a coating method, as in the case of the raw material film.

  Although FIG. 2A shows an example using the raw material film having the structure shown in FIG. 3A, the structure of the raw material film is not limited to this.

  FIG. 2A (b) illustrating (Step A2) shows the first substrate 101 and the transparent substrate for stamper in a state where the raw material film and the transparent resin layer are in contact with each other. Shows a step of performing laser transfer by irradiating the raw material film 102 with a laser pulse 107 from the base material 101 and transferring and depositing only the portion of the raw material film 102 irradiated with laser light on the transparent resin layer side. ing. Here, when irradiating the raw material film with laser light, the raw material film is irradiated with laser light in the same pattern as the pattern of the pattern structure (light intensity pattern or the like). Therefore, only the portion irradiated with the laser beam is transferred and deposited by laser transfer to form a convex pattern (step A3).

  The laser light for performing laser transfer needs to have a wavelength at which a layer that induces laser ablation of at least a raw material film or a convex pattern has light absorption.

  As shown in FIG. 2A (b), the raw material film 102 and the transparent resin layer 105 arranged to face each other are brought into close contact with each other, and weighted if necessary. It is possible to make contact with high density by weighting. The adhesion between the raw material film 102 and the transparent resin layer 105 on the stamper transparent substrate surface in the stamper manufacturing process is very important because it greatly affects the pattern quality of the convex pattern 109 formed on the stamper surface. If the adhesion is low, when the atoms, molecules, ions, clusters, and microdroplets formed by laser ablation induced by laser pulse irradiation are deposited on the opposing transparent resin layer 105, the pattern is the same as the raw film. This may increase according to the gap distance between the transparent resin layers, and may cause pattern bleeding of the convex pattern 109. Therefore, it is preferable to select a material that can provide high adhesion for the transparent resin layer 105. Moreover, since the first base material 101 and the transparent base material 106 for stamper may be damaged by the weighting, a weighting of 1 atm or less is preferable.

  Next, as shown in FIG. 2A (b), a single shot is irradiated with a laser pulse 107 from the first substrate 101 side which is a transparent support. A portion in the vicinity of the interface between the raw material film 102 and the first substrate 101 that is a transparent support becomes a light absorption layer 108 that absorbs a laser pulse. The laser pulse induces laser ablation in the light absorption layer 108, and an abrupt volume change accompanying a phase change from solid to gas / plasma due to ablation is used as a driving force to drive the upper part of the light absorption layer 108. Only the portion corresponding to the above (the portion from the ablation portion to the surface of the raw material film) is selectively extruded to the opposing transparent resin layer 105.

  The pulse width of the laser pulse 107 is preferably in the range of 10 femtoseconds to 100 milliseconds. However, if laser irradiation continues in a time range corresponding to the laser pulse width even after laser ablation as a driving force is generated, the portion around the irradiated portion of the raw material film 102, or in some cases, the first substrate 101 or Since unnecessary thermal damage may be induced to the members around the transparent resin layer 105, a time of about 10 femtoseconds to 100 nanoseconds is preferable.

  In FIG. 2A (c) illustrating (Step A3), the first base material 101 side and the transparent base material side are separated, and the stamper 110 including the transparent base material 106, the transparent resin layer 105, and the convex pattern 109 is formed. obtain. That is, in FIG. 2A (c), as a result of peeling off the first base material 101 and the stamper 110, the raw material film 102a remaining on the first base material after laser irradiation is transparent on the first base material 101 side. On the resin layer 105, there is a convex pattern (hereinafter also referred to as “stamper surface convex portion”) 109. The in-plane fine pattern of the stamper surface convex portion is formed corresponding to the light intensity pattern of the laser pulse of FIG. 2A (b).

  As a method of forming a light intensity pattern on the laser pulse 107, a generally known method can be used, and there is no particular limitation. For example, a mask reduction exposure method can be mentioned. In the mask reduction exposure method, a laser beam having a relatively large area having a flat light intensity such as a top hat beam is patterned with a mask, and then imaged exposure is performed so that a pattern of a desired size is formed on the sample surface. Although this method requires mask fabrication, a highly uniform fine pattern can be formed in a single shot over a relatively large area of the sample surface. If a spatial light modulator or a digital mirror device is used instead of a mask, pattern modulation can be easily performed, and laser pulses having a light intensity pattern can be freely formed. Further, by freely scanning the surface of the sample with a laser pulse using a galvano mirror, a single condensing point is one condensing point, but a pattern can be formed by scanning a plurality of shots.

  The stamper surface convex portion, that is, the convex pattern 109, preferably has a height from the surface of the resin layer of about 10 nm to 100 μm. The upper limit of this height is determined by the thickness of the raw material film. On the other hand, the lower limit of the height is determined by the thickness obtained by subtracting the thickness of the portion of the light absorption layer 108 that absorbs the laser pulse from which the laser ablation occurs from the original thickness of the raw material film 102. Further, the propulsive energy obtained by laser ablation needs to cover the energy for extruding the upper part of the ablation site and then depositing and fixing it on the transparent resin layer, which is also a determinant of the upper limit film thickness.

  In order to manufacture the stamper of FIG. 1B, the steps of FIGS. 2A (a), (b), and (c) may be repeated for each substance. In the case of repeating this, alignment is performed while observing a fine pattern previously formed on the stamper surface, or marking for alignment is performed on the stamper 110 and the raw material film 102 / first substrate 101. Can be aligned. In either case, in the case of the present invention, it is not necessary to mark the final target 113 having a device shape or the like in preparation for complicated alignment.

  In order to manufacture the stamper shown in FIG. 1 (c), a convex pattern consisting of a multilayer film can be obtained by using the raw material film shown in FIG. 3 (c).

  The stamper manufacturing method is not limited to the method of FIG. 2A. For manufacturing the convex pattern on the stamper surface, a method known as a method for forming a fine pattern of an inorganic material such as a metal or metal oxide can be used. For example, a lithography method, an inkjet method, or the like can be used. The method of FIG. 2A is preferable because the fine convex pattern of the stamper can be created with higher definition.

[Method of manufacturing pattern structure by laser transfer using stamper]
The manufacturing of the pattern structure mainly includes the following steps.
(Step B1) In a state where the stamper according to the embodiment of the present invention and the pattern structure base material are brought into contact with each other so that the convex pattern of the stamper and the pattern structure base material face each other, laser light is emitted. The process of transferring the said convex pattern to the base material for pattern structures by irradiating.
(Process B2) The process of isolate | separating the said base material for pattern structures and the said stamper, and obtaining the pattern structure which has a pattern.

  2B (d) and 2 (e) show how the fine pattern structure is transferred to the transfer destination base material 113 using the stamper 110 manufactured in FIG. 2A (c). The stamper surface convex portion 109 and the transfer destination base material 113 are arranged to face each other. In this state, a single shot of laser pulse 111 is irradiated from the back of the stamper, that is, the stamper transparent substrate 106 side, and at the position of the light absorption layer 112 in the vicinity of the interface between the transparent resin layer 105 and the stamper surface convex portion 109, Induces laser pulse absorption. As a result, laser ablation is caused in a part of the light absorption layer 112, and the stamper surface convex portion 109 is transferred by using the pressure generated by the rapid volume increase due to the phase change from solid to gas / plasma accompanying laser ablation as a driving force. A pattern 114 of a pattern structure made of an inorganic substance transferred onto the transfer destination substrate in FIG. 2B (e) is obtained by being transferred and deposited on the substrate 113. Similarly, when the stamper surface convex portion is a multilayer film, the pattern of the multilayer film is transferred to the transfer destination substrate.

  The laser pulse 111 irradiated in FIG. 2B (d) is only required to be able to be irradiated uniformly over the area covering the stamper surface convex portion 109 to be transferred, and is desirably uniform. The laser fluence needs to be equal to or greater than the laser ablation threshold of the stamper surface convex portion 109. However, as the energy for cutting the bond, since the stamper surface convex portion 109 is not a continuous film, the energy for cutting the bond in the film is unnecessary, and only the energy for cutting the bond at the interface with the transparent resin layer 105 may be used. Compared with the process of FIG. 2A (b), the laser fluence of the same level or less may be used.

  The laser light used for laser transfer in the production of the pattern structure that is the final product is such that the laser energy is equal to or higher than the laser energy that causes melting or evaporation of at least a part of the raw material film, and the melt or vapor is scattered. The transfer can be performed by laser light set in an energy range smaller than the laser energy that spreads, for example, by 1.1 times or more of the original pattern. The above 1.1 times is merely an example, and can be appropriately selected and set according to the required pattern definition.

  The transfer destination base material is not particularly limited as long as it is a member used as a base material of a conventional pattern structure. For example, the board | substrate for electronic devices, a flexible substrate, the base material for medical member coating, etc. are mentioned. The material may be either an inorganic material or an organic material. For example, a semiconductor wafer such as silicon, ceramics such as alumina, quartz glass, a polymer film, and a polymer substrate are preferable.

  Next, it demonstrates in detail by an Example and a comparative example.

Example 1
In this example, silver (Ag), which is a representative metal for electronic substrate wiring, is used as the inorganic material film 102. An Ag film having a thickness of 400 nm formed on the first base material (quartz glass transparent support) 101 by sputtering without heating the substrate was used as a raw material film / transparent support (thickness of about 2 mm). The transparent resin layer 105 and the transparent base material 106 for stamper were used as PDMS (thickness about 1 mm) and quartz glass (thickness about 1 mm), respectively. A pressure of about 0.1 atm was applied so that the Ag raw material film and the PDMS transparent resin layer were brought into contact with each other and adhered.

The laser pulse 107 irradiated in the stamper manufacturing process was KrF excimer laser light with a wavelength of 248 nm, and the pulse half-width was about 20 nanoseconds. This excimer laser beam has a top hat beam shape, and after passing through a mask having a 400 μm square grid pattern, an 8 × image formation is performed, and an optical system capable of forming a 50 μm square grid pattern on the source film / transparent support interface. Using, single shot irradiation was performed from the first substrate (transparent support) 101 side. The irradiation laser fluence was 1.2 J / cm ² .

  FIGS. 4A and 4B show the observation results of the surface of the stamper 110 having the Ag convex pattern obtained on the surface by the laser confocal microscope, obtained by the stamper manufacturing process. (B) is a partially enlarged view of (a). A 50 μm square Ag pattern corresponding to the irradiated laser beam intensity pattern is uniformly formed on the PDMS.

Next, transfer production of the fine pattern structure from the stamper will be described. Quartz glass was used as the transfer destination base material 113 as the final target. In order to bring the stamper surface convex portion of the stamper into contact with the quartz glass of the transfer destination base material, pressurization of about 0.1 atm was performed in order to make the contact more closely. In this state, KrF excimer laser light having a wavelength of 248 nm (pulse half width: about 20 nanoseconds) was irradiated from the transparent substrate 106 side for the stamper as a single shot. In this case, since a mask is not necessary, a uniform top hat beam was used to irradiate the interface between the stamper surface convex portion 109 and the transparent resin layer 105 so as to be about 1 mm square. The irradiation laser fluence was 1.2 J / cm ² .

  FIGS. 4C and 4D show the observation results of the surface of the Ag fine pattern structure on the quartz glass produced according to Example 1 with a laser confocal microscope. (D) is a partially enlarged view of (c). It can be seen that the Ag fine pattern on the stamper surface is transferred and deposited on the quartz glass as the final target while maintaining the pattern shape. The average film thickness of Ag was about 100 nm. The reason why the obtained film thickness is thinner than the original material film is that the laser irradiation part of the material film remaining on the first substrate side at the time of manufacturing the stamper forms a through hole, but a rim structure is formed around the through hole. This is because it is consumed for forming the rim structure. This is presumably because when the high temperature distribution in the raw material film was formed by laser irradiation, a part of the melted raw material that was in the temperature range below the ablation temperature and above the melting temperature formed a rim structure around by flow.

(Example 2)
In this example, ITO (indium tin oxide), which is a representative of transparent conductive oxides, is used as the inorganic oxide material film 102. An ITO film formed on the first base material (quartz glass transparent support) 101 with a thickness of 250 nm by sputtering without heating the substrate was used as a raw material film / transparent support (thickness of about 2 mm). The transparent resin layer 105 and the transparent base material 106 for stamper were used as PDMS (thickness about 1 mm) and quartz glass (thickness about 1 mm), respectively. A pressure of about 0.1 atm was applied so that the Ag raw material film and the PDMS transparent resin layer were brought into contact with each other and adhered.

The laser pulse 107 irradiated in the stamper manufacturing process was KrF excimer laser light with a wavelength of 248 nm, and the pulse half-width was about 20 nanoseconds. This excimer laser beam has a top hat beam shape, and after passing through a mask having a 400 μm square grid pattern, an 8 × image formation is performed, and an optical system capable of forming a 50 μm square grid pattern on the source film / transparent support interface. Using, single shot irradiation was performed from the first substrate (transparent support) 101 side. The irradiation laser fluence was set to 0.8 J / cm ² .

Next, transfer production of the fine pattern structure from the stamper will be described. Quartz glass was used as the transfer destination base material 113 as the final target. In order to bring the stamper surface convex portion of the stamper into contact with the quartz glass of the transfer destination base material, pressurization of about 0.1 atm was performed in order to make the contact more closely. In this state, KrF excimer laser light having a wavelength of 248 nm (pulse half width: about 20 nanoseconds) was irradiated from the transparent substrate 106 side for the stamper as a single shot. In this case, since a mask is not necessary, a uniform top hat beam was used to irradiate the interface between the stamper surface convex portion 109 and the transparent resin layer 105 so as to be about 1 mm square. The irradiation laser fluence was set to 0.8 J / cm ² .

  5A and 5B show the observation results of the surface of the ITO fine pattern structure on the quartz glass produced in Example 2 with a laser confocal microscope. (B) is a partially enlarged view of (a). It can be seen that an ITO fine pattern structure of about 50 μm square corresponding to the 50 μm grid pattern of the laser pulse 107 used in the stamper manufacturing process is transferred and formed on the quartz glass. The average film thickness of ITO was about 100 nm.

(Comparative Example 1)
In Examples 1 and 2, the case of using a stamper with a surface resin layer coat having high adhesion and elasticity was shown, but a comparative example different from this will be described.

  The material film / transparent support (thickness: about 2 mm) was formed using Ag as a raw material film on a quartz glass transparent support with a thickness of 200 nm by sputtering without heating the substrate. Further, the transfer destination base material to be opposed was made of quartz glass (thickness 2 mm). The Ag raw material film and the transfer destination substrate were brought into contact with each other, and pressurization was further performed at about 0.1 atm.

In a state where the Ag raw material film and the transfer destination base material were in contact with each other, a laser pulse with a pulse half width of 20 nanoseconds from a KrF excimer laser with a wavelength of 248 nm was irradiated. This excimer laser beam has a top hat beam shape, and after passing through a mask having a 400 μm square grid pattern, an 8 × image formation is performed, and an optical system capable of forming a 50 μm square grid pattern on the source film / transparent support interface. The single shot was irradiated from the transparent support side. The irradiation laser fluence was 0.6 J / cm ² .

  FIG. 6 shows an observation result in the case where the laser material transfer method of Comparative Example 1 is directly transferred and deposited on the opposing quartz glass substrate from the Ag raw material film on the glass substrate. (A) is an Ag raw material film (a raw material film remaining on the glass substrate) after laser transfer, in which the right figure is a partially enlarged view of the left figure. (B) is a laser confocal photomicrograph of the transferred Ag pattern, in which the left figure is a live image image, and the right figure is an image with a deeper focal depth obtained by ultra-depth measurement. From (a), it can be seen that the laser irradiation portion of the raw material film forms a through hole, and that a rim structure is formed around the through hole. On the other hand, when the transferred Ag pattern (b) is observed, the laser ablation species such as atoms, molecules, ions, etc. are deposited over approximately 100 μm square around the 50 μm square pattern. There is a pattern that seems to be blurred. Furthermore, a large number of dots were confirmed even in a 50 μm square pattern in the center, and a smooth transfer structure was not obtained, making it difficult to form a high quality pattern.

  The examples shown in the above embodiments and examples are described for easy understanding of the invention, and are not limited to these embodiments.

  INDUSTRIAL APPLICABILITY According to the stamper of the present invention and the method for producing a pattern structure using the same, it can be applied to the production of a coating material for medical members such as an electronic device having a fine pattern, a flexible electronic device, and an implant, and is industrially useful. is there.

101 First base material 102 Raw material film 102a Raw material film 103 remaining on first base material after laser irradiation Sacrificial layer 104 Multilayer film raw material 105 Transparent resin layer 106 Transparent base material 107, 111 Laser pulse 108, 112 Light absorption layer 109 convex pattern, stamper surface convex part 110 stamper 113 transfer destination base material 114 pattern structure pattern 115, 116 convex part pattern 117 multilayer convex part pattern

Claims (12)

A stamper for forming a pattern structure,
A transparent substrate, a transparent resin layer on the transparent substrate, and a convex pattern on the transparent resin layer,
The bumper pattern includes a single or a plurality of types of inorganic materials that form the pattern of the pattern structure.   The stamper according to claim 1, wherein the convex pattern has substantially no solvent.   The stamper according to claim 1, wherein the convex pattern includes at least one layer.   The stamper according to any one of claims 1 to 3, wherein the convex pattern is made of one or more of an inorganic thin film and a coating film.   The stamper according to claim 1, wherein the transparent resin layer has elasticity.   The stamper according to any one of claims 1 to 5, wherein the transparent resin layer is polydimethylsiloxane having a highly adhesive surface.   The stamper according to any one of claims 1 to 6, wherein the stamper is a laser transfer stamper for forming a pattern structure. A method of manufacturing a stamper for forming a pattern structure,
A first base material on which a raw material film to be a pattern raw material is formed and a transparent base material provided with a transparent resin layer are prepared,
Laser light from the first base material or the transparent resin layer side in a state where the first base material and the transparent base material are in contact with each other so that the raw material film and the transparent resin layer face each other. Is projected onto the raw material film, and a convex pattern is formed by performing laser transfer in which only the portion of the raw material film irradiated with laser light is transferred and deposited on the transparent resin layer side. Stamper manufacturing method. In the laser transfer step of transferring and depositing on the transparent resin layer side,
Laser energy that is greater than or equal to the laser energy that causes melting or evaporation of at least part of the raw material film, and the energy that is smaller than the laser energy that causes the melt or evaporation to scatter and produce two or more transfer patterns from one irradiation section 9. The stamper manufacturing method according to claim 8, wherein the transfer is performed by a laser beam set in a range. A method for producing a pattern structure using the stamper according to any one of claims 1 to 7,
By uniformly irradiating a laser beam with the stamper and the pattern structure base material in contact with the convex pattern of the stamper and the pattern structure base material facing each other, the convex A method for producing a pattern structure, comprising transferring a pattern to a substrate for a pattern structure.   The convex pattern is irradiated with a laser beam from the transparent resin layer side of the stamper, and the convex pattern is transferred to a pattern structure substrate disposed oppositely by turning on / off the light. The manufacturing method of the pattern structure of Claim 10. A method of manufacturing a pattern structure,
A first base material on which a raw material film to be a pattern raw material is formed and a transparent base material provided with a transparent resin layer are prepared,
Laser light from the first base material or the transparent resin layer side in a state where the first base material and the transparent base material are in contact with each other so that the raw material film and the transparent resin layer face each other. Irradiating the raw material film, performing a laser transfer to transfer and deposit only the portion of the raw material film irradiated with laser light on the transparent resin layer side, and manufacturing a stamper;
Using the stamper, the stamper and the pattern structure base material are uniformly irradiated with laser light in a state where the convex pattern of the stamper is in contact with the pattern structure base material. The process of transferring the said convex pattern to the base material for pattern structures by this, The manufacturing method of the pattern structure characterized by the above-mentioned.

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