JP2010158805A - Method of manufacturing mold for photo imprinting - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a mold for photo imprinting economically without the need of a step of forming mask by photo lithography necessary when dry-etching a quartz substrate, a dry-etching step for the quartz substrate after that and the like. <P>SOLUTION: A light shielding film 5 is formed on the surface of projecting parts 13a of an uneven part 3 formed on a light transmissive resin (base materia) by forming a forming mold 4 provided with a projecting and recessed part 3 having a desired pattern and transferring the shape of the projecting and recessed part of the forming mold to the light transmissive resin 11b (base material 11a). The light shielding film is formed on the surface of the projecting part of the light transmissive resin, by depositing ink to become the light shielding film, forming a plating film or depositing a vapor deposition film. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a mold for optical imprint used when a pattern is formed by an optical imprint method in a process of producing an electronic element, an optical element, or the like.

  In recent years, an optical imprint method has been used as a method for forming a fine pattern in a manufacturing process of a semiconductor device, an optical element, or the like.

  This optical imprinting method is a kind of imprinting method, which is a molding technique for transferring a concavo-convex pattern onto a resin thin film by pressing a mold having a concavo-convex pattern onto a substrate coated with a resin thin film. This is a technique in which a photo-curing resin is used as a material, and the resin is cured and transferred by pressing a mold and irradiating with ultraviolet rays. This optical imprint method has a feature that a fine pattern can be formed more easily and at a lower cost than photolithography and direct electron beam drawing. Furthermore, by providing a light shielding film at the tip of the convex portion of the mold, only the resin under the convex portion of the mold can be maintained in an uncured state when irradiated with ultraviolet rays, and the film can be removed by development.

By the way, as a method of manufacturing a mold (mold for photoimprint) used in this photoimprint method, for example, an electron beam resist is applied to the surface of a quartz substrate on which an etching mask film is formed, and an electron beam is applied. A resist pattern is formed on a quartz substrate by irradiating and developing a desired portion of the resist with an electron beam, and the quartz substrate is dry-etched using the resist pattern as an etching mask to provide a desired pattern. A method of obtaining a mold for optical imprinting is known (see Patent Document 1).
At this time, the film for the etching mask is directly used as the light shielding film for the mold projection.

  In recent years, a method as described below has been proposed as a method for producing a mold for photoimprinting having a photocatalytic titanium oxide film on the surface (see Patent Document 2, paragraphs 0037 and 0038, etc.).

(1) In this method, first, an electron beam resist 117 is applied on a quartz substrate 115 as shown in FIG. 11A, as shown in FIG. 11B, and shown in FIG. As described above, a desired portion of the electron beam resist 117 is irradiated with an electron beam and then developed to form a resist pattern 117 a on the quartz substrate 115.
(2) Then, as shown in FIG. 11D, the quartz substrate 115 is dry-etched using the resist pattern 117a as an etching mask to form a pattern 115a.
(3) Next, the unnecessary electron beam resist 117 is removed, and the surface of the quartz substrate 115 is washed to obtain a quartz substrate 115 on which a pattern 115a as shown in FIG. 11E is formed.
(4) Then, a photocatalytic titanium oxide film 111 is formed on the surface of the quartz substrate 115 on which the pattern 115a is formed by sputtering and baking, and a mold for photoimprinting as shown in FIG. Get 110.

However, these conventional optical imprint mold manufacturing methods are manufactured through a process of dry-etching the quartz substrate, and an expensive apparatus is required to dry-etch the quartz substrate, which increases the cost. There is a problem of inviting.
JP 2005-354017 A JP 2007-144959 A

  The present invention solves the above-mentioned problems, and uses a quartz substrate and dry-etches it to produce a photo-imprint mold, which is necessary for mask formation by photolithography and subsequent drying. An object of the present invention is to provide a method for producing a mold for optical imprinting that is excellent in economic efficiency and that can be produced without using an expensive production apparatus without requiring a step such as etching.

In order to solve the above problems, the method for producing a mold for optical imprinting according to the present invention comprises
A step of forming a molding die provided with uneven portions having a desired pattern;
Transferring the shape of the concavo-convex portion of the mold to a light-transmitting resin;
And a step of forming a light-shielding film on a convex surface of the concave and convex portion of the light transmitting resin, which is formed by transferring the concave and convex portion of the molding die.

Further, the step of forming the light shielding film on the convex surface of the light transmissive resin,
A step of applying a light-shielding ink that becomes the light-shielding film after curing to the concave portion of the concave-convex portion of the molding die in advance, and then pouring the light-transmitting resin into the molding die from above Yes.

Further, the step of forming the light shielding film on the convex surface of the light transmissive resin,
The light-transmitting resin is a step of bringing the light-shielding ink that becomes the light-shielding film into contact with the convex surface of the concave-convex portion of the light-transmitting resin.

Further, the step of forming the light shielding film on the convex surface of the light transmissive resin,
Using a vacuum vapor deposition method, the light shielding film material is applied to the surface of the convex portion under the condition that the angle between the surface of the convex portion of the light transmitting resin and the light shielding film material source to be deposited is 30 degrees or less. It is the process of vapor-depositing.

The step of forming the light shielding film on the convex surface of the light transmissive resin,
Using a vacuum film forming method, after forming a conductive film on the surface of the light-transmitting resin provided with the concavo-convex portion, the light-shielding film is formed by electrolytic plating, and then from the region other than the surface of the convex portion. It is a process of removing the light shielding film together with the conductive film.

The step of forming the light shielding film on the convex surface of the light transmissive resin,
After embedding a resist in the concave portion of the concavo-convex portion of the light-transmitting resin, the light-shielding film is formed on the surface of the light-transmitting resin provided with the concavo-convex portion, and then from a region other than the surface of the convex portion. The light shielding film is removed together with the resist.

  The optical imprint mold of the present invention is not formed by processing a quartz material such as a quartz substrate like a conventional optical imprint mold, and is mainly composed of a light-transmitting resin. A process for processing a quartz substrate with high accuracy using an expensive equipment such as a dry etching apparatus is unnecessary, and an optical imprint mold can be produced economically.

  That is, in the method for producing a mold for optical imprinting of the present invention, a molding die having a concavo-convex portion having a desired pattern is used, and after the shape of the concavo-convex portion is transferred to a light-transmitting resin, the molding die Since the light-shielding film is formed on the convex surface of the concave and convex portions formed on the light-transmitting resin by transferring the concave and convex portions, general photolithography is performed on the quartz substrate as in the conventional method. After applying and forming a Ni film pattern, etc., there is no need for a mask forming process by photolithography, a process of dry etching a quartz substrate, etc., as in the method of dry etching using the Ni film pattern as a mask. The mold for optical imprinting can be produced economically.

  Moreover, since the mold for optical imprinting of the present invention is formed from a light-transmitting resin, it is characterized in that chipping is less likely to occur compared to an optical imprinting mold made of quartz.

  In the present invention, a light-shielding ink is applied in advance to the concave portions of the concave and convex portions of the molding die, and then a light-transmitting resin is poured into the molding die from above to shield the light from the side surfaces of the convex portions. It is possible to efficiently form the light shielding film on the surface of the convex portion of the light transmissive resin while preventing the film from being formed.

  In the present invention, the light shielding film is also formed on the side surface of the convex portion by bringing the light-shielding ink into contact with the convex surface of the concave and convex portion formed on the light-transmitting resin by transferring the concave and convex portion of the molding die. The light-shielding film can be efficiently formed on the surface of the convex portion of the light-transmitting resin while preventing this.

  In addition, when vacuum deposition is used, the light shielding film material is deposited on the convex surface under the condition that the angle between the convex surface of the light-transmitting resin and the light shielding film material source is 30 degrees or less. The light shielding film can be selectively formed on the surface of the convex portion, and the light shielding film is formed on the surface of the convex portion of the light-transmitting resin while preventing the light shielding film from being formed on the side surface of the convex portion. It can be formed efficiently.

  Moreover, after forming a conductive film on the surface provided with the concavo-convex part of the light-transmitting resin by using a vacuum film forming method, a light-shielding film is formed by electrolytic plating, and then the conductive film is formed from a region other than the surface of the convex part. By removing the light shielding film, it is possible to efficiently form the light shielding film on the surface of the convex portion of the light-transmitting resin while preventing the light shielding film from being formed on the side surface of the convex portion.

  In addition, after embedding a resist in the concave portion of the light-transmitting resin concavo-convex portion, a light-shielding film is formed on the surface on which the light-transmitting resin concavo-convex portion is provided. By removing the film, the light shielding film can be efficiently formed on the surface of the convex portion of the light-transmitting resin while preventing the light shielding film from being formed on the side surface of the convex portion.

  Embodiments of the present invention will be described below to describe the features of the present invention in more detail.

<1> Production of mold for molding (mother mold) In manufacturing a mold for optical imprinting, first, a method for explaining a mold for molding (mother mold) in which only a desired pattern portion has a convex portion having a step of 10 μm is described below. It was produced by.

(1) First, as shown in FIG. 1A, a Ni film 2 having a desired pattern is formed on a quartz substrate 1.
(2) Then, as shown in FIG. 1B, the quartz substrate 1 is etched using the Ni film 2 as an etching mask.
In the etching of the quartz substrate 1, in Example 1, ICP-RIE (inductive coupling type reactive ion etching apparatus) was used, and dry etching was performed using a CF-based (Freon-based) gas. .
(3) Thereafter, by removing the Ni film 2, as shown in FIG. 1 (c), the molding die 4 having the concavo-convex portions 3 having a desired pattern and having the convex portions 3a and the concave portions 3b is obtained.

  Then, an F-based silane coupling agent is applied to the molding die 4 as a release agent. In addition, about the kind of mold release agent, it is not restricted to this, A silicone type thing etc. can also be used.

In forming the concavo-convex portion having a desired pattern on the quartz base material, it is possible to use other apparatuses, and it is also possible to produce them by other methods.
Further, the constituent material of the molding die is not limited to quartz, and other materials such as a Si base material may be used.

  Further, the etching mask is not limited to the Ni film 2, and it is also possible to form an etching mask using another resist material and perform dry etching.

  In Example 1, in order to produce the molding die 4, the quartz substrate was processed using an inductively coupled reactive ion etching apparatus. Since it can be used repeatedly to produce the optical imprint mold of the present invention made of a transmissive resin, the overall cost is greatly increased compared to the case of producing an optical imprint mold from a conventional quartz material. Can be reduced.

  In Example 1, the step of the concavo-convex portion constituting the pattern portion is 10 μm. However, the step is not necessarily 10 μm, and a desired step is usually set in the range of about 10 nm to 50 μm. Is possible.

<2> Formation of light-shielding film As described above, an ink jet method is applied to the concave portion 3b of the concave and convex portion provided with the convex portion 3a and the concave portion 3b of the molding die 4 coated with an F-based silane coupling agent as a release agent. Then, an ink (ink containing a light shielding material) 5a which becomes the light shielding film 5 after curing is poured (FIG. 2A). At this time, by providing the ink 5a with appropriate fluidity, the ink 5a can be sufficiently distributed to a narrow portion of the recess 3b.
Further, if necessary, the mold 4 can be heated to optimize the leveling / fluidity of the ink 5a.

Thereafter, the mold 4 is placed in an oven and heated to dry and cure the ink 5a. The light shielding film 5 formed by curing the ink 5a is preferably black in terms of light shielding properties and antireflection properties.
In Example 1, the coating amount of the ink 5a was controlled so that the thickness of the light-shielding film 5 formed by curing the ink 5a was about 1 μm (at least 50 nm).

  Alternatively, by spraying the entire surface of the concavo-convex portion 3 of the molding die 4 by using a spraying method, the surface of the concavo-convex portion 3 can be polished and only the surface of the concavo-convex portion 3 can be polished as shown in FIG. As shown, the recess 3b can be in a state in which an ink (ink containing a light shielding material) 5a that becomes the light shielding film 5 after curing is applied.

<3> Molding of substrate of optical imprint mold and peeling from mold for molding As schematically shown in FIG. 2 (b), a mold 4 is made of a light-transmitting resin (PDMS in this Example 1). (Polydimethylsiloxane)) 11b. The light transmissive resin 11b becomes a base material 11a (see FIG. 2C) constituting the optical imprint mold 11 after curing.

  Thereafter, the light-transmitting resin (PDMS) 11b is cured by heating to 100 ° C. in an oven. Thereby, the molding of the optical imprint mold 11 (base material 11a) made of a light-transmitting resin, to which the shape of the concavo-convex portion 3 of the molding die 4 is transferred, is performed.

Next, as shown in FIG. 2C, the optical imprint mold 11 is peeled from the molding die 4.
At this time, the light-shielding film 5 in close contact with the convex portion 13a of the concavo-convex portion 13 of the base material 11a constituting the optical imprint mold 11 is removed from the molding die 4 together with the base material 11a constituting the optical imprint mold 11. Peel off.

The optical imprint mold 11 (base material 11a) includes convex and concave portions 13a and concave portions 13b corresponding to the concave and convex portions 3 of the molding die 4 and having a predetermined pattern. The light shielding film 5 formed by curing the ink 5a disposed on the bottom surface of the concave portion 3b in the concave and convex portion 3 of the molding die 4 is in close contact with the surface of the convex portion 13a in the concave and convex portion 13. Yes.
In addition, as the base material 11a of the mold 11 for optical imprinting, a light transmissive resin other than PDMS can be used.

Thereby, as shown in FIG.2 (c), the mold 11 for optical imprints provided with the light shielding film 5 on the surface of the convex part 13a in the uneven part 13 of the base material 11a is obtained.
In the optical imprint mold 11 of the present invention, since the base material 11a is made of a light-transmitting resin, the optical imprint mold 11 is similar to a dry etching apparatus as in the case of manufacturing an optical imprint mold made of quartz. The optical imprint mold can be efficiently and economically manufactured without requiring an expensive apparatus.

  In Example 1, an inductive coupling type reactive ion etching apparatus is used for processing the quartz base material to manufacture the molding die 4, but the manufactured molding die is made of a light-transmitting resin. Can be used repeatedly to produce the optical imprint mold of the present invention, so that the overall cost is greatly reduced compared to the case of producing the optical imprint mold from a conventional quartz material. What you can do is as described above.

  Further, since the mold for optical imprinting of Example 1 is formed of a light-transmitting resin, it has a feature that chipping and the like are less likely to occur as compared with the one made of quartz.

<4> Optical Imprinting Next, a method for performing optical imprinting using the optical imprinting mold 11 produced as described above will be described.

(1) First, as shown in FIG. 3A, a photocurable resin 22 is applied onto a substrate 21 on which a pattern is to be formed.
As the light transmissive resin, for example, an acrylic negative resist is used and is applied by spin coating. However, the type of resin and the coating method are not limited to this.

(2) As shown in FIG. 3 (b), the optical imprint mold 11 made of the light transmissive resin produced in the above <3> is pressed onto the photocurable resin 22.
As the pressing condition, an appropriate condition is selected depending on the characteristics of the photocurable resin 22 to be used. Generally, the proper ranges are 0.1 to 100 MPa and room temperature to 100 ° C., but are not limited thereto.

(3) Then, as shown in FIG. 3 (c), the photocurable resin 22 is irradiated with UV light through the photoimprint mold 11.
At this time, since the light shielding film 5 is not formed in the concave portion 13b of the concave-convex portion 13 of the optical imprint mold 11, UV light is irradiated to the region 22a of the photocurable resin 22 corresponding to the concave portion 13b. , Cure. On the other hand, since the light shielding film 5 is formed on the surface of the convex portion 13a of the photoimprint mold 11, the region 22b corresponding to the convex portion 13a of the photocurable resin 22 is not irradiated with UV light and cured. do not do.
The UV irradiation amount was 100 mJ / cm ^{2 in} Example 1. However, the UV irradiation amount is not limited to this.

  (4) Thereafter, the mold 11 for photoimprinting is released from the photocurable resin 22 (see FIG. 3D).

(5) Then, the photocurable resin 22 is exposed to a developing solution to remove the uncured portion of the region 22b (see FIG. 3E).
In Example 1, tetramethylammonium hydroxide (TMAH) (2.38%) was used as the developer. However, the developer is not limited to this, and various types can be used depending on the type of the photocurable resin.
By performing optical imprinting by the above-described method, a pattern schematically shown in FIG. 3E can be efficiently formed.

<1> Production of Mold for Mold (Mother Mold) Mold 4 for mold (see FIG. 1C) is produced by the same method as in Example 1 above.

<2> Application of light-transmitting resin As shown in FIG. 4A, a light-transmitting resin is used as a light-transmitting resin on the upper surface of a quartz substrate 31 on which a primer (not shown) serving as an adhesion layer is applied. A functional fluororesin 32 is applied. In applying the light-transmitting fluororesin 32, application is performed under predetermined conditions using a spin coating method (in Example 2, the application was performed under the condition of 600 rpm).
The spin coating condition may be about 500 to 4000 rpm, and is preferably set according to the target film thickness.
However, the light transmitting resin applied by spin coating is not limited to this.

Moreover, the coating method of the light transmissive fluororesin 32 is not limited to spin coating, and a spray method, a screen printing method, or the like may be used.
Further, it is desirable that the coating thickness of the light-transmitting fluororesin 32 be larger than 1 μm so that a step of the uneven portion constituting the pattern portion of the optical imprint mold can be secured by 1 μm or more.

  In the case of Example 2, there is no particular restriction on the size of the step of the concavo-convex portion, but it is usually preferable to set the desired step in the range of about 10 nm to 50 μm.

  The light transmissive resin is not limited to the light transmissive fluororesin, and for example, polymethyl methacrylate (PMMA) can also be used. However, by using a light-transmitting fluororesin, it becomes possible to improve the releasability when releasing the light imprint mold from the light curable resin in the light imprint process. It is desirable to use a transparent fluororesin.

  In Example 2 as well, the primer as the adhesion layer is applied to the quartz substrate 31 as described above, but the primer does not necessarily have to be applied.

<3> Press of Mold for Molding The mold for molding 4 produced in the above <1> is pressed into the light transmissive resin 32 as shown in FIG.
The pressing conditions are 10 MPa and 140 ° C. The pressing conditions are not limited to this, and conditions suitable for the light transmissive resin to be used are selected. Usually, it is desirable that the press pressure is about 1 to 100 MPa and the press temperature is a temperature higher than the glass transition point.
Thereafter, the light transmissive resin 32 is cured by cooling.

  In addition, you may press the shaping | molding type | mold 4 in a vacuum atmosphere as needed. In that case, the degree of vacuum is desirably 10 Pa or less. When pressing is performed in a vacuum atmosphere, it is preferable because defects due to air entrapment can be prevented.

<4> Mold release (release)
Next, the molding die 4 pressed in the step <3> is released from the light transmissive resin 32 (see FIG. 4C).
Thereby, the base material 11a which consists of the light-transmitting resin provided with the uneven | corrugated | grooved part 13 of the predetermined pattern which has the convex part 13a and the recessed part 13b is obtained.

<5> Formation of light-shielding film Then, the convex portion 13a in the concave-convex portion 13 of the base material 11a made of light-transmitting resin, prepared in the above <4>, is applied to the light-shielding ink 5a as shown in FIG. After the immersion, the base material 11a is pulled up and heated in an oven or the like to cure the base material 11a.
Thereby, as shown in FIG.4 (e), the mold 11 for optical imprints provided with the light shielding film 5 on the surface of the convex part 13a of the uneven | corrugated | grooved part 13 of the base material 11a is obtained.

<6> Optical Imprint When optical imprinting is performed using the optical imprint mold 11 of Example 2, it can be performed in the same manner as in Example 1 above.

<1> Production of mold for molding (mother mold) First, a mold for molding (mother mold) in which only a desired pattern portion has a convex portion having a step of 10 μm was fabricated by the method described below.

  A Ni film 2 having a desired pattern is formed on the quartz substrate 1 (FIG. 5 (a)), and the quartz substrate 1 is etched using the Ni film 2 as an etching mask, thereby providing projections 3a and recesses 3b. A molding die 4 having the uneven portions 3 is obtained (FIG. 5B).

  Etching is performed using CF gas under conditions of an input power of 1800 W and a processing pressure of 1 Pa, thereby realizing a desired shape. However, the etching conditions are not limited to this. Alternatively, wet etching may be performed.

Moreover, the constituent material of the mold may be other than quartz, and for example, a Si base material may be used.
Further, the step to be formed is not necessarily 10 μm, and a desired step can be selected in the range of about 10 nm to 50 μm.

  Thereafter, an F-based silane coupling agent is applied to the molding die 4 as a release agent. The type of release agent is not limited to this, and a silicone-based release agent can also be used.

<2> Application of light-transmitting resin As shown in FIG. 5C, a primer 33 serving as an adhesion layer is applied on a quartz substrate 31, and a light-transmitting resin (in this embodiment, light-transmitting fluorine is used). Resin) 32 is applied. The light transmissive resin 32 is applied by spin coating at 600 rpm.

  The light-transmitting resin is not limited to the fluororesin, and for example, PMMA may be used. When the fluororesin is used, the optical imprinting process described in (4) of <5> of Example 1 is used. It is possible to improve the releasability in the step of releasing the resin from the mold for photoimprinting, which is preferable.

The spin coating condition may be about 500 to 4000 rpm, and is preferably set according to the target film thickness.
Further, the viscosity of the light transmissive resin may be in the range of about 100 to 2000 mPa · s, and an appropriate value is selected in consideration of other conditions.
Further, the method of applying the light transmissive resin is not limited to spin coating, and screen printing or the like can also be used.
The coating thickness of the light-transmitting resin is set to be at least larger than the convex step of the molding die (for example, 10 μm in this embodiment).
It is not always necessary to apply the primer 33 which is an adhesion layer.

<3> Press of molding die and subsequent peeling of molding die As shown in FIG. 5 (d), the molding die 4 prepared in the above <1> is applied onto the quartz substrate 31 in the above <2>. Press the pressed light transmissive resin (light transmissive fluororesin) 32. The pressing conditions are 10 MPa and 140 ° C. The pressing conditions are not limited to this, and conditions suitable for the light transmissive resin 32 to be used are selected. In general, the press pressure is suitably about 1 to 100 Mpa, and the press temperature is suitably a temperature above the glass transition point.

Next, the light transmissive resin 32 is cured by cooling. Note that a light curable material may be used for the light transmissive resin 32 and the resin may be cured by light irradiation.
Moreover, it presses in a vacuum atmosphere as needed. The degree of vacuum is desirably 10 Pa or less.

Next, as shown in FIG. 5E, the molding die 4 is released from the base material 11a formed by curing the light-transmitting resin 32.
Thereby, the base material 11a provided with the uneven | corrugated | grooved part 13 of a predetermined pattern which has the convex part 13a and the recessed part 13b is obtained.

<4> Formation of light-shielding film As shown in FIG. 6A, the base material 11a provided with the concavo-convex portion 13 formed in the above <3> is deposited so that the formation surface of the concavo-convex portion 13 becomes a film formation surface. Set in the device. At this time, the base material 11a and the light-shielding film material source 12 to be deposited are set so that the incident angle of the evaporated particles to the surface of the convex portion 13a of the base material 11a is 30 ° or less.

  By performing vapor deposition in this manner, the vapor deposition particles reach only the vicinity of the surface of the convex portion 13a of the base material 11a made of a light-transmitting resin, and do not reach the concave portion. Thereby, as shown in FIG.6 (b), the optical imprint mold 11 in which the light shielding film (vapor deposition film) 5 was selectively formed only in the convex part 13a can be obtained.

In addition, the constituent material of the light shielding film 5 should just be a material which has light-shielding property, For example, Cr, Ni etc. can be used. Further, a Ti film may be inserted as an adhesion layer.
Further, an antireflection layer such as CrO can be provided on the surface of the light shielding film 5.
The thickness of the light shielding film 5 only needs to be thick enough to shield light, and about 100 nm is appropriate, but is not limited thereto.
Further, when forming the light shielding film 5, the film forming method is not limited to vapor deposition, and other methods such as sputtering can be used.

<5> Optical Imprint When optical imprinting is performed using the optical imprint mold 11 of Example 3, it can be performed in the same manner as in Example 1 above. The same effect can be obtained.

  In Example 3 above, in the step of forming the light shielding film of <4>, as shown in FIG. 6A, the incident angle of the evaporated particles on the surface of the convex portion 13a of the base material (light transmissive resin) 11a is 30. The substrate 11a and the light-shielding film material source 12 to be deposited were set so as to be less than or equal to 0 °, and the light-shielding film 5 was formed. In Example 4, as shown in FIG. Thus, the base material 11a and the vapor deposition material (conductive material) source 12a to be vapor-deposited are set so that the incident angle of the evaporated particles on the surface of the convex portion 13a of the base material 11a is 90 °. A film 15 was formed.

  Thereby, as shown in FIG.7 (b), the electrically conductive film 15 is formed in the surface of the convex part 13a and the recessed part 13b of the base material 11a, respectively. However, no conductive film is deposited on the side surface of the convex portion 13a. Note that Cu, Ni, or the like is used as the conductive material to be deposited. The thickness of the conductive film 15 only needs to be a thickness necessary for an electrode for electrolytic plating in the next step, and about 100 nm is appropriate.

  Then, Ni electroplating is performed using the conductive film 15 deposited on the convex portion 13a of the base material (light transmissive resin) 11a as an electrode, and as shown in FIG. 7C, the surface of the convex portion 13a on the conductive film 15 is formed. Then, a Ni plating film to be the light shielding film 5 is formed. The type of plating film used as the light shielding film 5 is not limited to the Ni film, and any material having a light shielding property such as Cr or Cu may be used. Further, the thickness of the plating film is a value obtained by adding the amount of shaving by etching in the next step to the thickness necessary for the light shielding film. Usually, it is 200 nm or more, but this is not a limitation. At this time, since the convex portion 13a and the concave portion 13b of the base material (light-transmitting resin) 11a are electrically insulated, the plating film (light-shielding film) is deposited only on the surface of the convex portion 13a. It does not deposit on the surface (see FIG. 7 (c)).

  Then, the substrate 11a on which the light shielding film (plating film) 5 and the conductive film (deposited film) 15 are deposited is dry-etched to remove the conductive film (deposited film) 15 on the surface of the recess 13b (FIG. 7D). )), A mold for optical imprinting is obtained.

Dry etching is performed by making Ar ions incident using an ECR (Electron Cyclotron Resonance) etcher. The ECR conditions are an RF power of 400 W, an acceleration voltage of 250 V, a magnet current of 17 A, and a degree of vacuum of 0.06 Pa. The ECR condition is not limited to this.
Also, other methods can be used as the dry etching method.
By this etching process, the deposited film on the surface of the convex portion 13a (plating film to be the light shielding film 5) is also etched. However, since the convex portion 13a is preliminarily formed with a deposited film having a thickness in consideration of the etching amount. The light shielding function is not impaired.

  In the case of the method of Example 4, since the light-shielding film does not adhere to the side surface of the convex portion 13a of the substrate 11a, the step of exposing the photocurable resin when performing photoimprinting (<4> of Example 1) In the optical imprint (refer to step (3)), it becomes possible to accurately control the exposure amount to the photocurable resin, and the development step (<4> optical imprint (5) The development residue in the process (see step) can be reduced.

  In Example 3 above, the light shielding film <4> was formed after the pressing of the <3> molding die and the subsequent peeling of the molding die. In Example 5, <4> in Example 3 was performed. Instead of the step of forming the light shielding film, the following steps were performed. Other steps are the same as those in Example 3. A description will be given below.

(1) After the mold is pressed and the mold is subsequently peeled off, as shown in FIG. 8 (a), the convex portion 13a and the concave portion 13b of the base material (light transmissive resin) 11a are provided. A resist 41 is applied on the surface.
As the resist 41, an acrylic negative resist is used and is applied by a spin coating method. Other resists can be used as the resist 41.

  (2) Then, pre-bake is performed. The prebaking condition is suitably about 80 ° C. and about 1 minute, but is not limited thereto. Then, the resist 41 is subjected to oxygen ashing to remove the upper portion of the resist 41, thereby exposing the surface of the convex portion 13a of the base material (light transmissive resin) 11a as shown in FIG. 8B. Oxygen ashing was performed at 200 W and 30 Pa, but the oxygen ashing conditions are not limited to this.

(3) Next, as shown in FIG. 8C, the light shielding film 5 is deposited on the surface of the resist 41 and the surface of the convex portion 13a exposed from the resist 41 of the base material (light transmissive resin) 11a. To do.
As a constituent material of the light shielding film 5, Cu, Ni or the like is used, but is not limited thereto.

(4) Then, as shown in FIG. 8D, the light shielding film 5 and the resist 41 in a region other than the light shielding film 5 formed on the surface of the convex portion 13a are removed using a resist stripping solution 43. Thereby, the optical imprint mold 11 in which the light shielding film 5 is selectively formed only on the surface of the convex portion 13a can be obtained.
In the case of the fifth embodiment, the same effect as in the fourth embodiment can be obtained. In addition, in Example 4, since electroplating is performed, it is desirable that each conductive film 15 on the upper surface of each convex portion 13a is conductive. For this reason, the pattern is restricted, but in the case of this example, There is no such restriction and the degree of freedom is high.

  In Example 5 described above, after pre-baking in the step (2), the resist 41 is subjected to oxygen ashing to remove the upper surface side portion of the resist 41, so that as shown in FIG. (Light transmissive resin) The surface of the convex portion 13a of the 11a is exposed, but in this Example 6, as described below, the resist is formed using normal photolithography without performing oxygen ashing. 41 was patterned and the surface of the convex part 13a of the base material 11a was exposed. A description will be given below.

  (1) In the same manner as in step (1) of Example 5 above, a resist 41 is applied on the surface of the base material (light transmissive resin) 11a provided with the convex portions 13a and the concave portions 13b (FIG. 8 ( a)).

(2) Then, as shown in FIG. 9A, exposure is performed under a condition of 100 mJ / cm ² using a photomask 42 having an opening corresponding to at least the recess 13b of the base material (light-transmitting resin) 11a. .

  (3) Next, as shown in FIG. 9B, the resist 41a (FIG. 9A) in the unexposed area is removed by developing with a developer. As the developer, triethanolamine or the like is used. Thereafter, it is exposed to oxygen plasma as necessary to perform a descum treatment.

(4) Next, as shown in FIG. 9 (c), light is shielded from the surface side where the convex portions 13a and the concave portions 13b of the base material (light transmissive resin) 11a from which the resist of the unexposed portions has been removed is formed. A film 5 is deposited.
As a constituent material of the light shielding film 5, Cu, Ni or the like is used, but is not limited thereto.

  (5) Then, as shown in FIG. 9 (d), the light shielding film 5 and the resist 41 in the region other than the light shielding film 5 formed on the surface of the convex portion 13 a are removed using a resist stripping solution 43. Thereby, the optical imprint mold 11 in which the light shielding film 5 is selectively formed only on the surface of the convex portion 13a can be obtained.

  In the case of the sixth embodiment, the same effect as that of the fifth embodiment can be obtained. In the state where the resist of the unexposed portion shown in FIG. 9C is removed, that is, in the state where the light shielding film 5 is formed, the surface of the resist 41 is the convex portion 13a of the base material (light transmissive resin). Since the position is higher than the surface, the resist 41 can be easily peeled after the light shielding film 5 is formed, and it is possible to suppress the occurrence of burrs in the light shielding film 5 when the resist 41 is removed. The yield in the formation process can be improved.

[Modification]
For example, in Example 3, the quartz substrate 31 is used as a material to which the light-transmitting resin is applied in the step (2) of applying the light-transmitting resin (see FIG. 5C). According to the method described in (1), an optical imprint mold can be manufactured without using an expensive quartz substrate. A description will be given below.

First, a glass substrate 51 is prepared instead of the quartz substrate used for applying the light transmissive resin in Example 3, and before applying the light transmissive resin 32 as shown in FIG. A release layer 52 is formed on the glass substrate 51.
As the release layer 52, for example, a heat release sheet, a PMGI (polymethylglutarimide) sheet or the like is suitable, but not limited thereto.

  Then, as shown in FIG. 10 (b), the molding die 4 is pressed to cure the light-transmitting resin 32, and then the molding die 4 is turned into the light-transmitting resin as shown in FIG. 10 (c). 32 (base material 11a) is released.

Then, as shown in FIG. 10 (d), the base material 11 a made of a light transmissive resin is peeled from the peeling layer 52. The peeling method can be determined according to the type of the peeling layer 52 selected in the previous step. For example, when a heat release sheet is employed for the release layer 52, the release layer 52 is peeled off by heating to a temperature equal to or higher than the temperature at which the heat release sheet functions.
According to this method, an inexpensive substrate such as a glass substrate can be used without using a quartz substrate.

  In each of the above-described embodiments, various manufacturing methods of optical imprint molds and conditions of each process are shown. However, the present invention is not limited to each of the above-described embodiments, and the scope of the invention. It is possible to add various applications and modifications.

(a)-(c) is a figure which shows the manufacturing process of the shaping | molding die used for manufacture of the mold for optical imprints in the Example (Example 1) of this invention. (a)-(c) is a figure explaining the method to manufacture the mold for optical imprints using the shaping | molding die of FIG. 1 in Example 1 of this invention. (a)-(e) is a figure explaining the method of performing an optical imprint using the mold for optical imprints of FIG. (a)-(e) is a figure which shows the manufacturing method of the mold for optical imprint concerning the other Example (Example 2) of this invention. (a)-(e) is a figure explaining the manufacturing method of the mold for optical imprint concerning the further another Example (Example 3) of this invention. (a), (b) is a figure which shows the manufacturing method of the mold for optical imprint concerning Example 3, Comprising: It is a figure which shows the process after the process shown in FIG. (a)-(d) is a figure explaining the manufacturing method of the mold for optical imprint concerning other Example (Example 4) of this invention. (a)-(d) is a figure explaining the manufacturing method of the mold for optical imprint concerning the further another Example (Example 5) of this invention. (a)-(d) is a figure explaining the manufacturing method of the mold for optical imprint concerning the further another Example (Example 6) of this invention. (a)-(d) is a figure explaining the modification of the manufacturing method of the mold for optical imprint of this invention. It is a figure which shows the manufacturing method of the conventional mold for optical imprint.

DESCRIPTION OF SYMBOLS 1 Quartz base material 2 Ni film 3 Uneven | corrugated | grooved part of a shaping | molding type | mold 3a Convex part in the uneven | corrugated | grooved part of a shaping | molding die 3b Recessed part in the uneven | corrugated | grooved part of a shaping | molding die 4
DESCRIPTION OF SYMBOLS 11 Optical imprint mold 11a Base material 11b Light-transmitting resin 12 Light shielding film material source 12a Vapor deposition material (conductive material) source 13 Uneven portion of optical imprint mold 13a Convex portion of uneven portion of optical imprint mold 13b Light Concave portion in the uneven portion of the imprint mold 15 Conductive film 21 Substrate on which the pattern is to be formed 22 Photocurable resin 22a Region of the photocurable resin corresponding to the concave portion of the photoimprint mold 22b Light of the photocurable resin Area corresponding to convex part of imprint mold 31 Quartz substrate 32 Light transmissive resin (light transmissive fluororesin)
33 Primer 41 Resist 41a Unexposed resist 42 Photomask 43 Resist stripper 51 Glass substrate 52 Stripping layer

Claims (6)

A step of forming a molding die provided with uneven portions having a desired pattern;
Transferring the shape of the concavo-convex portion of the mold to a light-transmitting resin;
And a step of forming a light-shielding film on a convex surface of the concavo-convex portion of the light-transmitting resin, which is formed by transferring the concavo-convex portion of the molding die. . The step of forming the light shielding film on the convex surface of the light transmissive resin,
A step of applying a light-shielding ink that becomes the light-shielding film after curing to the concave portion of the concave-convex portion of the molding die in advance, and then pouring the light-transmitting resin into the molding die from above The method for producing a mold for optical imprinting according to claim 1. The step of forming the light shielding film on the convex surface of the light transmissive resin,
2. The process for producing a mold for optical imprinting according to claim 1, wherein the light-shielding ink that becomes the light-shielding film after curing is brought into contact with the convex surface of the concave-convex part of the light-transmitting resin. Method. The step of forming the light shielding film on the convex surface of the light transmissive resin,
Using a vacuum vapor deposition method, the light shielding film material is applied to the surface of the convex portion under the condition that the angle between the surface of the convex portion of the light transmitting resin and the light shielding film material source to be deposited is 30 degrees or less. 2. The method for producing a mold for optical imprinting according to claim 1, wherein the method is a step of vapor deposition. The step of forming the light shielding film on the convex surface of the light transmissive resin,
Using a vacuum film forming method, after forming a conductive film on the surface of the light-transmitting resin provided with the concavo-convex portion, the light-shielding film is formed by electrolytic plating, and then from the region other than the surface of the convex portion. 2. The method for producing an optical imprint mold according to claim 1, wherein the light shielding film is removed together with the conductive film. The step of forming the light shielding film on the convex surface of the light transmissive resin,
After embedding a resist in the concave portion of the concavo-convex portion of the light-transmitting resin, the light-shielding film is formed on the surface of the light-transmitting resin provided with the concavo-convex portion, and then from a region other than the surface of the convex portion. The method for producing a mold for optical imprinting according to claim 1, wherein the light shielding film is removed together with the resist.

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