JP5428449B2 - Method for producing master plate for producing stamp for micro contact printing, and master plate for producing stamp for micro contact printing - Google Patents

Description

  The present invention relates to a master plate for producing a microcontact printing stamp used for manufacturing a microcontact printing stamp (hereinafter referred to as “μCP stamp”) used in a microcontact printing (hereinafter referred to as “μCP”) method. The following relates to a “manufacture plate for μCP stamp production”) and a μCP stamp manufacturing method.

  Among various ultra-fine processes that can be used as patterning techniques for microstructures and nanostructures, soft lithography is employed in many studies. “Soft lithography” is a patterning technique that uses a pattern elastomer, a template or a mask as a stamp to create a micropattern, microstructure or nanopattern, or nanostructure. Examples of such soft lithography include micro contact printing, replication molding, ultra-fine transfer molding, ultra-fine molding using capillary phenomenon, ultra-fine molding using a solvent, phase shift photolithography, casting molding, emboss molding, injection molding. However, in recent years, since it is possible to print a fine pattern on the nano order with high accuracy, it has been considered to use microcontact printing in a method for manufacturing a semiconductor element. ing.

  Here, the microcontact printing (μCP) method is a method of G. M.M. This is a fine patterning technology developed by Whitesides et al. “Plate”, which is a pattern made by photolithography on a silicon or quartz substrate and mastered with silicone rubber called polydimethylsiloxane (heat-curing PDMS) Is a technique for printing a fine pattern up to several tens of nanometers in size. Such a μCP method is disclosed in, for example, Patent Documents 1 and 2.

JP 2002-206033 A JP 2002-353436 A

  In micro contact printing (μCP), printing is performed in the same pattern as the stamp used. Accordingly, in order to perform a desired pattern printing by the μCP method, it is indispensable to manufacture a stamp having the pattern with high accuracy. The μCP stamp used in the μCP method is generally manufactured by the following method. First, using a master plate for stamp production for μCP in which a predetermined fine concavo-convex pattern is formed, an application step of applying an elastomer such as PDMS (polydimethylsiloxane) on the master plate, and using an arbitrary support material, A shape in which the concave and convex shape of the master plate is reversed on the surface of the support material by an adhesion process for bonding the support material on the coated elastomer film and a peeling process for peeling the elastomer film from the master plate. A method of manufacturing a stamp for μCP in which a PDMS layer having the above pattern is formed is used. According to such a method, the stamp for μCP on which nano-order fine irregularities are formed can be manufactured by a relatively simple process.

  A method of manufacturing such a μCP stamp will be described with reference to the drawings. FIG. 6 is a schematic view showing an example of a method for manufacturing the above-described μCP stamp. As illustrated in FIG. 6, a μCP stamp production master plate 200 in which a predetermined fine concavo-convex pattern is formed is usually used as the μCP stamp (FIG. 6A), and the μCP stamp production master plate is used. An application step of applying an elastomer such as PDMS (polydimethylsiloxane) on 200 (FIG. 6B), and using an arbitrary support material 102, the support material 102 is adhered onto the applied elastomer film 101 (FIG. 6C), and a peeling step of peeling the PDMS film 101 and the support material 102 from the μCP stamp producing master plate 200 (FIG. 6D). And a method of manufacturing a μCP stamp 100 having a PDMS layer 101 having a concavo-convex pattern obtained by inverting the concavo-convex shape of the master plate on the surface. (FIG. 6E).

  As described above, when performing the μCP method, it is necessary to first prepare a stamp for μCP having a desired uneven shape, and as a premise thereof, for μCP in which the desired uneven shape is formed in a pattern. The premise is that a master plate for stamp production can be produced. Here, as a method of manufacturing a master plate for μCP stamp production, a method of forming a fine concavo-convex shape on the surface by etching a silicon substrate in a pattern has been conventionally used. However, in the future, such a method has various problems in making the μCP method highly versatile as a patterning technique for microstructures and nanostructures. Some examples are listed below.

  First, in order to make the μCP method highly versatile, it is essential to be able to realize pattern printing in a large area. This is indispensable for the future application of the μCP method to a method for manufacturing display members and the like. As described above, the method for producing the μCP stamp is performed by forming the concave and convex shape of the master plate for producing the μCP stamp on the elastomer film. Therefore, in order to produce the μCP stamp with a large area, Prior to that, it is necessary to produce a master plate for producing a stamp for μCP in a large area. However, in the method of forming a fine concavo-convex shape on the surface by etching the silicon substrate into a pattern, there is a limit to increasing the area due to restrictions such as the size of the silicon substrate.

  Second, the method of etching a silicon substrate in a pattern has a problem that the etching depth varies depending on the line width of the pattern to be etched due to the so-called microloading effect. This point will be described with reference to the drawings. FIG. 7 is a schematic diagram for explaining the above problem. As illustrated in FIG. 7, when the μCP stamp production master plate 200 is produced by etching a silicon substrate in a pattern, the etched depth has a corresponding relationship with the line width due to the microloading effect. Therefore, the recess a having a narrow line width has a shallower etching depth, and the recess b having a wide line width has a deeper etching depth. For this reason, in the μCP stamp manufactured by using the μCP stamp manufacturing master plate manufactured by such a method, the height of the convex portion to which the ink adheres differs depending on the line width. As a result, when a pattern is printed using the μCP stamp, only a pattern having a higher line width is printed, and a pattern having a lower line width is not printed. There is a problem. In particular, in the pattern printing in the μCP method, such a problem is remarkable because the pressing of the stamp is weaker than that of the normal stamp method.

Third, the master plate for stamp production for μCP produced by the method of etching the silicon substrate in a pattern is often roughened on the wall surface and bottom surface of the etched etching surface, depending on the etching method. As a result, the μCP stamp manufactured using the μCP stamp manufacturing master plate has a problem in that the top and wall surfaces of the protrusions become rough. Here, the top of the stamp for μCP is an area used to transfer ink. If the surface of the area is rough, the amount of ink transferred will vary, realizing uniform pattern printing. There is a problem that it becomes difficult to do. In particular, since the μCP method performs pattern printing by transferring 100% of the ink adhered to the μCP stamp, such a problem occurs remarkably.
Further, the wall surface and the bottom surface become rough, so that it becomes difficult to release the mold after releasing the PDMS. In particular, this difficulty becomes more prominent as the pattern irregularities become higher in definition.

  Further, in the method of etching a silicon substrate other than the above, since it is essential to use an expensive and special apparatus such as a stepper, it is difficult to make the μCP method highly versatile by such a method. There was a problem of being.

  The present invention has been made in view of these problems, and is for producing a stamp for μCP capable of producing a stamp for μCP capable of performing uniform pattern printing in a large area by a simple method. The main purpose is to provide a method for producing a master plate.

  In order to solve the above-mentioned problems, the present invention uses a substrate and forms a light-shielding portion on the substrate and forms a light-shielding portion on the substrate, and a photosensitive resin made of a photosensitive resin on the substrate so as to cover the light-shielding portion. A photosensitive resin film forming step for forming a photosensitive resin film, an exposure step for pattern exposure to the photosensitive resin film by irradiating light from the substrate side, and developing the photosensitive resin film subjected to the pattern exposure. Thus, a method for producing a master plate for producing a stamp for microcontact printing, comprising a development step of patterning the photosensitive resin film is provided.

In the present invention, by using a method of forming a concavo-convex shape using a resist, it becomes possible to manufacture a master plate for producing a large-area μCP stamp by a simple method.
Further, in the present invention, light is irradiated from the substrate side in the exposure step, and pattern exposure corresponding to the pattern of the light shielding portion is performed on the photosensitive resin film, so that the pattern is uniform regardless of the line width of the pattern. Uneven shape can be formed with a sufficient depth. Furthermore, by using such an exposure method, in the present invention, the photosensitive resin film can be processed into a pattern having a smooth surface. For this reason, according to the present invention, a master plate for making a stamp for μCP capable of producing a stamp for μCP having a uniform height and a smooth surface regardless of the line width of the pattern is manufactured. Can do.
Therefore, according to the present invention, a master plate for μCP stamp production capable of producing a stamp for μCP capable of performing uniform pattern printing with a large area can be manufactured in a simple process. .

  In this invention, it is preferable that the said photosensitive resin used for the said photosensitive resin film formation process is a negative photosensitive resin. The master plate for making a stamp for μCP manufactured according to the present invention is formed in a pattern on a substrate and has a photosensitive resin layer made of a photosensitive resin. As the photosensitive resin, a negative photosensitive resin is used. Is used, the shape of the photosensitive resin layer can be tapered so that the line width becomes narrower from the substrate side to the surface with reference to the thickness direction (hereinafter referred to as “forward taper shape”). For this reason, when the μCP stamp is manufactured using the μCP stamp manufacturing master plate manufactured according to the present invention, it is easy to peel the μCP stamp from the master plate. is there.

  The present invention includes a substrate, a photosensitive resin layer formed in a pattern on the substrate and made of a photosensitive resin, and a light shielding portion formed on the substrate surface on which the photosensitive resin layer is not formed. A master plate for producing a stamp for microcontact printing is provided.

According to the present invention, the uneven shape formed when manufacturing the stamp for μCP is made of the photosensitive resin layer, and the light-shielding portion is arranged at the bottom of the pattern formed by the photosensitive resin layer. By having the configuration, the height of the photosensitive resin layer can be uniform regardless of the line width, and the surfaces of the photosensitive resin layer and the light shielding portion can be smooth.
Further, the master plate for making a μCP method stamp of the present invention can have a large area by having such a configuration.
Therefore, according to the master plate for producing a stamp for μCP of the present invention, a stamp for μCP capable of performing a uniform pattern printing in a large area can be manufactured.

  In the present invention, the photosensitive resin layer is preferably formed so that the line width on the substrate side is wider than the line width on the surface side with respect to the thickness direction. This is because, when a μCP stamp is manufactured using the μCP stamp manufacturing master plate of the present invention, it is easy to peel the μCP stamp from the μCP stamp manufacturing master plate.

  In the present invention, the photosensitive resin is preferably a negative photosensitive resin. This is because it becomes easy to form the photosensitive resin layer in the forward tapered shape as described above.

  Furthermore, the present invention uses a master plate for microcontact printing stamp preparation with a micro uneven pattern formed on the surface, and polydimethyl on the surface on which the micro uneven pattern of the micro contact printing stamp preparation master plate is formed. From a coating process for applying siloxane (PDMS), a bonding process for bonding the support material onto the applied polydimethylsiloxane (PDMS) film using a support material, and a master plate for making a microcontact printing stamp A method for producing a stamp for microcontact printing (μCP), comprising: a peeling step for peeling the polydimethylsiloxane (PDMS) film and the support material, wherein the master plate for making a microcontact printing stamp is a substrate. And a photosensitive resin layer formed in a pattern on the substrate and made of a photosensitive resin, and a light-shielding portion formed on the substrate surface on which the photosensitive resin layer is not formed. The manufacturing method of the stamp for micro contact printing characterized by these.

  According to the present invention, as the master plate for μCP stamp production, a substrate, a photosensitive resin layer formed in a pattern on the substrate and made of a photosensitive resin, and the photosensitive resin layer are not formed. By using what has the light-shielding part formed on the said substrate surface, the stamp for (micro | micron | mu) CP which can perform uniform pattern printing with a large area can be manufactured.

  The method for producing a master plate for producing a stamp for μCP according to the present invention is a simple process for producing a master plate for producing a stamp for μCP, which can produce a stamp for µCP capable of performing uniform pattern printing in a large area. The effect that it can be manufactured is produced.

It is the schematic which shows an example about the manufacturing method of the master plate for micro stamp creation for μCP of the present invention. It is a schematic sectional drawing which shows an example of the master plate for stamp production for μCP manufactured by the manufacturing method of the master plate for stamp production for μCP of the present invention. It is a schematic sectional drawing which shows the other example of the master plate for stamp production for μCP manufactured by the manufacturing method of the master plate for stamp production for μCP of the present invention. It is a schematic sectional drawing which shows an example of the master plate for stamp production for μCP of the present invention. It is the schematic which shows an example of the manufacturing method of the stamp for μCP of this invention. It is the schematic explaining the manufacturing method of the stamp for μCP. It is the schematic which shows an example of the master plate for stamp production for μCP manufactured by the conventional method.

The present invention relates to a method for producing a master plate for μCP stamp production, a master plate for μCP stamp production, and a method for producing a μCP stamp.
Hereinafter, these inventions will be described in order.

A. First, a method for producing a master plate for μCP stamp production according to the present invention will be described. As described above, the manufacturing method of the master plate for μCP stamp production according to the present invention uses a substrate and forms a light-shielding portion on the substrate to form a light-shielding portion in a pattern shape, and covers the light-shielding portion. A photosensitive resin film forming step of forming a photosensitive resin film made of a photosensitive resin on the substrate; an exposure step of performing pattern exposure on the photosensitive resin film by irradiating light from the substrate side; and the pattern exposure. And developing a step of patterning the photosensitive resin film by developing the photosensitive resin film formed.

  A method for producing such a master plate for producing a stamp for μCP of the present invention will be described with reference to the drawings. FIG. 1 is a schematic view for explaining an example of a method for producing a master plate for producing a μCP stamp according to the present invention. As illustrated in FIG. 1, the method for manufacturing a master plate for μCP stamp production according to the present invention uses a substrate 1 (FIG. 1A), and forms a light-shielding portion 2 having a pattern on the substrate 1. Part forming step (FIG. 1B), and a photosensitive resin film forming step of forming a photosensitive resin film 3 made of a photosensitive resin on the substrate 1 so as to cover the light shielding part 2 (FIG. 1C )), An exposure process for pattern exposure of the photosensitive resin film 3 by irradiating light to the photosensitive resin film 3 from the substrate 1 side (FIG. 1 (d)), and the photosensitivity subjected to the pattern exposure. And developing the resin film 3 to pattern the photosensitive resin film 3 (FIG. 1E).

In the present invention, a master plate for stamp production for μCP having a large area can be manufactured by using a method of forming a concavo-convex shape using a resist. Therefore, according to the present invention, a large-area μCP stamp can be manufactured. In addition to this, the method for producing a master plate for μCP stamp production according to the present invention has an advantage that it can be carried out by a simple method.
Further, in the present invention, light is irradiated from the substrate side in the exposure step, and pattern exposure corresponding to the pattern of the light-shielding portion is performed on the photosensitive resin film. A uniform uneven shape can be formed. Furthermore, by using such an exposure method, an uneven shape having a smooth surface can be formed in the present invention. For this reason, according to the present invention, a master plate for making a stamp for μCP capable of producing a stamp for μCP having a uniform height and a smooth surface regardless of the line width of the pattern is manufactured. Can do.
Therefore, according to the present invention, it is possible to manufacture a master plate for stamp production for μCP capable of producing a stamp for μCP capable of performing uniform pattern printing with a large area.

The manufacturing method of the master plate for μCP stamp production of the present invention includes at least the light shielding part forming step, the photosensitive resin film forming step, the exposure step, and the developing step, and other optional steps as necessary. It may have.
Hereinafter, these steps in the present invention will be described in order.

1. First, the light shielding part forming process in the present invention will be described. As described above, this step is a step of using a substrate and forming a patterned light shielding portion on the substrate. The method for forming the light shielding part in this step is not particularly limited as long as it can form the light shielding part with a desired pattern. Therefore, for example, a light shielding material may be used to form a patterned light shielding portion by directly applying a light shielding material in a pattern on the substrate, or a light shielding layer made of a light shielding material on the substrate. A method of forming a patterned light-shielding portion by etching the light-shielding layer into a predetermined pattern after forming the film. In this step, any of these methods can be suitably used, and which method should be used may be appropriately determined according to the type of the light shielding material to be used.

Examples of the light shielding material used for forming the light shielding part in this step include those made of metal and those made of a resin composition. Examples of the light shielding material made of metal include Cr, Al, Ni, Ti, Cu, or Ag.
On the other hand, examples of the light shielding material comprising the resin composition include a photosensitive resin in which a black light shielding pigment such as carbon black or titanium black is dispersed.

  The thickness of the light-shielding portion formed in this step is within a range in which the light-shielding property to the extent that the light irradiated from the substrate side can be shielded in the exposure step described later can be achieved depending on the type of the light-shielding material. There is no particular limitation. But the thickness of the light-shielding part formed in this process is usually in the range of 50 nm to 3000 nm. More specifically, the thickness is preferably 50 nm to 150 nm in formation by metal vapor deposition or sputtering, and in the resin system, it is preferably in the range of 1000 nm to 2000 nm.

  The pattern of the light shielding portion formed in this step is appropriately determined according to the use of the μCP stamp manufactured using the μCP stamp manufacturing master plate manufactured according to the present invention.

  Next, the board | substrate used for this process is demonstrated. The substrate used in this step is not particularly limited as long as it can transmit light used for pattern exposure of the photosensitive resin film in an exposure step described later. As long as the substrate has such light transmittance, a substrate made of an inorganic material such as glass or quartz may be used, or a substrate made of a resin material may be used.

2. Photosensitive resin film forming step Next, the photosensitive resin film forming step in this step will be described. This step is a step of forming a photosensitive resin film made of a photosensitive resin on the substrate so as to cover the light shielding portion formed in the light shielding portion forming step.

  The photosensitive resin used for forming the photosensitive resin film in this step has a desired durability by being subjected to pattern exposure in an exposure step described later and then patterned in a development step described later. There is no particular limitation as long as the photosensitive resin layer can be formed. Here, the master plate for making a stamp for μCP manufactured according to the present invention is repeatedly used for making a stamp for μCP. Therefore, the photosensitive resin layer formed by the photosensitive resin has a CP In addition to resistance to elastomers such as PDMS used in manufacturing a stamp for use, physical durability that can withstand repeated contact / peeling is required.

The photosensitive resin used in this step is not particularly limited as long as the photosensitive resin layer having the durability described above can be formed. Therefore, the photosensitive resin used in this step may be a positive photosensitive resin or a negative photosensitive resin. Examples of the positive photosensitive resin include novolak-based and polyimide-based photosensitive resins.
On the other hand, examples of the negative photosensitive resin include photosensitive resins such as epoxy, acrylic, polyimide, polyamide, cardo, novolac, PS, and PMMA.
In this step, any of these negative photosensitive resins and positive photosensitive resins can be suitably used, but among these, negative photosensitive resins are preferably used. By using a negative photosensitive resin as the photosensitive resin, the μCP stamp production master plate manufactured according to the present invention can easily have a photosensitive resin layer formed in a forward tapered shape. As a result, the master plate for producing a stamp for μCP produced according to the present invention can be made excellent in releasability when producing a stamp for μCP.

  Here, the case where the master plate for stamp production for μCP manufactured according to the present invention has a photosensitive resin layer formed in a forward taper shape will be described with reference to the drawings. FIG. 2 is a schematic cross-sectional view showing an example of a master for producing a stamp for μCP manufactured according to the present invention. As illustrated in FIG. 2, the master plate 10 for μCP stamp production manufactured according to the present invention includes a substrate 1 and a photosensitive resin layer 3 ′ formed on the substrate 1 in a pattern and made of a photosensitive resin. And the light-shielding portion 2 formed on the surface of the substrate 1 where the photosensitive resin layer 3 is not formed. The photosensitive resin layer 3 ′ is on the substrate 1 side with respect to the thickness direction. It is preferable that the line width is formed so as to be wider than the line width on the surface side.

  Here, in the present invention, as described above, a state in which the line width on the substrate side is wider than the line width on the surface side with reference to the thickness direction is referred to as “forward taper shape”. On the other hand, a state in which the line width on the substrate side is narrower than the line width on the surface side with respect to the thickness direction is referred to as “reverse taper shape”.

Next, the reason why it is easy to manufacture a master plate for μCP stamp production in which a tapered photosensitive resin layer is formed in the present invention by using a negative photosensitive resin as the photosensitive resin used in this step is as follows. It is as follows.
That is, in the exposure process in the present invention, the photosensitive resin film is irradiated with light from the substrate side. Since the light shielding part is formed in a pattern on the substrate, pattern exposure is performed on the photosensitive resin film corresponding to the pattern of the light shielding part.
When a negative photosensitive resin is used as the photosensitive resin film, the portion irradiated with light in the development process remains without being selectively removed, but the region where the amount of light irradiation is large is more sure. Even in the region where the photosensitive resin film remains and the amount of light irradiation is small, a part of the photosensitive resin film is removed by development. Then, in the exposure process of the present invention, since exposure is performed from the substrate side, by controlling the amount of light irradiation, the region closer to the substrate in the region of the photosensitive resin film irradiated with light is exposed to light. Because it is sufficiently irradiated, it is difficult to be removed by development, while the area near the surface relatively reduces the amount of light irradiated due to the light attenuation effect, and the photosensitive resin film is partially removed easily. be able to.
For this reason, by using a negative photosensitive resin as the photosensitive resin, it becomes easy to manufacture a master plate for stamp production for μCP in which a forward-tapered photosensitive resin layer is formed.

  In this step, the method for forming the photosensitive resin film on the substrate so as to cover the light shielding portion is not particularly limited as long as the method can form a photosensitive resin film having a smooth surface. As such a method, for example, a resist solution in which a photosensitive resin is dissolved, spin coating method, blade coating method, bar coating method, slit coating method, die coating method, roll coating method, dip coating method, spray coating method, The method of apply | coating by the dispenser method etc. can be mentioned.

  In addition, the thickness of the photosensitive resin film formed in this step can be appropriately determined according to the application of the μCP stamp manufactured using the μCP stamp manufacturing master plate manufactured according to the present invention. It is a thing and is not specifically limited. However, the thickness of the photosensitive resin film corresponds to the height of the photosensitive resin layer in the master plate for μCP stamp production manufactured according to the present invention, and the height is determined using the master plate for μCP stamp production. This corresponds to the height of the convex portion of the produced μCP stamp. Therefore, if the thickness of the photosensitive resin film is small, the height of the convex portion of the μCP stamp manufactured using the μCP stamp manufacturing master plate manufactured according to the present invention is lowered, and in some cases, when pattern printing is performed. There is a possibility that a problem of so-called 'soil stains' occurs in which ink adheres to regions other than the convex portions. On the other hand, if the thickness of the photosensitive resin film is too large, the height of the convex portions in the μCP stamp becomes too high, and adjacent convex portions come into contact with each other, making it difficult to print according to a desired pattern. There is a possibility that. From such a viewpoint, the thickness of the photosensitive resin film formed in this step is preferably in the range of 100 nm to 100 μm, more preferably in the range of 500 nm to 50 μm, and 1 μm to 10 μm. More preferably, it is within the range. When the thickness of the photosensitive resin film is in the above range, when pattern printing is performed using the μCP stamp manufactured using the μCP stamp manufacturing master plate manufactured according to the present invention, the “background stain” This is because 'can be prevented and printing according to the pattern can be performed reliably.

3. Exposure Step Next, the exposure step in the present invention will be described. This step is a step of pattern exposure of the photosensitive resin film by irradiating light from the substrate side to the photosensitive resin film formed on the substrate. Since the pattern-shaped light shielding portion is formed on the substrate in the above-described light shielding portion forming step, the photosensitive resin film is exposed in a pattern corresponding to the pattern of the light shielding portion in this step. Become.

  In this step, the method of exposing the photosensitive resin film is not particularly limited as long as it is a method of exposing from the substrate side. About the light source used for exposure, it will be suitably determined according to the kind of photosensitive resin which comprises the said photosensitive resin film.

  In addition, the amount of light irradiated to the photosensitive resin film in this step is set according to the type of the photosensitive resin constituting the photosensitive resin film. The solubility is appropriately adjusted so that the solubility can be changed to a desired level. Here, as described above, when the photosensitive resin film is made of a negative photosensitive resin, the substrate side of the photosensitive resin film of the portion irradiated with light is utilized by utilizing the light attenuation effect. By adjusting the amount of light irradiation so that more light is irradiated than on the surface side, a forward-tapered photosensitive resin layer can be formed.

4). Development Step Next, the development step in this step will be described. This step is a step of patterning the photosensitive resin film by developing the photosensitive resin film subjected to pattern exposure in the exposure step. The method for developing the photosensitive resin film in this step is appropriately determined according to the type of the photosensitive resin constituting the photosensitive resin film, and is not particularly limited. As such a method, generally known methods can be used as a method for developing the photosensitive resin film.

5. Optional Process The manufacturing method of the master plate for μCP stamp production according to the present invention includes at least the light shielding part forming process, the photosensitive resin film forming process, the exposure process, and the developing process. It may have an optional step. The optional step used in the present invention is not particularly limited as long as it can impart a desired function to the master plate for μCP stamp production manufactured according to the present invention.

6). Next, a master plate for μCP stamp production manufactured according to the present invention will be described. As described above, the master plate for making a stamp for μCP manufactured by the present invention by having the light shielding part forming step, the photosensitive resin film forming step, the exposure step and the developing step is a pattern on the substrate and the substrate. The light shielding portion is formed in a pattern, and the photosensitive resin layer is formed in a pattern on the substrate and made of a photosensitive resin. Here, the master plate for making a stamp for μCP manufactured according to the present invention has a positional relationship between the light shielding portion and the photosensitive resin layer depending on whether the photosensitive resin is a negative photosensitive resin or a positive photosensitive resin. It will be divided into two modes.
That is, when a negative photosensitive resin is used as the photosensitive resin, the master plate for μCP stamp production manufactured according to the present invention includes a substrate, and a photosensitive resin layer formed in a pattern on the substrate. And a light-shielding portion formed in a pattern in a region where the photosensitive resin layer of the substrate is not formed. On the other hand, when a positive photosensitive resin is used as the photosensitive resin, the master plate for making a stamp for μCP manufactured according to the present invention includes a substrate, a light shielding portion formed in a pattern on the substrate, And a photosensitive resin layer formed only on the light shielding portion.

As described above, the fact that the master plate for stamp production for μCP produced according to the present invention has two aspects will be described with reference to the drawings. FIG. 3 is a schematic sectional view showing an example of a master plate for making a stamp for μCP manufactured according to the present invention. As described above, when a negative photosensitive resin is used in the photosensitive resin film forming step, the μCP stamp producing master plate 10 manufactured according to the present invention has a pattern on the substrate 1 and the substrate 1. A photosensitive resin layer 3 ′ formed of a photosensitive resin and a light shielding portion 2 formed in a pattern in a region where the photosensitive resin layer 3 ′ of the substrate 1 is not formed ( FIG. 3 (a)).
On the other hand, when a positive photosensitive resin is used in the photosensitive resin film forming step, the μCP stamp producing master plate 10 manufactured according to the present invention is formed in a pattern on the substrate 1 and the substrate 1. The light-shielding part 2 and the photosensitive resin layer 3 ′ made of a photosensitive resin formed only on the light-shielding part 2 (FIG. 3B).

  In addition, the master plate for producing a stamp for μCP manufactured according to the present invention can have a larger area than the conventional one. In the conventional method of etching a silicon substrate in a pattern, since the size of the silicon substrate is limited, only a master plate of about 8 inches φ can be used at most. However, since there is no particular limitation on the size of the substrate that can be used in the present application, a master plate for producing a large-area μCP stamp having a desired area can be manufactured as necessary.

B. Next, the master plate for μCP stamp production according to the present invention will be described. As described above, the μCP stamp production master plate according to the present invention includes a substrate, a photosensitive resin layer formed in a pattern on the substrate, made of a photosensitive resin, and the photosensitive resin layer. And a light-shielding portion formed on the substrate surface.

  Such a master plate for producing a stamp for μCP of the present invention will be described with reference to the drawings. FIG. 4 is a schematic cross-sectional view showing an example of a master plate for producing a stamp for μCP of the present invention. As illustrated in FIG. 4, the μCP stamp production master plate 10 of the present invention includes a substrate 1, a photosensitive resin layer 3 ′ formed on the substrate 1 in a pattern and made of a photosensitive resin, and the photosensitive resin. And a light-shielding portion 2 formed on the surface of the substrate 1 on which the conductive resin layer 3 ′ is not formed.

According to the present invention, the uneven shape formed when manufacturing the stamp for μCP is made of the photosensitive resin layer, and the light-shielding portion is arranged at the bottom of the pattern formed by the photosensitive resin layer. By having the configuration, the height of the photosensitive resin layer can be uniform regardless of the line width, and the surfaces of the photosensitive resin layer and the light shielding portion can be smooth.
In addition, the master plate for making a μCP method stamp of the present invention can have a large area by having the above-described configuration.
Therefore, according to the present invention, a master plate for producing a stamp for μCP capable of producing a stamp for μCP capable of performing uniform pattern printing in a large area can be obtained.

The master plate for making a stamp for μCP of the present invention has at least a substrate, a light-shielding part and a photosensitive resin layer, and may have any other configuration as necessary.
Hereafter, each structure used for this invention is demonstrated in order.

1. Substrate First, the substrate used in the present invention will be described. The substrate used in the present invention is not particularly limited as long as it can support the light-shielding part and the photosensitive resin layer. For the use of the master plate for μCP stamp production of the present invention, the production method, etc. Any substrate can be used accordingly. As a board | substrate used for this invention, what consists of inorganic materials, such as glass and quartz, what consists of transparent resin, etc. can be mentioned, for example.

2. Photosensitive resin layer Next, the photosensitive resin layer in this invention is demonstrated. The photosensitive resin layer in the present invention is formed in a pattern on the substrate and is made of a photosensitive resin.

  About the photosensitive resin which comprises the photosensitive resin layer used for this invention, if the photosensitive resin layer which has desired durability can be formed, it will not specifically limit. Here, since the master plate for stamp production for μCP of the present invention is repeatedly used for fabricating the stamp for μCP, the photosensitive resin layer in the present invention is PDMS used for fabricating the stamp for μCP. In addition to resistance to an elastomer such as the above, physical durability that can withstand repeated contact and peeling is also required. Therefore, in the present invention, a photosensitive resin satisfying such required characteristics is appropriately selected and used.

  The photosensitive resin used in the present invention is not particularly limited as long as the photosensitive resin layer having the above-mentioned durability can be formed. Among these, a negative photosensitive resin is used. preferable. This is because a photosensitive resin layer having the durability described above can be formed by using a negative photosensitive resin. In addition, by using a negative photosensitive resin in the method for producing a μCP stamp production master plate according to the present invention, the photosensitive resin layer is formed in a forward taper shape as the μCP stamp production master plate of the present invention. It is because it becomes easy to manufacture what was manufactured.

  Here, the negative photosensitive resin is the same as that described in the section “A. Production method of master plate for stamp production for μCP”, and therefore the description thereof is omitted here.

  Further, the photosensitive resin layer in the present invention is formed so that the line width on the substrate side is wider than the line width on the surface side with respect to the thickness direction, that is, formed in a forward tapered shape. Is preferred. Since the photosensitive resin layer is formed in a forward tapered shape, the μCP stamp can be easily peeled off from the master plate when the μCP stamp master plate is prepared using the μCP stamp preparation master plate of the present invention. This is because it has the advantage of becoming.

  Furthermore, the height of the photosensitive resin layer in the present invention can be appropriately determined according to the use of the μCP stamp produced using the master plate for μCP stamp production of the present invention, and is particularly limited. Is not to be done. However, since the thickness of the photosensitive resin layer corresponds to the height of the convex portion of the μCP stamp produced using the master plate for μCP stamp production of the present invention, it is produced if the thickness is too small. In the μCP stamp, the height of the convex portion is lowered, and there is a possibility that a problem of so-called 'soil stains' may occur in which ink adheres to a region other than the convex portion when pattern printing is performed. . On the other hand, if the thickness of the photosensitive resin layer is too large, the height of the convex portion becomes too high in the μCP stamp produced using the master plate for μCP stamp production of the present invention, and adjacent convex portions are May come into contact with each other and it may become difficult to print in a desired pattern. From such a viewpoint, the thickness of the photosensitive resin layer in the present invention is preferably in the range of 100 nm to 100 μm, more preferably in the range of 500 nm to 50 μm, and in the range of 1 μm to 10 μm. More preferably it is. When the thickness of the photosensitive resin film is within the above-mentioned range, when the pattern printing is performed using the μCP stamp manufactured using the μCP stamp manufacturing master plate of the present invention, 'background stains' are generated. This is because it is possible to prevent this and to perform printing according to the pattern with certainty.

  In addition, the height of the photosensitive resin layer in the present invention is preferably uniform regardless of the line width of the photosensitive resin layer. Thereby, in the μCP stamp manufactured using the μCP stamp manufacturing master plate of the present invention, the height of the convex portion can be made uniform, so that the desired pattern can be accurately obtained using the μCP stamp. This is because it becomes possible to perform printing with this.

3. Next, the light shielding part used in the present invention will be described. The light-shielding portion used in the present invention is formed in a pattern on the substrate surface on which the photosensitive resin layer is not formed.

  The light-shielding part in the present invention is not particularly limited as long as it uses a light-shielding material and is formed in a manner that shields light of a predetermined wavelength to a desired extent. Here, as the light shielding material, the same materials as those described in the section of “A. Production method of master plate for producing μCP stamp” can be used.

  In addition, the thickness of the light shielding part in the present invention is not particularly limited as long as the desired light shielding property can be achieved according to the type of the light shielding material. In particular, the thickness of the light shielding part in the present invention is usually in the range of 50 nm to 3000 nm. More specifically, the thickness is preferably 50 nm to 150 nm in formation by metal vapor deposition or sputtering, and in the resin system, it is preferably in the range of 1000 nm to 2000 nm.

4). Arbitrary Configuration The master plate for making a μCP stamp of the present invention has at least a substrate, a photosensitive resin layer, and a light-shielding part, but may have other arbitrary configurations as necessary. . As an arbitrary configuration used in the present invention, a configuration having a predetermined function is appropriately selected and used for the purpose of improving manufacturing efficiency when manufacturing using the master plate for μCP stamp manufacturing of the present invention. Can do.

5. Master plate for μCP stamp preparation The master plate for μCP stamp preparation of the present invention can be of a large area because there are few restrictions on what is used as the substrate. For example, it is possible to achieve A4 size, or to realize a larger area if necessary.

6). Method for Producing Master Plate for μCP Stamp Production The master plate for μCP stamp production of the present invention can be produced, for example, by the method described in the above section “A. Method for producing master plate for μCP stamp production”. it can.

C. Next, a method for manufacturing a μCP stamp according to the present invention will be described. As described above, the μCP stamp manufacturing method of the present invention uses the micro contact printing stamp preparation master plate having a fine uneven pattern formed on the surface, and the micro contact printing stamp preparation master plate has fine unevenness. An application step of applying polydimethylsiloxane (PDMS) on the surface on which the pattern is formed; an adhesion step of adhering the support material on the applied polydimethylsiloxane (PDMS) film using a support material; A separation step of separating the polydimethylsiloxane (PDMS) film and the support material from the master plate for microcontact printing stamp production, wherein the master plate for microcontact printing stamp production is a substrate. And on the substrate A photosensitive resin layer formed of a photosensitive resin and having a light shielding portion formed on the substrate surface on which the photosensitive resin layer is not formed. It is.

A method for manufacturing the μCP stamp of the present invention will be described with reference to the drawings. FIG. 5 is a schematic view showing an example of a method for producing a μCP stamp of the present invention. As illustrated in FIG. 5, in the μCP stamp manufacturing method of the present invention, a μCP stamp manufacturing master plate 10 is used (FIG. 5A), and a PDMS film 21 is applied on the master plate 10. Application step (FIG. 1 (b)), using the support material 22, an adhesion step for adhering the support material 22 onto the applied PDMS film 21 (FIG. 1 (c)), from the master plate 10 to the above And a peeling step for peeling the PDMS film 21 and the support material 22 (FIG. 1D), and the μCP stamp 10 having the PDMS film 21 having an uneven shape formed on the surface on the support material 22. Is to be manufactured.
In such an example, the μCP stamp manufacturing method of the present invention is such that the μCP stamp producing master plate 10 is formed in a pattern on the substrate 1 and a photosensitive resin made of a photosensitive resin. It has a layer 3 ′ and a light-shielding portion 2 formed on the surface of the substrate 1 where the photosensitive resin layer 3 ′ is not formed.

  According to the present invention, as the master plate for μCP stamp production, a substrate, a photosensitive resin layer formed in a pattern on the substrate and made of a photosensitive resin, and the photosensitive resin layer are not formed. By using what has the light-shielding part formed on the said substrate surface, the stamp for (micro | micron | mu) CP which can perform a uniform pattern printing with a large area can be manufactured.

The μCP stamp manufacturing method of the present invention includes at least a coating process, an adhesion process, and a peeling process, and may include other processes as necessary.
Hereafter, each process used for the manufacturing method of the stamp for μCP of the present invention is explained in order.

1. Application Process First, the application process used in the present invention will be described. This step is a step of applying a PDMS film on the master plate using a master plate for μCP stamp production. Then, as the master plate for making the μCP stamp, a substrate, a photosensitive resin layer formed in a pattern on the substrate and made of a photosensitive resin, and on the surface of the substrate on which the photosensitive resin layer is not formed And a light-shielding portion formed on the substrate.

  In this step, the method of applying PDMS on the master plate for μCP stamp production is not particularly limited as long as it can form a PDMS film having a smooth surface on the master plate. Examples of such coating methods include spin coating, die coating, roll coating, bar coating, LB, dip coating, spray coating, blade coating, dispenser, and casting. Can do.

  Note that the master plate for μCP stamp preparation used in this step is the same as that described in the above section “B. Master plate for μCP stamp preparation”, and the description thereof is omitted here.

2. Next, the bonding process used in the present invention will be described. This step is a step of adhering a support material on the PDMS film formed on the master plate in the coating step described above.

  In this step, the mode of contacting the support material with the PDMS film is not particularly limited, and any mode can be used depending on the type of the support material. Such an embodiment may be an embodiment in which the surface of the support material and the surface of the PDMS film are kept in contact with each other while maintaining a parallel state, or in a state where both surfaces have a certain angle. It may be a mode of contact. In particular, the former mode is preferably used in this step. By bringing the surface of the support material and the surface of the PDMS film into contact with each other while maintaining a parallel state, the uneven pattern from the master plate to the PDMS plate can be obtained with high accuracy even in a nano-order ultra-fine uneven pattern. It is because it becomes possible to transcribe | transfer.

  In this step, after the support material and the PDMS film are brought into contact with each other, the support material may be pushed into the PDMS film side so that the PDMS film is further compressed with the support material. By performing such pushing, even if a very small amount of air bubbles are mixed between the support material and the PDMS film immediately after they are brought into contact with each other, it can be discharged afterwards. is there.

  The amount of pressing when the pressing is performed can be appropriately determined according to the thickness of the PDMS film, the area of the μCP stamp to be manufactured, and the like, and is not particularly limited. In particular, the indentation amount in this step is preferably within a range of 10 mm or less, more preferably within a range of 5 mm or less, and even more preferably within a range of 1 mm or less.

  In this step, the support material and the PDMS film are brought into contact with each other, and then the PDMS film is cured to be bonded. However, the method for curing the PDMS film is not particularly limited. Here, since the PDMS has a property of being cured by heating, the degree of curing depends on temperature and time. Therefore, when it is necessary to cure the PDMS film in a short time, after the PDMS film and the support material are brought into contact with each other, heat treatment may be performed to promote the curing of the PDMS film. On the other hand, when there is no restriction on the time for curing the PDMS film, it may be left at room temperature.

  Next, the support material used in this step will be described. The support material used in this step can be appropriately determined according to the application of the stamp for μCP produced according to the present invention, and is not particularly limited. Especially, it is preferable that the support material used for this invention is flat form. By using the substrate having such a shape, it is possible to transfer the concavo-convex pattern from the master plate to the PDMS plate with high accuracy even with a nano-order ultra-fine concavo-convex pattern.

  The support material used in the present invention preferably has a water contact angle of 5 ° to 45 °, more preferably 5 ° to 35 °, and a range of 5 ° to 30 °. More preferably, it is within. This is because, when the contact angle of the support material with respect to water is within the above range, bubbles can be prevented from being mixed between the substrate and the PDMS film in this step.

The supporting material used in this step may be a rigid substrate such as a glass substrate, a Si substrate, or a SiO ₂ substrate, or a flexible film such as a film made of a plastic resin. A flexible substrate may be used. Examples of the plastic resin include PET, PEN, PES, PI, PEEK, PC, PPS, and PEI.

  Moreover, the support material used in this step may be subjected to a surface treatment in order to make the contact angle with water within a certain range.

3. Peeling process Next, the peeling process used for this invention is demonstrated. This step is a step of peeling the PDMS film and the support material from the master plate. In this step, the method for peeling the PDMS film and the support material from the master plate is not particularly limited as long as the method can peel the pattern so as not to be lost. As such a method, a method of physically separating the PDMS film from the master plate is usually used.

4). Other Steps In the manufacturing method of the stamp for μCP of the present invention, at least the coating step, the bonding step, and the peeling step are used. In the present invention, any other steps other than these are used. Also good. The optional step used in the present invention is not particularly limited, and a step capable of imparting a desired function to the μCP stamp manufactured according to the present invention can be appropriately selected and used. Examples of such an optional process include a master plate decompression process after application of a PDMS film for reducing bubble contamination.

5. μCP Stamp The μCP stamp manufactured according to the present invention has a configuration in which a PDMS film having a concavo-convex shape formed on a surface is formed on a support material. Such a stamp for μCP is used for microcontact printing (μCP), and can be used, for example, in a process of forming various electrodes of an organic semiconductor element using an organic transistor.

  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.

  Hereinafter, the present invention will be described more specifically by showing examples.

[Example 1]
1. Production of master plate for μCP stamp production (1) Shading part forming step First, AZ 5206-E (AZ Electronic Materials) is formed on the surface of a glass substrate (Cr film thickness 150 nm) with Cr having a size of 300 mm × 400 mm × 0.7 mm. (Positive resist made by the company) was spin coated. The spin coating at this time was held at 800 rpm for 20 seconds. Thereafter, the substrate was dried at 130 ° C. for 3 minutes and then subjected to pattern exposure at 50 mJ / cm ² . The photomask used at this time is a positive mask having a size of 420 mm × 550 mm. Thereafter, the photoresist was developed to obtain a pattern equivalent to a photomask. Next, Cr other than the pattern portion was etched with a Cr etching solution, and then the resist was stripped with a stripping solution. Next, the substrate was washed with pure water using an ultrasonic cleaner.

(2) Photosensitive resin film formation process Next, the said board | substrate was spin-coated with the solution (Epoxy negative resist by Kayaku Macrochem Co., Ltd.) which diluted SU-3000 which is photosensitive resin 90%. The spin coating at this time was held at 700 rpm for 60 seconds. Thereafter, the substrate was dried at 100 ° C. for 3 minutes.

(3) Exposure process Next, back exposure was performed at 30 mJ / cm ² from the glass back side. Further, it was dried at 65 ° C. for 1 minute in order to accelerate curing.

(4) Development step Thereafter, the photosensitive resin present on the upper part of Cr was developed and removed with a dedicated developer, and then rinsed with IPA. Thereafter, it was dried in an oven at 150 ° C. for 30 minutes to obtain a master plate for producing a stamp for μCP.

(5) Master plate for μCP stamp preparation When the prepared master plate for μCP stamp preparation was observed with a reflection optical microscope, an intaglio plate coated with a photosensitive resin in addition to the Cr portion was formed. Moreover, it was confirmed that the width | variety of the recessed part has resolved to 1 micrometer-10 micrometers. Furthermore, when measured with a stylus type film thickness meter, the depth of the recess was 10 μm regardless of the line width.

2. Manufacture of stamp for μCP Using the master plate for stamp preparation for μCP prepared by the above method, a release agent (Durasurf, manufactured by Harves) is held at 1000 rpm in order to improve the release property of PDMS on the master plate. Spin coating was performed for 30 seconds.
Next, PDMS (KE-106 manufactured by Shin-Etsu Chemical Co., Ltd.) in which 90 g of the main agent and 9 g of the curing agent are mixed with the master plate for μCP stamp production that has been subjected to the mold release treatment is about 2 mm thick with a dispenser (manufactured by Saneitec Co., Ltd.). A uniform coating was applied to the entire surface. After that, in order to remove bubbles in the pattern, it was put in a vacuum dryer and the pressure was reduced to 0.1 torr and held for 5 minutes.
Next, the adhesion process of the master plate for producing the stamp for μCP with PDMS and the supporting material (size 300 mm × 400 mm, glass 0.7 mm in thickness) was performed using ST-50 manufactured by Toshiba Machine. At this time, the contact speed between the upper head and the lower head can be controlled to a minimum of 1 μm / s. Thereafter, the upper head was lowered at 500 μm / s until just before the support material and the PDMS film contacted each other. Subsequently, the PDMS membrane and the support were brought into contact at 1 μm / s in the low speed mode immediately before contact. Further, the contact speed was maintained after contact at 1 μm / s, and the contact was pushed in until the gap between the upper head and the lower head was 1 mm, that is, the PDMS thickness was about 1 mm. Then, after pushing into a predetermined position at the same speed, it was left at room temperature for 16 hours to cure PDMS.
Next, the support material and the master plate for μCP stamp preparation were taken out from the apparatus, and the substrate with the PDMS film was manually peeled from the master plate for μCP stamp preparation to prepare a μCP stamp.
When the surface of the peeled PDMS film was observed with an optical microscope, a reversal pattern of the master plate for making a stamp for μCP was observed, and it was confirmed that a relief plate having a height of 10 μm and a minimum L & S of 1 μm was formed.

[Evaluation]
When compared with the intaglio plate produced by etching Si, which is a conventional technique, a 300 mm × 400 mm large area polymer plate and a μCP stamp could be produced. Furthermore, the intaglio produced by Si etching had a different depth depending on the width of the recess due to the microloading effect. In the present invention, it was confirmed that the depth was uniform at 10 μm regardless of whether the recess width was 1 μm or 10 μm. It was done. Moreover, the linearity of the wall surface and the bottom surface of the concave portion generated in the conventional Si etching intaglio was improved by using the photosensitive polymer, and a significant effect was seen in the PDMS mold release and the PDMS convex shape. This effect enables fine printing with high accuracy and accuracy.

DESCRIPTION OF SYMBOLS 1 ... Substrate 2 ... Light-shielding part 3 ... Photosensitive resin film 3 '... Photosensitive resin layer 10 ... Master plate for stamp production for μCP 20 ... Stamp for μCP 21 ... PDMS film 22 ... Support material 20 ... Master plate 100 ... For μCP Stamp 101… PDMS film 102… Support material 200… Master plate for μCP stamp production

Claims (3)

A light shielding part forming step of forming a patterned light shielding part on the substrate using a substrate;
Forming a photosensitive resin film made of a negative photosensitive resin on the substrate so as to cover the light shielding portion;
An exposure step of pattern exposure on the photosensitive resin film by irradiating light from the substrate side;
By developing the pattern exposed photosensitive resin layer, have a developing step of patterning the photosensitive resin film,
A method for producing a master plate for producing a stamp for microcontact printing, wherein the photosensitive resin film has a thickness in the range of 1 to 10 μm . A substrate,
A photosensitive resin layer formed in a pattern on the substrate and made of a negative photosensitive resin;
Wherein the photosensitive resin layer is not formed the light-shielding portion formed on the substrate surface, it was closed,
A master plate for producing a stamp for microcontact printing, wherein the photosensitive resin layer has a thickness in the range of 1 μm to 10 μm . 3. The microcontact printing according to claim 2 , wherein the photosensitive resin layer is formed so that a line width on a substrate side is wider than a line width on a surface side with respect to a thickness direction. Master version for stamp production.

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