JP6149481B2 - Pattern forming body and manufacturing method thereof - Google Patents

Description

  The present invention relates to a method for producing a pattern forming body using laser ablation.

  Currently, various methods have been proposed as pattern forming methods for forming various patterns such as designs, images, characters, circuits, etc. on a substrate. As a typical pattern forming method, a printing method is known, and the printing method has been widely used because it has an advantage that a pattern can be easily formed. However, high-definition patterning is difficult with the printing method, and it cannot be applied in applications where pattern miniaturization is required.

  On the other hand, in recent years, a photolithography method has become the mainstream as a method replacing the printing method. The photolithographic method enables high-definition patterning as compared with the conventional printing method, and can realize pattern miniaturization. However, in the photolithographic method, there is a problem that a waste liquid needs to be processed because it is necessary to use a photoresist, develop with a developer after exposure, and perform etching. Therefore, the photolithography method is not always highly productive. In addition, it has been pointed out that when a functional substance is used as a photoresist, there is a problem that the material is deteriorated by an alkaline solution or the like used during development, and the range of material selection is narrow.

  As another pattern forming method, a laser ablation method is known. Since the laser ablation method is a dry process that does not require the use of a developer, which is a drawback of the photolithography method, it is useful in that a pattern-formed body can be produced with high productivity.

  Under such circumstances, a method for producing a pattern forming body using a photocatalyst (see, for example, Patent Document 1) and a method for producing a pattern forming body by irradiation with vacuum ultraviolet rays (for example, see Patent Documents 2 to 5) have been proposed. ing. Since the manufacturing method of such a pattern formation body is a dry process like the above-mentioned laser ablation method, it is useful compared with the photolithography method.

  In pattern formation by photocatalyst or vacuum ultraviolet rays, the organic matter is decomposed and removed by the action of the photocatalyst accompanying the irradiation of energy such as ultraviolet rays or the action of vacuum ultraviolet rays, that is, the molecular bonds of the organic matter are broken or the organic matter is A pattern is formed by oxidative decomposition. Therefore, in such a method, it is necessary that oxygen that acts on a photocatalyst, vacuum ultraviolet rays, or the like is present on the surface of the pattern forming substrate on which the pattern is formed.

In the manufacturing method of the pattern formation body using a photocatalyst, energy, such as an ultraviolet-ray, is irradiated to the pattern formation board | substrate through the photomask which has a photocatalyst content layer, for example. Moreover, in the manufacturing method of the pattern formation body by irradiation of a vacuum ultraviolet ray etc., a vacuum ultraviolet ray etc. are irradiated to a pattern formation board | substrate via a photomask, for example.
In this case, in order to secure oxygen that acts with a photocatalyst or vacuum ultraviolet rays, it is preferable to dispose the pattern forming substrate and the photomask at a predetermined interval. However, the oxygen radicals generated by the excitation of oxygen or the oxygen radicals enter the non-irradiated part, resulting in poor resolution and reduced patterning accuracy. In particular, since organic materials used in these methods are materials that are generally less sensitive than photoresists and the like, pattern formation requires a certain amount of time, and the wraparound of light and oxygen radicals becomes a problem.
On the other hand, if the pattern formation substrate and the photomask are brought close to or in contact with each other, the wraparound of light and oxygen radicals can be reduced, but the oxygen acting on the photocatalyst or vacuum ultraviolet rays is insufficient, resulting in the sensitivity of pattern formation. There is a problem that the patterning is reduced and it takes a long time to form a pattern.

JP 2000-249821 A Japanese Patent No. 4678574 Japanese Patent No. 4502382 JP 2009-212127 A JP 2012-33617 A

  The present invention has been made in view of the above problems, and a main object of the present invention is to provide a pattern forming body having a high-definition pattern and a manufacturing method thereof.

  In order to achieve the above object, the present invention includes an absorption layer that absorbs ultraviolet rays, and a transmission layer that is formed in a pattern on the absorption layer and that transmits ultraviolet rays. Provided is a pattern forming body characterized in that an absorption layer is exposed.

  In the present invention, since the transmission layer transmits ultraviolet rays and the absorption layer absorbs ultraviolet rays, the absorption layer is irradiated with an ultraviolet laser in a pattern from the transmission layer side, and the transmission layer is removed in a pattern by laser ablation. Thus, a pattern forming body having a concavo-convex pattern with or without a transmission layer can be obtained. Since the laser is excellent in straightness, the transmission layer can be patterned with high definition, and a pattern forming body having a fine uneven pattern can be obtained.

  In the said invention, it is preferable that the exposed said absorption layer surface has lyophilic property, and the said permeation | transmission layer surface has liquid repellency. Although it has been difficult to form a high-definition pattern with different wettability by a conventional method for producing a pattern forming body using a photocatalyst or vacuum ultraviolet ray, in the present invention, the exposed absorption layer surface has a lyophilic property. In the case where the surface of the transmissive layer has liquid repellency, a pattern forming body having a high-definition pattern having different wettability can be obtained.

  Moreover, in this invention, it is preferable that the said absorption layer and the said permeation | transmission layer have insulation. When the absorption layer and the transmission layer have insulating properties, the pattern forming body of the present invention can be used to form a conductive pattern such as an electrode or a wiring. It can be suitably used for required electronic devices.

  The present invention also includes a lamination step of laminating a transmission layer that transmits ultraviolet light on an absorption layer that absorbs ultraviolet light, and irradiating the absorption layer with an ultraviolet laser in a pattern from the transmission layer side, and then transmitting the transmission by laser ablation. And a patterning step of exposing the absorbing layer by removing the layer in a pattern and providing a method for producing a pattern forming body.

  In the present invention, since the transmission layer transmits ultraviolet rays and the absorption layer absorbs ultraviolet rays, the transmission layer is removed in a pattern by laser ablation by irradiating the absorption layer with an ultraviolet laser from the transmission layer side. Accordingly, a concavo-convex pattern can be formed depending on the presence or absence of a transmissive layer. Since the laser is excellent in straightness, the transmission layer can be patterned with high definition.

  In the said invention, it is preferable that the exposed said absorption layer surface has lyophilic property, and the said permeation | transmission layer surface has liquid repellency. As described above, it is difficult to form a high-definition pattern with different wettability by the conventional method for producing a pattern forming body using a photocatalyst or vacuum ultraviolet ray. When lyophilic and the surface of the transmission layer has liquid repellency, a high-definition pattern having different wettability can be formed.

  Moreover, the manufacturing method of the pattern formation body of this invention may further have the lyophilic process process of performing a lyophilic process on the exposed said absorption layer surface after the said patterning process. When the absorbing layer has an insulating property, generally the insulating resin often has a liquid repellency, so that the wettability between the absorbing layer surface and the transmitting layer surface exposed by the lyophilic treatment is high. The difference can be increased. Further, when the lyophilic treatment is a method using ultraviolet rays such as UV-ozone treatment or vacuum ultraviolet ray treatment, since the transmission layer transmits ultraviolet rays, only the exposed absorption layer surface can be lyophilic.

  In the present invention, there is an effect that high-definition patterning is possible.

It is a schematic sectional drawing which shows an example of the pattern formation body of this invention. It is process drawing which shows an example of the manufacturing method of the pattern formation body of this invention. It is process drawing which shows the other example of the manufacturing method of the pattern formation body of this invention.

  Hereinafter, the pattern forming body and the manufacturing method thereof of the present invention will be described in detail.

A. Pattern Forming Body First, the pattern forming body of the present invention will be described.
The pattern formed body of the present invention has an absorption layer that absorbs ultraviolet rays and a transmission layer that is formed in a pattern on the absorption layer and transmits ultraviolet rays, and the absorption layer is exposed at the opening of the transmission layer. It is characterized by that.

The pattern forming body of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic sectional view showing an example of a pattern forming body of the present invention. A pattern forming body 1 illustrated in FIG. 1 includes a substrate 2, an absorption layer 3 that is formed on the substrate 2 and absorbs ultraviolet rays, and a transmission layer 4 that is formed on the absorption layer 3 and transmits ultraviolet rays. ing. The absorption layer 3 is exposed at the opening of the transmissive layer 4, and the pattern forming body 1 has a concavo-convex pattern depending on the presence or absence of the transmissive layer 4.

  2A to 2D are process diagrams showing an example of the method for producing a pattern forming body of the present invention, and an example of manufacturing the pattern forming body shown in FIG. First, as illustrated in FIG. 2A, the absorption layer 3 and the transmission layer 4 are sequentially laminated on the substrate 2. Next, as illustrated in FIGS. 2B to 2C, when the absorption layer 3 is irradiated with the ultraviolet laser L in a pattern from the transmission layer 4 side, the transmission layer 4 transmits the ultraviolet laser L, and the absorption layer 3 Since 3 absorbs the ultraviolet laser L, ablation occurs from the interface between the transmission layer 4 and the absorption layer 3 toward the transmission layer 4, and the transmission layer 4 is removed in a pattern by the laser ablation, so that the absorption layer 3 is exposed. As a result, as illustrated in FIG. 2D, the pattern forming body 1 having a concavo-convex pattern with or without the transmission layer 4 can be obtained. In this pattern forming body 1, since the ultraviolet laser L is absorbed by the absorption layer 3, ablation occurs from the interface between the transmission layer 4 and the absorption layer 3 toward the transmission layer 4. Therefore, the transmission layer 4 is removed. In the region, it is considered that the surface of the absorption layer 3 is slightly depressed.

  In the present invention, since the transmission layer transmits ultraviolet rays and the absorption layer absorbs ultraviolet rays, the absorption layer is irradiated with an ultraviolet laser in a pattern from the transmission layer side, and the transmission layer is removed in a pattern by laser ablation. Thus, a pattern formed body can be obtained. Since the laser is excellent in straightness, the transmission layer can be patterned with high definition, and a pattern forming body having a fine concavo-convex pattern, particularly a fine concave portion can be obtained.

  Further, in the present invention, as illustrated in FIG. 1, the pattern forming body 1 has a concave / convex pattern composed of a portion where the transmissive layer 4 is present and a portion where the transmissive layer 4 is absent. Various patterns can be formed by applying ink or the like. In this case, since the pattern is formed in the concave portion, the adhesion of the pattern can be improved.

  Furthermore, in the example shown in FIG. 1, when the exposed surface of the absorbing layer 3 has lyophilicity and the surface of the transmissive layer 4 has liquid repellency, the exposed surface of the absorbing layer 3 and the surface of the transmissive layer 4 The difference in wettability can also be used for pattern formation, and a pattern can be formed with high accuracy.

Here, in a conventional method for producing a pattern forming body using a photocatalyst or vacuum ultraviolet ray, a liquid repellent material such as a fluororesin is used as an organic substance that is oxidatively decomposed by the action of the photocatalyst associated with energy irradiation or the action of vacuum ultraviolet ray. When is used, it is very difficult to completely decompose and remove the layer containing the liquid repellent material. In general, a photoresist containing fluorine is inferior in resolution.
In contrast, in the present invention, even when a liquid repellent material is used for the transmission layer, the transmission layer transmits ultraviolet rays and the absorption layer absorbs ultraviolet rays. Thus, the transmission layer can be removed by laser ablation, and high-definition patterning is possible. When the permeable layer contains a liquid repellent material, a pattern forming body having patterns with different wettability between the surface of the permeable layer and the exposed surface of the absorbing layer can be obtained. Therefore, the present invention is particularly useful when a high-definition pattern is required in a pattern forming body having patterns with different wettability.

  Hereinafter, each structure in the pattern formation body of this invention is demonstrated.

1. Absorbing layer The absorbing layer in the present invention absorbs ultraviolet rays, and the absorbing layer is exposed at the opening of the transmitting layer.

The absorbing layer only needs to absorb ultraviolet rays, and the ultraviolet ray transmittance of the absorbing layer may be such that laser ablation can occur by irradiation with an ultraviolet laser, but specifically, it should be 50% or less. Of these, 30% or less, particularly 15% or less is preferable. This is because if the transmittance is in the above range, the transmission layer can be efficiently removed by laser ablation by irradiating the absorption layer with an ultraviolet laser from the transmission layer side.
In addition, the transmittance | permeability of said ultraviolet-ray points out the transmittance | permeability of the wavelength of the ultraviolet laser to be used. Specifically, the transmittance of ultraviolet rays is calculated by measuring the transmission spectrum of a sample based on Lambert-Beer's law using light having a wavelength of 190 nm to 380 nm.

  Moreover, it is preferable that the exposed absorption layer surface has a small contact angle with a liquid compared with the permeation | transmission layer surface, and it is preferable to have lyophilicity. This is because various patterns can be formed by utilizing the difference in wettability between the exposed absorption layer surface and the transmission layer surface. In addition, as described above, it has been difficult to form a high-definition pattern having different wettability by a conventional method for producing a pattern forming body using a photocatalyst or vacuum ultraviolet ray. It can be set as the pattern formation body which has a different high-definition pattern.

The contact angle with the liquid on the surface of the exposed absorbent layer may be smaller than the contact angle with the liquid on the surface of the permeable layer, but the contact angle with the liquid on the surface of the exposed absorbent layer and the contact angle with the liquid on the surface of the transmissive layer Is preferably 10 ° or more, more preferably 30 ° or more, and particularly preferably 60 ° or more.
Further, the contact angle of the exposed absorbing layer surface with the liquid is preferably 80 ° or less, more preferably 60 ° or less, and particularly preferably 40 ° or less, with the liquid having a surface tension of 70 mN / m. . Since the wettability of the exposed absorbent layer surface is in the above range, a high-definition pattern can be easily formed by utilizing the difference in wettability between the exposed absorbent layer surface and the transmissive layer surface. It is.
Here, the contact angle with the liquid is measured using a contact angle measuring device (PCA-1 manufactured by Kyowa Interface Science Co., Ltd.) with a liquid having various surface tensions. 30 seconds later), and the results were obtained or graphed. In this measurement, as a liquid having various surface tensions, a wetting index standard solution manufactured by Pure Chemical Co., Ltd. was used.

  Moreover, it is preferable that an absorption layer has insulation. In the case where various patterns are formed by utilizing the recessed portion where the absorption layer is exposed and further utilizing the difference in wettability between the exposed absorption layer surface and the transmission layer surface, the absorption layer has an insulating property. By having it, it is possible to form conductive patterns such as electrodes and wirings. Therefore, the pattern formed body of the present invention can be suitably used for an electronic device that requires pattern miniaturization.

  The material constituting the absorption layer is not particularly limited as long as it is a material that absorbs ultraviolet rays and can cause laser ablation by irradiation with an ultraviolet laser, and any of organic materials and inorganic materials can be used. it can. Of these, organic materials are preferred. This is because laser ablation is likely to occur in organic materials, and energy required for laser ablation is low. Moreover, it is preferable that the material which comprises an absorption layer is what can form the absorption layer which has insulation and has a lyophilic surface, for example, resin which has insulation can be used.

When the exposed absorbing layer surface has lyophilic properties, the absorbing layer may contain a lyophilic material or the surface may be subjected to lyophilic treatment. In general, since many insulating resins have liquid repellency, the exposed absorbent layer surface has been made lyophilic so that the exposed absorbent layer surface and the transparent layer surface are wettable. The difference can be increased.
The lyophilic material is not particularly limited as long as it satisfies the contact angle with the liquid on the surface of the absorption layer, and can be appropriately selected from known organic materials. Examples of hydrophilic materials include polyvinyl alcohols and urea resins.
Examples of the lyophilic treatment include UV-ozone treatment, vacuum ultraviolet treatment, oxygen plasma treatment, and the like. The material capable of lyophilic treatment is not particularly limited as long as it satisfies the contact angle with the liquid on the surface of the absorption layer after lyophilic treatment. For example, polyacrylate, polycarbonate, polyethylene, polypropylene And polymer materials such as polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, cellulose triacetate, polystyrene, and organopolysiloxane.

  The thickness of the absorption layer is not particularly limited as long as the absorption layer has a thickness that allows the absorption layer to remain when laser ablation occurs by irradiation with an ultraviolet laser. It is preferably in the range of 1 μm to 10 μm, more preferably in the range of 0.2 μm to 5 μm, and particularly preferably in the range of 0.5 μm to 1 μm.

  In the present invention, as illustrated in FIGS. 2A to 2D, the pattern forming body 1 irradiates the absorption layer 3 with the ultraviolet laser L in a pattern from the transmission layer 4 side, and transmits the transmission layer by laser ablation. It can be formed by removing 4 in a pattern. Ablation occurs from the interface between the transmission layer 4 and the absorption layer 3 to the transmission layer 4 by the absorption of the ultraviolet laser L by the absorption layer 3, and therefore the region where the transmission layer 4 is removed in the pattern forming body 1 Then, it is thought that the absorption layer 3 is exposed and the surface of the absorption layer 3 is slightly depressed. Therefore, it is sufficient that the absorption layer is exposed at the opening of the transmission layer, but it is assumed that the exposed absorption layer has a concave shape on the surface. In the case of forming a pattern by applying a functional material on the exposed absorption layer, the adhesiveness of the pattern made of the functional material can be improved by forming a pattern.

  The method for forming the absorption layer will be described in detail in the section “B. Method for producing pattern-formed body”, which will be described later.

2. Transmission Layer The transmission layer in the present invention is formed in a pattern on the absorption layer and transmits ultraviolet rays.

The UV transmittance of the transmission layer is as follows. When the absorption layer is irradiated with UV laser from the transmission layer side, the UV laser is transmitted through the transmission layer and absorbed by the absorption layer, and the transmission layer is removed in a pattern by laser ablation. However, it is preferably 60% or more, more preferably 75% or more, and particularly preferably 85% or more. This is because if the transmittance is in the above range, the transmission layer can be efficiently removed by laser ablation by irradiating the absorption layer with an ultraviolet laser from the transmission layer side.
The definition of the ultraviolet transmittance and the method for measuring the ultraviolet transmittance are the same as those described in the section of the absorption layer.

Further, the surface of the transmissive layer preferably has a larger contact angle with the liquid than the exposed surface of the absorbing layer, and preferably has liquid repellency. This is because various patterns can be formed by utilizing the difference in wettability between the surface of the transmission layer and the exposed absorption layer surface. In addition, as described above, it has been difficult to form a high-definition pattern having different wettability by a conventional method for producing a pattern forming body using a photocatalyst or vacuum ultraviolet ray. It can be set as the pattern formation body which has a different high-definition pattern.
The contact angle with the liquid on the surface of the permeable layer may be larger than the contact angle with the liquid on the surface of the exposed absorption layer. Specifically, the contact angle with the liquid with a surface tension of 70 mN / m is 90 ° or more. Of these, 95 ° or more, particularly 100 ° or more is preferable. This is because when the wettability of the surface of the transmissive layer is in the above range, a high-definition pattern can be easily formed using the difference in wettability between the surface of the transmissive layer and the exposed absorbent layer surface. .
In addition, about the measuring method of a contact angle with a liquid, it is the same as that of the method described in the term of the said absorption layer.

  The transmissive layer preferably has an insulating property. Since the transmission layer has an insulating property, it is possible to form conductive patterns such as electrodes and wirings by utilizing the uneven pattern and also the difference in wettability. Can be suitably used for electronic devices that require the above.

  The material constituting the transmission layer is not particularly limited as long as it is a material that transmits ultraviolet rays and can be removed by laser ablation by irradiating the absorption layer with ultraviolet laser from the transmission layer side. Examples of the fluororesin include polytetrafluoroethylene and CYTOP (registered trademark) manufactured by Asahi Glass Co., Ltd. The material constituting the transmission layer may be a material other than the fluororesin so long as the transmittance at the wavelength of the irradiated ultraviolet laser is in the above range. In addition, the material constituting the transmissive layer is preferably an insulating material capable of forming a transmissive layer having a liquid repellent surface, and can be appropriately selected from the above materials. .

When the surface of the transmissive layer has liquid repellency, the permeable layer may contain a liquid repellant material, or may have a surface that has been subjected to a liquid repellency treatment, and is a self-assembled film. Also good.
The liquid repellent material is not particularly limited as long as it satisfies the contact angle with the liquid on the surface of the transmission layer, and examples thereof include a fluororesin.
In addition, as the liquid repellency treatment, for example, a fluorine plasma treatment can be given. The material capable of the liquid repellency treatment is not particularly limited as long as it satisfies the contact angle with the liquid on the surface of the transmission layer after the liquid repellency treatment. For example, organopolysiloxane, polyvinyl alcohol, polycarbonate , Polymer materials such as polyvinyl chloride, polystyrene, polyamide, polyimide, epoxy resin, and phenol resin.
As the self-assembled film, a self-assembled monomolecular film, a Langmuir-Blodgett film, an alternating adsorption film, or the like can be used. For example, examples of the material for the self-assembled monolayer include silanes such as octadecyltrichlorosilane and perfluoroalkylsilane. The self-assembled monomolecular film, the Langmuir-Blodgett film, and the alternately adsorbed film can be the same as those described in, for example, Japanese Patent Application Laid-Open No. 2003-195029. Is omitted.

The pattern shape of the transmissive layer is appropriately selected according to the use of the pattern forming body and can be an arbitrary shape.
Further, the pattern dimension of the transmission layer is not particularly limited, but in the present invention, the concave / convex pattern can be miniaturized, and in particular, a concave / convex pattern having fine concave portions can be obtained. Specifically, it can be formed if the width of the opening of the transmission layer is about 2 μm.

  The thickness of the transmission layer is not particularly limited as long as it can satisfy the above-described transmittance and can be removed by laser ablation by irradiation of an ultraviolet laser to the absorption layer from the transmission layer side. Specifically, the thickness is preferably in the range of 1 nm to 300 nm, more preferably in the range of 2 nm to 100 nm, and particularly preferably in the range of 2 nm to 20 nm. This is because, if the thickness of the transmission layer is within the above range, the transmission layer can be efficiently removed by laser ablation by irradiating the absorption layer with the ultraviolet laser from the transmission layer side.

  The method for forming the transmissive layer will be described in detail in the section “B. Method for producing pattern-formed body”, which will be described later.

3. Substrate In the present invention, an absorption layer and a transmission layer may be formed on the substrate.
The board | substrate should just be a thing which can support an absorption layer and a permeation | transmission layer, and is suitably selected according to the use etc. of a pattern formation body. As a board | substrate, what consists of glass, a resin film, a ceramic, a metal etc. can be mentioned, for example.

4). Uses Examples of uses of the pattern forming body of the present invention include formation of electrodes and semiconductor layers in semiconductor elements, wirings on wiring boards, and the like. In particular, the pattern formed body of the present invention can be suitably used for an electronic device that requires a fine pattern.

B. Next, the manufacturing method of the pattern formation body of this invention is demonstrated.
The method for producing a patterned product of the present invention comprises a laminating step of laminating a transmission layer that transmits ultraviolet light on an absorption layer that absorbs ultraviolet light, and irradiating the absorption layer with an ultraviolet laser in a pattern from the transmission layer side. And a patterning step of removing the transmission layer in a pattern by laser ablation and exposing the absorption layer.

The manufacturing method of the pattern formation body of this invention is demonstrated referring drawings.
2A to 2D are process diagrams showing an example of a method for producing a pattern forming body of the present invention. First, as illustrated in FIG. 2A, an absorption layer 3 that absorbs ultraviolet rays and a transmission layer 4 that transmits ultraviolet rays are stacked on the substrate 2. Next, as illustrated in FIGS. 2B to 2C, when the absorption layer 3 is irradiated with the ultraviolet laser L in a pattern from the transmission layer 4 side, the transmission layer 4 transmits the ultraviolet laser L, and the absorption layer 3 Since 3 absorbs the ultraviolet laser L, ablation occurs from the interface between the transmission layer 4 and the absorption layer 3 toward the transmission layer 4, and the transmission layer 4 is removed in a pattern by the laser ablation, so that the absorption layer 3 is exposed. As a result, as illustrated in FIG. 2D, a pattern forming body 1 having a concavo-convex pattern with or without the transmission layer 4 is obtained. In this pattern forming body 1, since the ultraviolet laser L is absorbed by the absorption layer 3, ablation occurs from the interface between the transmission layer 4 and the absorption layer 3 toward the transmission layer 4. Therefore, the transmission layer 4 is removed. In the region, it is considered that the surface of the absorption layer 3 is slightly depressed.

  In the present invention, since the transmission layer transmits ultraviolet rays and the absorption layer absorbs ultraviolet rays, the transmission layer is removed in a pattern by laser ablation by irradiating the absorption layer with an ultraviolet laser from the transmission layer side. It is possible to form a concavo-convex pattern with or without a transmissive layer. Since the laser is excellent in straightness, the transmission layer can be patterned with high definition, and a fine concavo-convex pattern, particularly a concavo-convex pattern having fine concavo-convex portions can be formed.

  Further, in the present invention, since a concavo-convex pattern can be formed depending on the presence or absence of a transmissive layer, various patterns can be formed by applying ink or the like to the recesses where the permeable layer is removed and the absorbing layer is exposed. It is. In this case, since ink etc. are given to a crevice, a pattern excellent in adhesiveness can be formed.

  Furthermore, when the exposed absorbent layer surface is lyophilic and the permeable layer surface is lyophobic, various patterns are formed depending on the wettability difference between the exposed absorbent layer surface and the permeable layer surface. Is possible. In this case, since ink or the like is applied to the recess that is a lyophilic region, a pattern can be easily formed.

  As described above, it is difficult to form a high-definition pattern having different wettability in the conventional method for producing a pattern forming body using a photocatalyst or vacuum ultraviolet ray. It is possible to form a fine pattern.

  3A to 3E are process diagrams showing another example of the method for producing a pattern forming body of the present invention. First, as illustrated in FIG. 3A, an absorption layer 3 that absorbs ultraviolet rays and a transmission layer 4 that transmits ultraviolet rays are stacked on a substrate 2. Next, as illustrated in FIGS. 3B to 3C, when the absorption layer 3 is irradiated with the ultraviolet laser L in a pattern from the transmission layer 4 side, the transmission layer 4 transmits the ultraviolet laser L, and the absorption layer Since 3 absorbs the ultraviolet laser L, ablation occurs from the interface between the transmission layer 4 and the absorption layer 3 toward the transmission layer 4, and the transmission layer 4 is removed in a pattern by the laser ablation, so that the absorption layer 3 is exposed. As a result, as illustrated in FIG. 3D, a concavo-convex pattern is formed depending on the presence or absence of the transmissive layer 4. Next, as illustrated in FIG. 3E, a lyophilic treatment 11 such as UV-ozone treatment or vacuum ultraviolet treatment is performed on the entire surface of the exposed absorption layer 3 and transmission layer 4. Since the transmission layer 4 transmits ultraviolet rays, the surface of the transmission layer 4 is not lyophilic, and only the exposed surface 3a of the absorption layer 3 is lyophilic. Thereby, the pattern formation body 1 which has a pattern from which the wettability differs by the surface 3a of the exposed absorption layer 3 and the surface of the permeation | transmission layer 4 is obtained.

  In the present invention, when the lyophilic treatment is performed after the patterning step, the difference in wettability between the exposed absorption layer surface and the transmission layer surface can be increased. The absorbing layer preferably has an insulating property, and since many insulating resins generally have a liquid repellency, the exposed absorbing layer surface is preferably subjected to a lyophilic treatment.

  In addition, when the lyophilic treatment is a method using ultraviolet rays such as UV-ozone treatment or vacuum ultraviolet ray treatment, the transmissive layer transmits ultraviolet rays, so the permeable layer surface is not lyophilic, and the exposed absorption layer surface Can only be lyophilic.

Here, the conventional method for producing a pattern forming body using a photocatalyst or vacuum ultraviolet rays can also be applied to a method for forming patterns having different wettability. In these methods, when the pattern forming substrate is irradiated with ultraviolet rays or the like through a photomask, oxygen that acts on the photocatalyst, vacuum ultraviolet rays, or the like is placed when the pattern forming substrate and the photomask are arranged at a predetermined interval. Although it can be ensured, since ultraviolet rays and the like are diffused light, light and oxygen radicals wrap around the unirradiated portion, and patterning accuracy is reduced. On the other hand, if the pattern formation substrate and the photomask are brought close to or in contact with each other, light and oxygen radicals will not circulate to the unirradiated part, but oxygen that acts on the photocatalyst or vacuum ultraviolet rays will be insufficient, making pattern formation difficult. become.
On the other hand, in the present invention, when the lyophilic treatment is performed, as illustrated in FIG. 3E, the transmissive layer 4 functions as a mask, and the transmissive layer 4 and the absorbing layer 3 are in contact with each other. In addition, since the absorption layer 3 is exposed in the region where the transmission layer 4 is removed, it is necessary to sufficiently secure oxygen that acts on vacuum ultraviolet rays and the like while preventing light and oxygen radicals from entering the unirradiated portion. Thus, only the surface 3a of the absorbing layer 3 exposed with high accuracy and good resolution can be made lyophilic. Therefore, it is possible to form a high-definition pattern with different wettability.

  Hereinafter, each process in the manufacturing method of the pattern formation body of this invention is demonstrated.

1. Lamination process The lamination process in this invention is a process of laminating | transmitting the permeation | transmission layer which permeate | transmits an ultraviolet-ray on the absorption layer which absorbs an ultraviolet-ray.
Hereinafter, the absorption layer and the transmission layer will be described separately.

(1) Absorbing layer In the present invention, the method for forming the absorbing layer is appropriately selected according to the material used for the absorbing layer, and for example, an absorbing layer forming coating solution is applied onto the substrate. Examples thereof include a CVD method such as a thermal CVD method and a plasma CVD method, a PVD method such as a vapor deposition method and a sputtering method. The application method is not particularly limited as long as it is a method capable of applying the coating liquid for forming an absorption layer over the entire surface of the substrate. For example, spin coating, die coating, roll coating, bar coating, General methods such as a dip coating method, a spray coating method, a blade coating method, a gravure printing method, a slit coating method, an ink jet method, and a flexographic printing method can be used.

  In addition, since the characteristics, material, thickness, etc. of the absorption layer were described in detail in the above section “A. Pattern formation body 1. Absorption layer”, description thereof is omitted here.

(2) Transmission layer In the present invention, the formation method of the transmission layer is appropriately selected according to the material used for the transmission layer, for example, a coating liquid for forming a transmission layer is applied on the absorption layer. A method is mentioned. The coating method is not particularly limited as long as it is a method that can apply the coating liquid for forming the transmission layer over the entire surface of the absorption layer. For example, spin coating method, die coating method, roll coating method, bar coating method General methods such as dip coating, spray coating, blade coating, gravure printing, slit coating, ink jet, and flexographic printing can be used.

  The characteristics, material, thickness, and the like of the transmissive layer are described in detail in the above section “A. Pattern formation body 2. transmissive layer”, and thus the description thereof is omitted here.

  Moreover, it is preferable that the surface of the transmission layer has liquid repellency. When the surface of the transmissive layer has liquid repellency, the permeable layer may contain a liquid repellant material, or may have a surface that has been subjected to a liquid repellency treatment, and is a self-assembled film. Also good.

  When forming a permeable layer containing a liquid repellent material, the method for applying the transmissive layer forming coating liquid can be used as a method for forming the transmissive layer.

In the case of forming a permeable layer whose surface is lyophobic, the lyophobic treatment is not particularly limited as long as it is a method capable of imparting lyophobicity to the surface of the transmissive layer. A fluorine plasma treatment in which plasma is used as an introduction gas can be given.
Examples of the fluorine compound used as the introduction gas include CF ₄ , NF ₃ , SF ₆ , CHF ₃ , C ₂ F ₆ , C ₃ F ₈ , and C ₅ F ₈ .
The introduced gas may be a mixture of a fluorine compound and another gas. As other gas, nitrogen, oxygen, argon, helium etc. can be mentioned, for example.
The plasma irradiation method is not particularly limited as long as it is a method capable of irradiating plasma using a fluorine compound as an introduction gas and imparting liquid repellency to the surface of the transmission layer. Plasma irradiation is performed under reduced pressure. Alternatively, plasma irradiation may be performed under atmospheric pressure. Atmospheric pressure plasma is advantageous in terms of cost and production efficiency.

  The presence of fluorine introduced to the surface of the transmission layer can be confirmed by measuring the ratio of the elemental fluorine in all elements detected from the surface of the transmission layer in the analysis by the X-ray photoelectron spectrometer.

  When the repellency treatment is performed on the surface of the transmissive layer, the repellency treatment is preferably performed so that the contact angle with the liquid on the transmissive layer surface is within a predetermined range. The contact angle with the liquid on the surface of the transmissive layer is described in the above section “A. Pattern forming body 2. transmissive layer”, and thus the description thereof is omitted here.

  Further, as the self-assembled film, a self-assembled monomolecular film, a Langmuir-Blodgett film, and an alternately adsorbed film can be used, and the formation method thereof is described in, for example, JP-A No. 2003-195029. The method that can be applied.

2. Patterning Step The patterning step in the present invention is a step of irradiating the absorbing layer in a pattern from the transmitting layer side, removing the transmitting layer in a pattern by laser ablation, and exposing the absorbing layer.

  The wavelength of the ultraviolet laser is not particularly limited as long as it can be transmitted through the transmission layer and absorbed by the absorption layer, and laser ablation can be caused by irradiating the absorption layer with the ultraviolet laser, but is usually 365 nm or less. In particular, it is preferably in the range of 190 nm to 355 nm, particularly in the range of 248 nm to 355 nm.

As the ultraviolet laser, for example, an excimer laser (F ₂ , ArF, KCl, KrF, XeCl, XeF, etc.), a YAG laser, or the like can be used.

  Also, the irradiation amount of the ultraviolet laser is such that the transmission layer can be removed by laser ablation by irradiating the absorption layer from the transmission layer side, and the absorption layer of the irradiated portion can be left. There is no particular limitation as long as it is present.

  The irradiation time of the ultraviolet laser is preferably relatively short. This is because if the irradiation time is long, the absorption layer in the irradiated portion may be removed. Therefore, it is preferable to use a high-power ultraviolet laser.

  When the absorption layer is irradiated with an ultraviolet laser from the transmission layer side in a pattern, the ultraviolet laser may be irradiated through a mask, or the ultraviolet laser may be condensed and irradiated.

  When the ultraviolet laser is irradiated, the temperature of the laminated body of the absorption layer and the transmissive layer is not particularly limited, but it is preferable to irradiate the ultraviolet laser while heating the laminated body of the absorption layer and the transmissive layer. This is because laser ablation is likely to occur. The heating temperature is not particularly limited as long as laser ablation is likely to occur. Specifically, the heating temperature is preferably in the range of 50 ° C to 150 ° C.

3. Lipophilic treatment step In the present invention, after the patterning step, a lyophilic treatment step of performing a lyophilic treatment on the exposed absorbent layer surface may be performed.

  The lyophilic treatment is not particularly limited as long as it is a method capable of imparting lyophilicity only to the exposed absorption layer surface. For example, UV-ozone treatment, vacuum ultraviolet treatment, lyophilic treatment on the absorption layer surface. For example, a plasma treatment in which plasma is irradiated using a compound capable of imparting properties as an introduction gas may be used. Among them, the lyophilic treatment is preferably a method using ultraviolet rays such as UV-ozone treatment and vacuum ultraviolet treatment. Since the transmission layer transmits ultraviolet rays, even when UV-ozone treatment or vacuum ultraviolet treatment is applied to the entire surface of the transmission layer and the exposed absorption layer, the surface of the transmission layer is not lyophilic, and only the exposed absorption layer surface is treated as the parent layer. This is because it can be liquefied and the lyophilic treatment can be performed with high accuracy and efficiency.

In the UV-ozone treatment, oxygen or air that generates ozone can be used.
The UV-ozone treatment may be performed on the entire surface of the transmission layer and the absorption layer, or may be performed only on the surface of the absorption layer exposed through the mask, but is preferably performed on the entire surface of the transmission layer and the absorption layer. As described above, since the transmission layer transmits ultraviolet rays, only the exposed absorption layer surface can be lyophilic even when the entire surface of the transmission layer and absorption layer is subjected to UV-ozone treatment.

  In addition, the vacuum ultraviolet treatment may be performed on the entire surface of the transmission layer and the absorption layer as in the case of the UV-ozone treatment, or may be performed only on the surface of the absorption layer exposed through the mask. Is preferably applied to the entire surface.

In the plasma treatment, the compound used as the introduction gas may be any compound that can impart lyophilicity only to the surface of the absorption layer, and examples thereof include oxygen, nitrogen, argon, and helium.
The plasma treatment may be performed on the entire surface of the transmission layer and the absorption layer, or may be performed only on the surface of the absorption layer exposed through the mask, but is preferably performed only on the surface of the absorption layer exposed through the mask. This is because the liquid repellency of the surface of the transmissive layer can be maintained.

  When the exposed absorbent layer surface is subjected to a lyophilic treatment, the lyophilic treatment is preferably performed so that the contact angle between the exposed absorbent layer surface and the liquid is within a predetermined range. The contact angle between the exposed surface of the absorbing layer and the liquid is described in the above section “A. Pattern forming body 1. Absorbing layer”, and thus the description thereof is omitted here.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

  The following examples illustrate the present invention in more detail.

[Example 1]
First, a 5 wt% toluene solution of a styrene polymer (198-12805 manufactured by Wako Pure Chemical Industries, Ltd.) is applied as an absorption layer on a polycarbonate film (manufactured by Teijin Ltd.) with a spin coater (MS-A200 manufactured by Mikasa) and dried to a thickness. A 1 μm film was formed. The contact angle meter (PCA-1 manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the contact angle of pure water on the surface of the absorption layer, and the result was 80 °. The transmittance of the absorption layer at a wavelength of 248 nm was 40%.
Next, Cytop (registered trademark) (CTX-809AP manufactured by Asahi Glass Co., Ltd.) was applied as a transmission layer on the surface of the absorption layer with a spin coater and dried to form a 20 nm thick film. The contact angle meter (PCA-1 manufactured by Kyowa Interface Science Co., Ltd.) measured the contact angle of pure water on the surface of the transmission layer was 110 °. In addition, the transmittance of the transmission layer at a wavelength of 190 nm to 380 nm was almost constant and was 95%.

Next, an excimer laser (manufactured by Tamarack) with a wavelength of 248 nm was irradiated from the transmission layer side of the above laminate with an output of 120 mW / cm ² to pattern the transmission layer by ablating the outermost layer of the absorption layer. As a result, a concavo-convex pattern depending on the presence or absence of the transmissive layer, which had different wettability patterns with a contact angle difference of 30 ° between the exposed absorption layer surface and the transmissive layer surface was formed.
Further, it was confirmed that the minimum line width by this patterning was 2 μm.

[Example 2]
In the patterns with different wettability obtained in Example 1, UV-ozone treatment was performed from the transmission layer side using a UV device (manufactured by TAKEDEN). When the contact angle of pure water on the surface of the absorption layer after UV-ozone treatment was measured with a contact angle meter (PCA-1 manufactured by Kyowa Interface Science Co., Ltd.), it was 20 °, and the wettability was improved only with the exposed absorption layer. As a result, patterns having different wettability with a difference in contact angle of 90 ° between the exposed absorption layer surface and the transmission layer surface were formed.

[Comparative Example 1]
First, in the same manner as in Example 1, an absorption layer was formed on a polycarbonate film (manufactured by Teijin Limited).
Next, the surface of the absorption layer was patterned by irradiating an excimer laser (manufactured by Tamarack) with a wavelength of 248 nm with an output of 120 mW / cm ² and ablating the outermost layer of the absorption layer. Thereby, the uneven | corrugated pattern was formed in the absorption layer surface.
It was confirmed that the minimum line width by this patterning was 2 μm. However, the contact angle between the concave and convex portions of the concave / convex pattern and the pure water was 80 °, and patterns having different wettability were not obtained. From the comparative example 1, the effect which provides the permeation | transmission layer which has water repellency on the absorption layer has been confirmed.

[Comparative Example 2]
First, Cytop (registered trademark) (CTX-809AP manufactured by Asahi Glass Co., Ltd.) is applied to the surface of a 0.7 mm thick glass substrate (OA10 manufactured by Nippon Electric Glass) with a spin coater and dried to form a 20 nm thick transmission layer. Formed. The contact angle meter (PCA-1 manufactured by Kyowa Interface Science Co., Ltd.) measured the contact angle of pure water on the surface of the transmission layer was 110 °. In addition, the transmittance of the transmission layer at a wavelength of 190 nm to 380 nm was almost constant and was 95%.
Next, an excimer laser (manufactured by Tamarack) with a wavelength of 248 nm was irradiated on the surface of the transmission layer with an output of 120 mW / cm ² , but ablation as in Example 1 and Comparative Example 1 did not occur. This is because the transmissive layer absorbs ultraviolet light having a wavelength of 248 nm, which is very weak at less than 10%, and the output is insufficient for ablation of the glass substrate. Comparative Example 2 confirmed the effect of introducing a layer that easily causes ablation as the base layer of the transmission layer.

DESCRIPTION OF SYMBOLS 1 ... Pattern formation body 2 ... Board | substrate 3 ... Absorption layer 4 ... Transmission layer L ... Ultraviolet laser

Claims (4)

A lamination step of laminating a transmission layer that transmits ultraviolet light on an absorption layer that absorbs ultraviolet light;
A patterning process comprising: irradiating the absorbing layer in a pattern from the transmitting layer side, removing the transmitting layer in a pattern by laser ablation, and exposing the absorbing layer Body manufacturing method. The method for producing a pattern forming body according to claim 1 , wherein the exposed surface of the absorption layer has lyophilicity and the surface of the transmission layer has liquid repellency. The method for producing a pattern forming body according to claim 1 , further comprising a lyophilic process step of performing a lyophilic process on the exposed surface of the absorption layer after the patterning process. The method for producing a pattern forming body according to any one of claims 1 to 3, wherein the absorption layer and the transmission layer have insulating properties .

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