JP2011005768A - Master plate used for manufacturing of stamp for micro contact print, method of manufacturing the same, stamp for micro contact print, method of manufacturing of the same and pattern forming method using stamp for micro contact print - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stamp for pattern transferring to a workpiece with high accuracy in the micro contact print, a master plate for manufacturing the stamp, a method of manufacturing these, and a pattern forming method of high accuracy by a micro contact print method.SOLUTION: The master plate 1 for manufacturing the stamp for the micro contact print includes a base board 2, resin protruded parts 3 disposed in a desired pattern on one face 2a of the base board 2, and flat protruded parts 4 disposed on the base board 2 on non-molded parts of the resin protruded parts 3. A peripheral wall part 4a of the flat protruded part 4 is separated from a side wall 3a of the resin protruded part 3 via minute space 5.

Description

  The present invention relates to microcontact printing, and more particularly to a stamp used for microcontact printing, a master plate for manufacturing the stamp, a manufacturing method thereof, and a pattern forming method using the stamp.

As a micro-to-nano-order fine patterning technique, there is soft lithography, which is a technique for transferring a fine three-dimensional structure by pouring a fluid material such as silicone resin into a fine mold and curing it as it is. As a technique for patterning a resin mold obtained by this soft lithography as a plate, there is a micro contact printing (hereinafter also referred to as “μCP”) method.
The μCP method was developed in 1993 by Harvard University, USA. M.M. This is a fine pattern forming technology developed by Whitesides et al. As shown in FIGS. 8 and 9, this fine pattern forming technique is applied to a master plate 41 (FIG. 9A) having a pattern produced by soft lithography on a substrate such as silicon or quartz, and polydimethylsiloxane. A liquid material 51 ′ such as (PDMS: two-component curable silicone resin) is poured (FIG. 9B) and cured as it is, and then the master plate 41 and the cured PDMS are separated to reverse the master plate 41. A stamp 51 made of PDMS having a pattern is obtained (FIG. 9C). Then, the ink 61 is placed on the transfer convex portion 52 of the stamp 51 (FIG. 10A), and the ink 61 is transferred to the workpiece 71 (FIGS. 10B and 10C) (patent). Reference 1).

  In principle, the μCP method can easily and inexpensively replicate a PDMS stamp as long as it has a master plate, and the stamp made of PDMS has its own flexibility, so that it can follow the workpiece. There are advantages such as. In recent years, the μCP method has attracted attention in the production of element patterns in large-area flexible panels such as organic electroluminescence panels.

JP 2002-353436 A

However, in practice, the μCP using the conventional stamp 51 in which the transfer convex portion 52 has a flat shape has the following problems. That is, as shown in FIG. 11A, when the ink 61 placed on the transfer convex portion 52 of the stamp 51 is transferred to the work piece 71, the ink 61 easily protrudes outside the transfer convex portion 52. was there. In particular, when the flatness of the workpiece is poor, if the printing pressure is increased for the purpose of improving transferability, the stamp 51 and the workpiece 71 are easily transferred at a place where the stamp 51 and the workpiece 71 are in contact as shown in FIG. There is a problem that the ink 61 protrudes outside the convex portion 52. When such ink sticking out occurs, variations occur in the line width L of the transfer pattern set by the stamp 51 and the interval S between adjacent patterns. Then, as shown in FIG. 11C, the original line width L is increased to L ′ and L ″, and the original interval S is decreased to S ′ and S ″. A portion where the workpiece is exposed may appear in the pattern. Therefore, for example, when the ink is a forming material such as wiring, a short circuit occurs between adjacent patterns, or the electrical resistance increases.
The present invention has been made in view of the above circumstances, and a stamp capable of transferring a pattern to a workpiece with high accuracy in μCP, a master plate for producing the stamp, and production thereof. It is an object of the present invention to provide a method and a highly accurate pattern forming method using the μCP method.

In order to solve such problems, a master plate for manufacturing a microcontact printing stamp according to the present invention includes a substrate, a resin convex portion arranged in a desired pattern on one surface of the substrate, A flat protrusion disposed on the substrate at a portion where the resin protrusion is not formed, and the peripheral wall of the flat protrusion and the side wall of the resin protrusion are separated via a minute gap. The configuration is as follows.
As another aspect of the present invention, the resin convex portion is configured such that the pattern width on the top side is smaller than the pattern width on the substrate side, and the side wall forms an inclined surface.
As another aspect of the present invention, the width of the minute gap existing between the peripheral wall portion of the flat protrusion and the side wall of the resin convex portion is configured to become smaller toward the substrate side. .
As another aspect of the present invention, the resin protrusion has a thickness in the range of 1 to 50 μm, and the flat protrusion has a thickness in the range of 50 to 1000 nm.

The method for producing a master plate for stamp production for microcontact printing according to the present invention comprises a step of forming a light shielding portion with a desired pattern on one surface of a transparent substrate, and a negative on the transparent substrate so as to cover the light shielding portion. A photosensitive resist coating, irradiating light from the transparent substrate side, exposing the coating film of the negative photosensitive resist using the light-shielding portion as a mask, and then developing to expose the light-shielding portion to a non-forming portion. Forming a resin convex portion, applying a positive photosensitive resist so as to cover the resin convex portion, irradiating light from the transparent substrate side, and forming a coating film of the positive photosensitive resist using the light shielding portion as a mask; A step of exposing and developing to form an etching resist layer on the light-shielding portion; an etchant is immersed from a gap existing between the resin convex portion and the etching resist layer; Then, by etching the peripheral portion of the light shielding portion, a flat protruding portion in which the peripheral wall portion is separated from the side wall of the resin convex portion via a minute gap is formed, and then the etching resist layer is removed. It was set as the structure which has a process.
As another aspect of the present invention, the thickness of the light shielding part is set within a range of 50 to 1000 nm.

Further, the stamp for microcontact printing of the present invention comprises a base, and a transfer convex part that protrudes from the base in a desired pattern and has a microprojection that is continuous with the peripheral part of the top plane. did.
As another aspect of the present invention, the microprojections have a wedge-shaped cross section.
As another aspect of the present invention, the height of the transfer convex portion is in the range of 1 to 50 μm, and the height of the fine protrusion from the top plane is in the range of 50 to 1000 nm. .
As another aspect of the present invention, the transfer protrusions are not uniform in width.

In addition, the method for manufacturing a microcontact print stamp according to the present invention includes a microcontact print including a base and a transfer convex portion that protrudes from the base in a desired pattern and has continuous microprotrusions on a peripheral portion of the top plane. A stamp is manufactured by applying a curable material to the surface of the master plate on which the resin convex portion is disposed, and curing a coating film of the curable material to form a base and a transfer convex portion. After forming, it was set as the structure which peels from the said master plate.
In addition, the manufacturing method of the stamp for microcontact printing according to the present invention includes a support substrate, a base disposed on one surface of the support substrate, a desired pattern protruding from the base, and a peripheral portion of the top plane. A method for manufacturing a stamp for microcontact printing comprising a transfer convex portion having continuous microprotrusions, wherein a molding substrate is formed by applying a curable material to a support substrate to form a coating film, and the support substrate The coating film side of the master plate is pressure-bonded to the surface of the master plate on which the resin convex portion is disposed, and the base film and the transfer convex portion are formed by curing the coating film of the curable material. It was set as the structure which joined the said support substrate and peeled from the said master plate after that.

Further, in the pattern forming method of the present invention, the ink for pattern formation is placed on the top plane of the transfer convex portion of the microcontact printing stamp described above, and then the ink is brought into contact with the workpiece, The contact printing stamp was peeled off.
As another aspect of the present invention, the ink for pattern formation placed on the top flat surface of the transfer convex portion is made into a semi-dried state, and then the ink is brought into contact with the workpiece.

  In the master plate used for manufacturing the microcontact printing stamp of the present invention, the peripheral wall portion of the flat protrusion and the side wall of the resin convex portion are spaced apart via a minute gap, and therefore, continuous with the peripheral portion of the top plane. Microcontact printing stamps with transfer protrusions with microprotrusions can be manufactured reliably and simply, and by adjusting the thickness of the flat protrusions, the height of the microprotrusions on the microcontact print stamps can be increased. Can be controlled. Further, when the pattern width of the resin convex portion is small toward the top side and the side wall of the resin convex portion forms an inclined surface, it exists between the peripheral wall portion of the flat protrusion and the side wall of the resin convex portion. When the width of the minute gap is reduced toward the substrate side, the stamp can be easily peeled off from the master plate in the manufacture of the microcontact printing stamp.

  Moreover, in the manufacturing method of the stamp manufacturing master plate for micro contact printing of the present invention, since the negative photosensitive resist coating film is exposed and developed from the transparent substrate side to form the resin convex portion, it is related to the width of the light shielding portion. Therefore, the resin protrusion can be formed at a uniform height without being affected by the interval between adjacent resin protrusions, and the peripheral wall portion of the flat protrusion can be adjusted by adjusting the thickness of the light shielding portion. The depth of the minute gap existing between the side wall of the resin convex portion can be controlled, and the width of the minute gap can be controlled by adjusting the etching time of the peripheral portion of the light shielding portion, the etchant conditions, etc. It can be performed by adjusting, and a desired master plate can be easily produced with high accuracy.

  In addition, since the microcontact printing stamp of the present invention has continuous micro-projections on the peripheral edge of the top flat surface of the transfer convex portion, the protrusion of ink to the outside of the transfer convex portion during micro contact printing is suppressed, and The thickness of the ink placed on the top flat surface of the transfer convex portion becomes uniform regardless of the pattern width of the transfer convex portion, and a highly accurate pattern can be formed.

  Further, in the method for manufacturing a microcontact printing stamp of the present invention, since the master plate of the present invention is used, it is possible to manufacture a highly accurate stamp with a uniform transfer convex portion height even in a large area. Moreover, the height of the fine protrusion of the stamp can be controlled by adjusting the thickness of the flat protrusion of the master plate to be used.

  In the pattern forming method of the present invention, since the ink placed on the top flat surface of the transfer convex portion is brought into contact with the workpiece using the microcontact printing stamp of the present invention, the ink placed on the top flat surface of the transfer convex portion The thickness of the ink becomes uniform regardless of the pattern width of the transfer convex portion, and the ink is prevented from protruding outside the transfer convex portion, so that a desired pattern can be formed with high accuracy.

It is a schematic fragmentary sectional view which shows one Embodiment of the master plate used for manufacture of the stamp for microcontact printing of this invention. It is a figure for demonstrating the example of the micro gap | interval which comprises a master plate. It is process drawing for demonstrating the manufacturing method of the master plate of this invention. It is process drawing for demonstrating the manufacturing method of the master plate of this invention. It is a general | schematic fragmentary sectional view which shows one Embodiment of the stamp of this invention. It is process drawing for demonstrating one Embodiment of the manufacturing method of the stamp of this invention. It is process drawing for demonstrating other embodiment of the manufacturing method of the stamp of this invention. It is process drawing for demonstrating one Embodiment of the pattern formation method of this invention. It is process drawing for demonstrating an example of the conventional microcontact printing. It is process drawing for demonstrating an example of the conventional microcontact printing. It is a figure for demonstrating the problem in the conventional microcontact printing.

Embodiments of the present invention will be described below with reference to the drawings.
[Master version]
FIG. 1 is a schematic partial cross-sectional view showing an embodiment of a master plate used for manufacturing a stamp for micro contact printing (μCP) of the present invention. In FIG. 1, a master plate 1 of the present invention includes a substrate 2, a resin convex portion 3 arranged in a desired pattern on one surface 2 a of the substrate 2, and a substrate 2 in a portion where the resin convex portion 3 is not formed. A flat protrusion 4 disposed on the top. Then, the peripheral wall 4 a of the flat protrusion 4 and the side wall 3 a of the resin protrusion 3 are separated via a minute gap 5.
The substrate 2 constituting the master plate 1 of the present invention is not particularly limited as long as it can support the resin protrusions 3 and the flat protrusions 4. For example, a substrate made of an inorganic material such as glass or quartz should be used. It may be made of a resin material.

The resin convex portion 3 constituting the master plate 1 has a resistance to a curable material used in the manufacture of a stamp as described later and a durability that can withstand repeated use in the manufacture of a stamp. It is obtained by curing a photosensitive resist such as epoxy, acrylic, polyimide, polyamide, cardo, novolac, polystyrene, polymethyl methacrylate and the like. The thickness of such a resin convex part 3 determines the height of the transfer convex part of the stamp to produce, for example, can be suitably set within the range of 1-50 micrometers. Further, the resin convex portion 3 may have a tapered shape in which the pattern width on the top portion 3b side is smaller than the pattern width on the substrate 2 side and the side wall 3a forms an inclined surface.
Moreover, the flat protrusion part 4 which comprises the master plate 1 may consist of metal materials, such as Cr, Al, Ni, Ti, Cu, Ag, for example. The flat protrusion 4 determines the flatness of the top surface of the transfer convex portion of the stamp to be manufactured and also determines the height of the fine protrusion of the stamp. The thickness of the flat protrusion 4 is, for example, 50 It can set suitably within the range of -1000 nm.

  Further, the minute gap 5 that exists so as to separate the peripheral wall portion 4a of the flat protrusion 4 and the side wall 3a of the resin convex portion 3 continuously exists on the peripheral portion of the top plane of the transfer convex portion of the stamp to be manufactured. The shape of the minute protrusion to be determined is determined. As shown in FIG. 1, the shape of the minute gap 5 is a wedge shape in which the width of the minute gap 5 is reduced toward the substrate 2, and the peripheral wall portion 4 a and the side wall 3 a are on the surface 2 a of the substrate 2. They may be in contact with each other. 2A, the peripheral wall 4a of the flat protrusion 4 and the side wall 3a of the resin protrusion 3 form an inclined surface, and a trapezoidal shape in which both are not in contact with each other, FIG. As shown in FIG. 2B, the peripheral wall 4a of the flat protrusion 4 has a curved surface, as shown in FIG. 2C, the peripheral wall 4a of the flat protrusion 4 and the resin. The side wall 3a of the convex part 3 may be substantially parallel and may have a rectangular shape or the like in which both are not in contact. Therefore, in the present invention, the separation between the peripheral wall portion 4a of the flat protrusion 4 and the side wall 3a of the resin convex portion 3 includes a state in which the peripheral wall portion 4a and the side wall 3a are not completely in contact with each other. 1 and a concept including a state in which the peripheral wall portion 4a and the side wall 3a are in contact with each other on the surface 2a of the substrate 2 as shown in FIG.

  In such a master plate 1 of the present invention, the peripheral wall portion 4a of the flat protrusion 4 and the side wall 3a of the resin convex portion 3 are separated from each other with a minute gap 5 therebetween, so that it continues to the peripheral portion of the top plane. A stamp for μCP having a transfer convex portion having minute protrusions can be reliably and easily manufactured. Further, by adjusting the thickness of the flat protrusion 4, the height of the minute protrusions of the μCP stamp can be controlled. Further, when the pattern width of the resin convex portion 3 is reduced toward the top portion 3b and the side wall 3a of the resin convex portion 3 forms an inclined surface, the width of the minute gap 5 is decreased toward the substrate 2 side. In this case, the stamp can be easily peeled off from the master plate 1 in the manufacture of the stamp for μCP.

[Manufacturing method of master plate]
Next, the manufacturing method of the stamp manufacturing master plate for micro contact printing (μCP) of the present invention will be described.
3 and 4 are process diagrams for explaining the method for producing a master plate according to the present invention, and the production of the master plate 1 described above is taken as an example. In FIG. 3, first, a light shielding portion 4 ′ is formed in a desired pattern on one surface 2a of the transparent substrate 2 (FIG. 3A). The transparent substrate 2 to be used is not particularly limited as long as it is a material that transmits exposure light because it exposes the negative photosensitive resist by irradiating light from the transparent substrate 2 side in the steps described later. For example, glass, quartz, etc. Examples thereof include those made of the above inorganic materials and those made of resin materials. Further, the light shielding portion 4 ′ is subjected to etching in the process described later to become the flat protrusion 4. For example, a vacuum film-forming method using a metal material such as Cr, Al, Ni, Ti, Cu, Ag, or the like. Can be formed by forming a thin film, and then forming a desired resist pattern and etching through the resist pattern. The thickness of the light-shielding portion 4 ′ determines the thickness of the flat protrusion 4 and can be set as appropriate within a range of 50 to 1000 nm, for example.

  Next, a negative photosensitive resist is applied on the transparent substrate 2 so as to cover the light-shielding portion 4 'to form a coating film 3' (FIG. 3B). As the negative photosensitive resist, for example, a photosensitive resist such as epoxy, acrylic, polyimide, polyamide, cardo, novolac, polystyrene, polymethylmethacrylate and the like can be used. The negative photosensitive resist can be applied by spin coating, blade coating, bar coating, slit coating, die coating, roll coating, dip coating, spray coating, dispenser coating, etc. it can. The thickness of the negative photosensitive resist coating film 3 'determines the thickness of the resin protrusion 3 of the master plate 1, and takes into account volume shrinkage after curing of the negative photosensitive resist to be used. And can be set as appropriate.

  Next, light is applied from the transparent substrate 2 side to expose the negative photosensitive resist coating film 3 ′ using the light shielding portion 4 ′ as a mask (FIG. 3C). The resin convex part 3 is formed in a non-formation site | part (FIG. 3 (D)). In the present invention, since the exposure of the negative photosensitive resist coating film 3 'is performed by so-called back exposure from the transparent substrate 2 side, high-precision exposure reflecting the pattern shape of the light-shielding portion 4' as a mask is possible. It is. Further, the amount of exposure energy in the thickness direction received by the coating film 3 ′ can be decreased on the transparent substrate 2 side and decreased on the surface side due to the light attenuation effect. As a result, as shown in the figure, the resin protrusion 3 formed by development can be formed into a tapered shape in which the pattern width is small toward the top 3b and the side wall 3a forms an inclined surface.

  Next, a positive photosensitive resist is applied so as to cover the resin convex portion 3 to form a coating film 6 ', light is irradiated from the transparent substrate 2 side, and the positive photosensitive resist is used with the light shielding portion 4' as a mask. The coating film 6 'is exposed (FIG. 4A) and then developed to form an etching resist layer 6 on the light shielding portion 4' (FIG. 4B). As the positive photosensitive resist, for example, a polyimide-based or novolak-based photosensitive resist can be used. The positive photosensitive resist can be applied by spin coating, blade coating, bar coating, slit coating, die coating, roll coating, dip coating, spray coating, dispenser coating, etc. it can. In the present invention, since the exposure of the positive photosensitive resist coating film 6 ′ is performed by so-called back exposure from the transparent substrate 2 side, the coating film 6 ′ in contact with the side wall 3 a of the resin protrusion 3 is also exposed. Will receive. Therefore, a gap 7 exists between the etching resist layer 6 obtained by development and the wall surface 3a of the resin protrusion 3 as shown in the drawing.

  Next, an etchant is infiltrated from the gap 7 existing between the resin convex portion 3 and the etching resist layer 6 to etch the peripheral portion of the light shielding portion 4 ′. Thereby, the flat protrusion part 4 in which the peripheral wall part 4a is spaced apart from the side wall 3a of the resin convex part 3 via the minute gap 5 is formed (FIG. 4C). Thereafter, the master plate 1 is obtained by removing the etching resist layer 6 (FIG. 4D). The etchant used for etching the light shielding part 4 ′ can be appropriately selected according to the material of the light shielding part 4 ′ in consideration of the material of the resin convex part 3 and the etching resist layer 6. In wet etching, for example, When the light shielding part 4 'is made of Cr, a cerium nitrate ammonium nitrate solution or the like can be used as the etchant. Further, as an etchant, a gas containing chlorine such as chloromethane, dichloromethane, trichloromethane, carbon tetrachloride, and chlorine gas, and one or more of these gases and a dilution gas such as oxygen, helium, and argon are used. You may etch the peripheral part of light-shielding part 4 'by dry etching using mixed gas etc. FIG.

  In such a master plate manufacturing method of the present invention, the negative photosensitive resist coating film 3 ′ is exposed and developed from the transparent substrate 2 side to form the resin convex portion 3, so that the width of the light shielding portion 4 ′ is increased. Regardless, therefore, the resin convex portion 3 can be formed at a uniform height without being affected by the interval between the adjacent resin convex portions 3. Further, by adjusting the thickness of the light shielding part 4 ′, the depth of the minute gap 5 existing between the peripheral wall part 4 a of the flat projecting part 4 and the side wall 3 a of the resin convex part 3 can be controlled. Further, the width of the minute gap 5 can be controlled by adjusting the etching time, etchant conditions, and the like of the peripheral portion of the light shielding portion 4 '.

[stamp]
Next, the micro contact print (μCP) stamp of the present invention will be described.
FIG. 5 is a schematic partial sectional view showing an embodiment of the stamp of the present invention. In FIG. 5, the stamp 11 of the present invention includes a support substrate 12, a base portion 13 disposed on one surface 12 a of the support substrate 12, and a transfer convex portion 14 protruding from the base portion 13 in a desired pattern. And a continuous microprotrusion 15 located at the peripheral edge of the top flat surface 14 a of the transfer convex portion 14.
The support substrate 12 constituting the stamp 11 is not particularly limited as long as it can support the base portion 13 and the transfer convex portion 14, and is not flexible, such as a glass substrate, a silicon substrate, or a substrate made of silicon oxide. A rigid substrate or a flexible substrate having flexibility can be used. As a flexible substrate, you may consist of resin materials, such as PET, PEN, PES, PI, PEEK, PC, PPS, PEI, for example. The thickness of the support substrate 12 can be appropriately set in consideration of the material, the use of the stamp 11 and the like.

The base 13 and the transfer convex 14 are made of, for example, polydimethylsiloxane (PDMS: two-part curable silicone resin), fluoroelastomer (SHIN-ETSU SIFEL manufactured by Shin-Etsu Chemical Co., Ltd.) or the like. Can do. The thickness of the base 13 can be appropriately set in consideration of the application of the stamp 11 and the like.
The height H of the transfer convex portion 14 is determined in consideration of the material, the use of the stamp 11 and the like so as to suppress the background dirt transferred to the workpiece by the ink attached to the support substrate 12 where the transfer convex portion 14 does not exist. For example, it can be set within a range of 1 to 50 μm.
Further, the height h from the top flat surface 14a of the microprotrusion 15 arranged continuously on the peripheral edge of the top flat surface 14a of the transfer convex portion 14 determines the use of the stamp 11, the characteristics of the ink used in the μCP, and the like. For example, it can be set within a range of 50 to 1000 nm. If the height h of the microprojections 15 is less than 50 nm, the thickness of the ink for pattern formation may be insufficient, or the ink may protrude outside the transfer convex portion 14, and if it exceeds 1000 nm, transfer failure may occur. It is possible that it may cause The cross-sectional shape of such a microprojection 15 may be a wedge shape with a sharp tip, a trapezoid with a narrow tip, a semicircle, a rectangle, or the like.

Since the stamp 11 of the present invention has the minute protrusions 15 that are continuous at the peripheral edge of the top flat surface 14a of the transfer convex portion 14, the protrusion of the ink to the outside of the transfer convex portion 14 at the time of μCP is suppressed. Further, the thickness of the ink placed on the top flat surface 14a of the transfer convex portion 14 becomes uniform regardless of the pattern width of the transfer convex portion 14, and a highly accurate pattern can be formed. Therefore, the stamp 11 of the present invention may have the transfer convex portion 14 having various widths, and by using such a stamp 11, patterns having various line widths can be formed with high accuracy. be able to.
Note that the stamp of the present invention may not include the support substrate 12.

[Stamp manufacturing method]
Next, a method for manufacturing a microcontact print (μCP) stamp according to the present invention will be described.
FIG. 6 is a process diagram for explaining an embodiment of the stamp manufacturing method of the present invention, and shows an example of manufacturing the stamp 11 using the above-described master plate 1 of the present invention. In FIG. 6, first, a curable material is applied to the surface of the master plate 1 on which the resin convex portions 3 are disposed to form a coating film 13 '(FIG. 6A). Examples of the curable material to be used include polydimethylsiloxane (PDMS: two-part curable silicone resin), fluorine elastomer (SHIN-ETSU SIFEL manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. Application of such a curable material to the master plate 1 is, for example, spin coating, blade coating, bar coating, slit coating, die coating, roll coating, dip coating, spray coating, dispenser coating, and the like. This can be done by law. Note that a release agent may be applied to the master plate 1 for the purpose of improving the peelability of the curable material after curing before applying the coating film 13 ′ of the curable material.

Next, the support substrate 12 is brought into contact with the surface of the coating film 13 ′ of the curable material (FIG. 6B), and then the curable material is cured to form the base portion 13 and the transfer convex portion 14. 13 and the support substrate 12 are joined (FIG. 6C). As the support substrate 12 to be used, for example, a rigid substrate such as a glass substrate, a silicon substrate, or a silicon oxide substrate, or a flexible substrate having flexibility can be used. As a flexible substrate, you may consist of resin materials, such as PET, PEN, PES, PI, PEEK, PC, PPS, PEI, for example.
In the contact between the support substrate 12 and the coating film 13 ′ of the curable material, the two surfaces can be kept in contact with each other while maintaining a parallel state, and the both surfaces are in contact with each other at a predetermined angle. May be. Further, after the support substrate 12 and the coating film 13 ′ of the curable material are brought into contact with each other, the support substrate 12 may be pushed in the direction of the coating film 13 ′, and the pushing amount is appropriately set within a range of 5 mm or less, for example. Can do.

The curing conditions of the curable material can be appropriately set according to the curable material to be used. In addition, in order to prevent gas and bubbles from being taken into the coating film 13 ′ of the curable material, a deaeration process may be performed in a vacuum before or during curing.
Next, the base portion 13 and the transfer convex portion 14 formed by curing the curable material are peeled from the master plate 1 together with the support substrate 12 to obtain the stamp 11 having a reverse pattern of the master plate 1 (see FIG. 6 (D)). The method for peeling the stamp 11 from the master plate 1 is not particularly limited as long as the stamp 11 is not damaged. Usually, a method of physically separating the stamp 11 from the master plate 1 can be used.

In the above-described embodiment, a curable material is applied to the surface of the master plate 1 on which the resin protrusions 3 are disposed to form a coating film 13 ′, and the support substrate 12 is formed on the surface of the coating film 13 ′. However, the method is not limited to this. For example, as shown in FIG. 7A, a molded substrate 17 in which a curable material is applied to the support substrate 12 to form a coating film 13 ′ is prepared in advance, and as shown in FIG. The molded substrate 17 may be pressure-bonded to the surface of the master plate 1 on which the resin convex portion 3 is disposed.
In such a stamp manufacturing method of the present invention, since the master plate 1 of the present invention is used, the stamp 11 having a uniform transfer convex portion 14 height and high accuracy can be manufactured even in a large area. . Moreover, the height of the microprotrusions 15 of the stamp 11 can be controlled by adjusting the thickness of the flat protrusion 4 of the master plate 1 to be used.

[Pattern formation method]
Next, the pattern forming method of the present invention will be described.
FIG. 8 is a process diagram for explaining an embodiment of the pattern forming method of the present invention, and shows an example using the above-described stamp 11 of the present invention. In FIG. 8, first, the pattern forming ink 21 is placed on the top flat surface 14a of the transfer convex portion 14 of the μCP stamp 11 of the present invention (FIG. 8A). As the ink 21, for example, a raw material solution corresponding to a pattern to be formed such as a semiconductor pattern, an electrode pattern, a wiring pattern, and a dielectric pattern can be used. Therefore, for example, when the pattern to be formed is an electrode pattern, a conductive paste containing conductive fine particles can be used as the ink 21. Such an ink 21 is designed so that the adhesion to the workpiece is higher than the adhesion to the top flat surface 14 a of the transfer convex portion 14. Further, the ink 21 can be supplied onto the top flat surface 14a of the transfer convex portion 14 by a spin coating method, a dip coating method, a spray coating method, a dispenser coating method, an ink jet method, or the like. Thus, the ink 21 placed on the top flat surface 14a of the transfer convex portion 14 is reliably held by the microprotrusions 15 continuously provided on the peripheral edge of the top flat surface 14a, and the thickness of the ink 21 is It becomes uniform regardless of the pattern width of the transfer convex portion 14 and is prevented from flowing down to the side wall of the transfer convex portion 14.

In the present invention, the ink 21 placed on the top flat surface 14a of the transfer convex portion 14 may be in a semi-dry state. This is for evaporating the solvent contained in the ink 21 to some extent to increase the adhesion of the ink 21 to the workpiece, and various drying and heating conditions can be set depending on the ink used.
Next, the ink 21 is brought into contact with the workpiece 31 (FIG. 8B), and then the μCP stamp 11 is peeled off (FIG. 8C). In the present invention, since the continuous minute protrusions 15 are disposed on the peripheral edge of the top flat surface 14a of the transfer convex portion 14 of the stamp 11 to be used, the ink 21 is prevented from protruding outside the transfer convex portion 14. . Accordingly, even if the flatness of the workpiece 31 is poor and the printing pressure is increased for the purpose of improving the transferability, the ink to the outside of the transfer convex portion 14 at the place where the stamp 11 and the workpiece 31 are easily in contact with each other. The protrusion 21 is prevented, and a desired pattern can be formed with high accuracy.
The above-described embodiments of the present invention are illustrative, and the present invention is not limited to these embodiments.

Next, the present invention will be described in more detail by showing specific examples.
[Example]
<Preparation of master version>
As a transparent substrate, a glass substrate (300 mm × 400 mm, thickness 0.7 mm) with a Cr thin film (thickness 150 nm) was prepared, and a photosensitive resist (AZ 5206-E manufactured by AZ Electronic Materials Co., Ltd.) was formed on the Cr thin film of this transparent substrate. Was applied by spin coating and dried at 130 ° C. for 3 minutes. Next, it was exposed (50 mJ / cm ² ) through a photomask having a comb-shaped light-transmitting portion with a line / space of 10 μm / 10 μm, and developed to form a resist pattern. Using this resist pattern as a mask, Cr was etched with a cerium nitrate ammonium nitrate solution, and then the resist pattern was peeled off. Thus, a light shielding portion made of Cr having a comb-shaped pattern equivalent to the light transmitting portion of the photomask was formed.

Next, a negative photosensitive resist (SU-8 manufactured by Nippon Kayaku Co., Ltd.) is applied on the transparent substrate 2 so as to cover the light shielding part by spin coating, and dried at 100 ° C. for 3 minutes. A film was formed.
Subsequently, light was irradiated from the transparent substrate side to perform back exposure (exposure amount 30 mJ / cm ² ), and further dried at 65 ° C. for 1 minute in order to promote curing. Then, it developed and formed the resin convex part in the non-formation site | part of the light-shielding part (refer FIG.3 (D)). The resin protrusion formed in this manner was a taper shape having a thickness of μm, a width of 10 μm on the transparent substrate side, and a width of 9.9 μm on the surface side.
Next, a positive photosensitive resist (AZ 5206-E manufactured by AZ Electronic Materials Co., Ltd.) was applied by a spin coating method so as to cover the resin convex portion, and dried at 130 ° C. for 3 minutes to form a coating film.

Subsequently, light was irradiated from the transparent substrate side to perform back exposure (exposure amount: 50 mJ / cm ² ). Then, it developed and formed the resist layer for an etching on the light-shielding part. The etching resist layer thus formed had a thickness of 1 μm, and there was a gap of about 0.1 μm between the wall surface of the resin protrusion (see FIG. 4B). .
Next, it is immersed in a cerium diammonium nitrate solution (liquid temperature: 23 ° C., concentration: 5%) as an etchant, left standing for 1 minute, then washed with water, and then the etching resist layer is removed to remove the master plate of the present invention. Obtained. By this etching, the peripheral part of the light shielding part was etched to form a flat protrusion. In this flat protrusion, the peripheral wall portion was separated from the side wall of the resin convex portion via a wedge-shaped minute gap.

<Production of stamp>
On the master plate produced as described above, a release agent (Durasurf manufactured by Harves Co., Ltd.) is applied by a spin coat method and dried for the purpose of improving the peelability of polydimethylsiloxane (PDMS: two-part curable silicone resin). did.
Next, a curable material (polydimethylsiloxane (PDMS: KE-106 manufactured by Shin-Etsu Chemical Co., Ltd.) in which 90 g of the main agent is mixed with 9 g of the curing agent) is applied to the surface of the master plate 1 on which the resin convex portions are disposed. Coating was performed by a dispenser coating method to form a coating film (thickness: about 2 mm). Thereafter, in order to remove bubbles in the coating film, a degassing treatment (held at 0.1 torr for 5 minutes) was performed in a vacuum dryer.
Next, a glass substrate (300 mm × 400 mm, thickness 0.7 mm) is prepared as a support substrate, and the surface of the support substrate is parallel to the coating film of the curable material using ST-50 manufactured by Toshiba Machine Co., Ltd. The support substrate was pushed into the coating film of the curable material with a pushing amount of 1 mm. Thereafter, the curable material was cured by being allowed to stand for 16 hours.

  Next, the cured curable material and the supporting substrate were peeled from the master plate to obtain a stamp for μCP. This stamp was provided with a base portion formed by curing a curable material and a transfer convex portion on a support substrate, and as a result of observation with an optical microscope, it was confirmed that the transfer convex portion was a reverse pattern of the master plate. Therefore, on the peripheral edge of the top flat surface of the transfer convex portion, there are continuous microscopic projections having a wedge-shaped cross section having a height (150 nm) corresponding to the thickness of the flat protrusion (Cr light shielding portion) of the master plate, The distance (corresponding to the line width) between the tips of the microprojections on each transfer convex portion was 10 μm.

<Pattern formation>
The ink for forming an electrode pattern (Ag nano ink) was applied to the stamp for μCP produced as described above by a spin coating method, and the ink was placed on the top plane of the transfer convex portion. Thereafter, the ink was semi-dried at 23 ° C. for 1 minute.
Next, after contacting the ink on the silicon substrate, which is the workpiece, the stamp is peeled off, the ink pattern is transferred onto the silicon substrate, and dried at 180 ° C. for 30 minutes to form a comb-shaped electrode pattern. did.
As a result of observing the formed electrode pattern with an optical microscope, the electrode width is 9.8 to 10.2 μm, the variation is extremely small, the stamp line width is 10 μm, and the thickness is 200 to 200 μm. It was uniform at 210 nm, and it was confirmed that the pattern was formed with high accuracy.

[Comparative example]
A master plate was prepared in the same manner as in the example, except that in the master plate preparation process, the formation of the etching resist layer and the etching of the light shielding portion (Cr thin film) by the etchant were not performed.
Further, using this master plate, a stamp for μCP was produced in the same manner as in the example. It was confirmed that this stamp was provided with a base portion formed by curing a curable material and a transfer convex portion on a support substrate, and the transfer convex portion was a reverse pattern of the master plate. Further, the top plane of the transfer convex portion was flat including the peripheral portion, and the width (corresponding to the line width) of the top plane of each transfer convex portion was 10 μm.
Next, using this stamp, a comb-shaped electrode pattern was formed as in the example.
As a result of observing the formed electrode pattern with an optical microscope, the electrode width was 10 to 11 μm, the pattern was thickened with respect to the stamp line width of 10 μm, and the thickness was in the range of 150 to 250 nm with large variations. The pattern accuracy was inferior to that of the example.

  It can be used for manufacturing various devices, parts, and devices that perform pattern formation by the micro contact printing method.

DESCRIPTION OF SYMBOLS 1 ... Master plate for micro contact printing stamp manufacture 2 ... Board | substrate 3 ... Resin convex part 3a ... Side wall 4 ... Flat protrusion part 4a ... Peripheral wall part 5 ... Micro gap 3 '... Coating film of negative photosensitive resist 4' ... Light-shielding part 6 '... Coating film of positive photosensitive resist 6 ... Etching resist layer 11 ... Micro contact printing stamp 12 ... Support substrate 13 ... Base part 14 ... Transfer convex part 14a ... Top plane 15 ... Small protrusion 13' ... Curing material 17 ... Molded substrate 21 ... Ink 31 ... Workpiece

Claims (14)

  A substrate, a resin protrusion disposed in a desired pattern on one surface of the substrate, and a flat protrusion disposed on the substrate at a non-formation portion of the resin protrusion, A master plate for producing a stamp for microcontact printing, characterized in that a peripheral wall portion of the flat protrusion and a side wall of the resin convex portion are separated via a minute gap.   2. The micro contact printing stamp manufacturing method according to claim 1, wherein the resin convex portion has a pattern width on the top side smaller than a pattern width on the substrate side, and the side wall forms an inclined surface. Master version.   The width of the minute gap existing between the peripheral wall portion of the flat protrusion and the side wall of the resin convex portion is reduced toward the substrate side. Master plate for manufacturing the stamp for micro contact printing described.   The thickness of the said resin convex part exists in the range of 1-50 micrometers, and the thickness of the said flat protrusion part exists in the range of 50-1000 nm, The micro in any one of Claim 1 thru | or 3 characterized by the above-mentioned. Master version for manufacturing stamps for contact printing. Forming a light-shielding portion with a desired pattern on one surface of the transparent substrate;
Applying a negative photosensitive resist on the transparent substrate so as to cover the light shielding portion, irradiating light from the transparent substrate side, exposing the coating film of the negative photosensitive resist using the light shielding portion as a mask, Then, developing, forming a resin convex portion in the non-forming portion of the light shielding portion,
A positive photosensitive resist is applied so as to cover the resin convex portion, light is irradiated from the transparent substrate side, the coating film of the positive photosensitive resist is exposed using the light shielding portion as a mask, and then developed. Forming a resist layer for etching on the light shielding portion;
An etchant is infiltrated from a gap existing between the resin convex portion and the etching resist layer to etch the peripheral portion of the light shielding portion, so that the peripheral wall portion passes from the side wall of the resin convex portion through a minute gap. The manufacturing method of the stamp manufacturing master plate for microcontact printing characterized by including the process of forming the flat protrusion part which is spaced apart, and removing the said resist layer for an etching after that.   6. The method for producing a master plate for stamp production for microcontact printing according to claim 5, wherein the thickness of the light shielding part is set within a range of 50 to 1000 nm.   A stamp for microcontact printing, comprising: a base portion; and a transfer convex portion projecting from the base portion in a desired pattern and having a minute protrusion continuous with a peripheral portion of the top plane.   The microcontact printing stamp according to claim 7, wherein the microprotrusion has a wedge shape in cross-sectional shape.   9. The height of the transfer convex portion is in the range of 1 to 50 [mu] m, and the height of the microprojection from the top plane is in the range of 50 to 1000 nm. The micro contact print stamp described.   The microcontact printing stamp according to any one of claims 7 to 9, wherein the width of the transfer convex portion is not uniform. In a manufacturing method of a stamp for microcontact printing, comprising a base, and a transfer convex portion that protrudes from the base in a desired pattern and has continuous microprotrusions on the peripheral edge of the top plane.
A curable material is applied to the surface of the master plate according to any one of claims 1 to 4 on which the resin convex portion is disposed, and a coating film of the curable material is cured to form a base portion and a transfer convex portion. Forming a part, and then peeling from the master plate. A support substrate, a base disposed on one surface of the support substrate, and a transfer convex portion that protrudes from the base in a desired pattern and has continuous microprotrusions on the peripheral edge of the top plane. In the method of manufacturing a contact print stamp,
5. A molded substrate in which a coating film is formed by applying a curable material to a support substrate, and the coating film side of the support substrate is formed on the resin convex portion of the master plate according to claim 1. Is bonded to the surface on which the substrate is disposed, and the coating film of the curable material is cured to form a base and a transfer convex portion, and the base and the support substrate are joined, and then peeled off from the master plate A manufacturing method of a stamp for microcontact printing, characterized in that:   A pattern forming ink is placed on the top plane of the transfer convex portion of the microcontact printing stamp according to any one of claims 7 to 10, and then the ink is brought into contact with a workpiece. A pattern forming method comprising peeling off a stamp for micro contact printing.   14. The pattern forming method according to claim 13, wherein the ink for pattern formation placed on the top flat surface of the transfer convex portion is brought into a semi-dried state, and then the ink is brought into contact with a workpiece.

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